Polymers Module

POLYMERS MODULE
7.1
POLYMERS
BATCH MODULE
MODULE
Contents
Chapter 1 Introduction to Polymers

Addition or Chain Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-1
Condensation or Step Growth Polymerization . . . . . . . . . . . . . . . . . . . .1-2
Terminology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1-3
Chapter 2 Using the Polymer Module with PRO/II

Selecting the Units of Measure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-1
Entering Polymer Segment and Component Data. . . . . . . . . . . . . . . . . .2-2
Calculating Molecular Weight Distributions . . . . . . . . . . . . . . . . . . . . . .2-3
Choosing Thermodynamic Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . .2-5
Building the Flowsheet and Selecting Polymer Reactors . . . . . . . . . . . .2-6
Chapter 3 Estimating Polymer Component Property Data

van Krevelen Group Contribution Method . . . . . . . . . . . . . . . . . . . . . . .3-1
Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-1
van Krevelen Structural Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3-3
Entering Polymer Segment and Component Data. . . . . . . . . . . . . . . . . .3-8
Chapter 4 Supplying Polymer Pure Component Property Data

Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-1
POLYMERS
Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-2

Polymer Temperature-Dependent Properties (optional) . . . . . . . . . .4-5
Example 4-1: WFE with Pseudocomponent Distribution. . . . . . . . .4-7
Entering Molecular Weight Distributions . . . . . . . . . . . . . . . . . . . . . . . .4-8
Chapter 5 Supplying Polymer Stream Data

Keyword Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .5-2
PRO/II 7.1 Add-On Modules Users Guide 3

MWD or MMWD Attributes for Free Radical (FR) Polymerization . . . 5-3
MWD or MMWD Attributes for Coordination Complex (ZN)
Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-4
MWD or MMWD Attributes for Step Growth (SG) Polymerization . . . 5-4
PCFRAC Attributes for Free Radical (FR) Polymerization . . . . . . . . . . 5-5
PCFRAC Attributes for Coordination Complex (ZN) Polymerization. . 5-5
(PCFRAC Attributes for Step Growth (SG) Polymerization . . . . . . . . . 5-6
Example 5-1: Component and Stream Attribute Input. . . . . . . . . . . 5-6
Example 5-2: Component and Stream Attribute Input. . . . . . . . . . . 5-7
Entering Stream Polymer Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-9
Chapter 6 Stream Output Report Options

Keyword Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Entering PWRATE and PCONV. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-2
Chapter 7 Specifying the Thermodynamic Method

Advanced Lattice Model (ALM). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-2
Example 7-1: ALM with Polyvinylacetate and Benzene . . . . . . . . . 7-6
UNIFAC Free Volume K-Value Method . . . . . . . . . . . . . . . . . . . . . . . . . 7-7
Example 7-2: UNIFAC with Polyisobutylene and Benzene. . . . . . . 7-9
Flory-Huggins Liquid Activity Method . . . . . . . . . . . . . . . . . . . . . . . . . 7-9
Example 7-3: Flory-Huggins with Polystyrene and Acetone. . . . . 7-15
SAFT and PHSC Equations of State. . . . . . . . . . . . . . . . . . . . . . . . . . . 7-15
Example 7-4: SAFT EOS with PVAC and Benzene . . . . . . . . . . . 7-22
Example 7-5: PHSC EOS with PVAC and Benzene . . . . . . . . . . . 7-23
Selecting Polymer Thermodynamic Methods. . . . . . . . . . . . . . . . . . . . 7-24
Chapter 8 User-Added Polymer Reactor

Kinetic Rate Constants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-2
CSTR Mass and Energy Operating Equations . . . . . . . . . . . . . . . . . . . . 8-2
PFR Mass and Energy Operating Equations . . . . . . . . . . . . . . . . . . . . . . 8-4
Heat Transfer Coefficient . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-5
Reactor Pressure Effects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-5
POLYMERS
Population Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-6

Moment Expansions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-7
Chapter 9 User-Added Free Radical Polymerization Model

Polymerization via Free-Radical Kinetics . . . . . . . . . . . . . . . . . . . . . . . 9-2
Free-Radical Kinetics Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-2
Free-Radical Initiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-7
4 Contents
Chain Propagation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-8
Chain Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-8
Free-Radical Recombination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-9
Chain Termination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-10
Gel and Glass Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-10
Required Data for the Polymer Reactor Unit . . . . . . . . . . . . . . . . . . . .9-12
User-Added Subroutines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .9-13
Communicating with PRO/II for Free-Radical Kinetics . . . . . . . .9-13
Using Reactor Unit US21 to Model Free-Radical Systems . . . . . .9-23
Example 9-1: Free-Radical Homopolymerization in a CSTR . . . .9-23
Example 9-2: Free-Radical Homopolymerization in a PFR. . . . . .9-29
Example 9-3: Free-Radical Copolymerization in a CSTR . . . . . . .9-33
Example 9-4: Free-Radical Copolymerization in a PFR . . . . . . . .9-38
Chapter 10 User-Added Coordination Complex Polymerization

Model
Polymerization via Coordination Complex Kinetics. . . . . . . . . . . . . . .10-2
Coordination Complex Kinetic Mechanisms . . . . . . . . . . . . . . . . .10-4
Communicating with PRO/II for Coordination Complex
Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10-10
Using Reactor Unit US21 to Model Coordination Polymerization Systems .10-15
Example 10-1: Single-Site Coordination Homopolymerization in a CSTR .10-15
Example 10-2: Multi-Site Coordination Copolymerization in a CSTR . .10-19
Example 10-3: Single-Site Coordination Polymerization in a CSTR . . . .10-24
Example 10-4: Multi-Site Coordination Polymerization in a PFR . . . . . .10-31
Chapter 11 User-Added Step Growth Polymerization Reactor

Model
Polymerization via Stepwise Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . .11-2
Stepwise Polymerization Chain Types . . . . . . . . . . . . . . . . . . . . . .11-3
Stepwise Polymerization Kinetic Mechanisms . . . . . . . . . . . . . . .11-5
POLYMERS

Communicating with PRO/II for Stepwise Kinetics. . . . . . . . . . . .11-8
Using Reactor Unit US21 to Model Step Growth Systems . . . . .11-12
Example 11-1: Type I Step Growth Polymerization in a CSTR . .11-12
Example 11-2: Type I Step Growth Polymerization in a PFR . . .11-15
Example 11-3: Type II Step Growth Polymerization in a CSTR .11-18
PRO/II 7.1 Add-On Modules Users Guide 5

Example 11-4: Type II Step Growth Polymerization in a PFR . . 11-21
Example 11-5: Type III Step Growth Polymerization in a CSTR 11-24
Example 11-6: Type III Step Growth Polymerization in a PFR. . 11-27
Chapter 12 Interpreting the Output

Polymer Characterization via Moments . . . . . . . . . . . . . . . . . . . . . . . . 12-3
Chapter 13 Wiped Film Evaporator

PRO/II Wiped Film Evaporator Model . . . . . . . . . . . . . . . . . . . . . . . . . 13-2
Operating Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-2
Feedback Ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-3
Blade Configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-5
Temperature Profiles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-6
Component and Melt Physical Properties . . . . . . . . . . . . . . . . . . . 13-6
Output . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-8
Data Required by the Wiped Film Evaporator Unit . . . . . . . . . . . . 13-8
Using the Wiped Film Evaporator to Model Systems. . . . . . . . . . . . . . 13-9
Wiped Film Evaporator Keyword Input . . . . . . . . . . . . . . . . . . . . . 13-9
General Information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-9
Example 13-1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13-14
Appendix A van Krevelen Structural Groups

POLYMERS
6 Contents
Chapter 1
Introduction to Polymers
Polymers form the basis of many useful, synthetic materials com-

mon today. A polymer is a large molecule that has been constructed
from atoms linked together by covalent bonds. This large molecule
is formed by systematically joining together groups of simpler mol-
ecules or monomers. The result is a high molecular weight, long-
chain component made up of various combinations of monomer
units having a recurring chemical structure. The monomer unit itself
has a fixed molecular weight. Monomers may be combined to pro-
duce a polymer by either of two basic mechanismsaddition or
chain polymerization or condensation or step polymerization.
Addition or Chain Polymerization

In this polymerization mechanism, a highly reactive center is cre-
ated, and the monomer is then incorporated into the live chain only
at this center. In the synthesis phase, the reactive center must be
maintained during monomer addition until a polymer of acceptable
molecular weight is generated. The monomer addition process con-
tinues rapidly until the reactive center is transferred away from the
growing chain or deactivated by a termination process. The transfer
or deactivation of the reactive center turns the live or growing poly-
mer chain radical into an inactive or dead polymer chain. Free radi-
cal, ionic, group transfer, metallocene or Ziegler-Natta
POLYMERS
polymerization are special types of addition polymerization.

The recurring unit of the polymer structure that results from addi-
tion polymerization is identical to that of the monomer. Most poly-
mers formed by addition polymerization are thermoplastic; i.e., the
polymer softens or hardens by the addition or removal of heat. Typ-
ical polymers formed by this process include:
PRO/II 7.1 Add-On Modules Users Guide 1-1

Polyethyleneused in packaging, pipes, and containers
Polystyreneused in insulation, pipes, and car panels
BATCH
Poly(vinylchloride) or PVCused in pipes, adhesives, and

shoes.
Condensation or Step Growth Polymerization

In this polymerization mechanism, monomers react with one
another to form larger monomers or macromolecules. These large
molecules essentially assume the role of macromonomers and con-
tinue to react with residual monomer and other macromonomers to
form progressively larger macromonomers. The terms monomer
and macromonomer will be used interchangeably unless some dis-
tinction between the two structures is required. Eventually, the
resulting molecules are of sufficient size that the term polymer is
applicable. This is the step growth polymerization method. In the
course of the polymerization reaction, a low molecular weight com-
ponent (such as H2O or HCl) is usually expelled, and therefore the
term condensation polymerization is common.
In this procedure, the recurring unit of the resulting polymer is not
identical to that of the monomer. Many polymers formed by con-
densation polymerization are thermosetting; i.e., the polymer
becomes rigid and insoluble when heat processed. In addition, poly-
mers created by condensation polymerization techniques may be
cross-linked; i.e., sections of the long-chain polymer react with
each other, resulting in an enhancement of their strength properties
(e.g., hardness or toughness). Typical polymers formed by conden-
sation polymerization include:
Polyesters (e.g., Mylar)used in valves, pumps, and coatings
Polyurethaneused in foam linings, adhesives, and insulation
Polyamides (e.g., Nylon and Kevlar)used in gears, bottles,
and appliances.
POLYMERS
Polymerization reactions are exothermic in nature and require

sophisticated heat controls. The molecular structure and the bulk
polymer morphology are highly temperature dependent.
Polymers also occur naturally as derivatives of animal and plant
products, e.g., cellulose resins, proteins (soybean, casein), and lig-
nin. Both synthetic and natural polymer products may be spun and
stretched to form a wide variety of fibers. These fibers can then be
1-2 Introduction to Polymers

modified (e.g., by adding water repellents or flame retardants),
dyed, and woven to produce natural and synthetic fabrics and yarns.
Terminology
Descriptions of common polymer terms are provided below.
Polymer chain A high molecular weight structure made up of a large

number of polymer segments. In a typical polymer, the
polymer chains may be of varying lengths, and their
distribution can, under certain polymerization condi-
tions, be represented by a Gaussian curve. The poly-
mer properties (e.g., molecular weight) are determined
by a statistical average of a sampling of the polymer
chains.
Polymer A representative section of the polymer chain that con-

segment tains a recurring chemical structural unit.
Cross-linking A process in which polymer chains react with each

other and increase the hardness of the polymer.
Monomer A building block unit of a polymer. Monomer units can

be combined by addition polymerization or
condensation polymerization to form a polymer.
Homopolymer A polymer formed by a single type of monomer unit.
Copolymer A polymer formed by two types of monomer units.
Thermosetting A polymer that remains rigid and insoluble when

polymer heated.
Thermoplastic A polymer that softens or hardens by the addition or

polymer removal of heat.
Polymer blend A non-homogeneous mixture of polymers that results

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in desired polymer properties. Special compatibilizers

are used to make the separate polymer components
adhere to each other while still maintaining distinct
phases.
Condensation or A process in which monomer units are combined by

step growth eliminating small molecules (e.g., HCl, or H2O).
polymerization

Chain or free A process in which monomer units are combined to
radical form polymers with recurring structures identical to
polymerization those of the monomer.
BATCH
Bulk A process in which monomer units are combined in

polymerization bulk in the vapor or liquid phase or on a solid surface.
Solution A process in which monomer units are combined in the

polymerization presence of a solvent to control and slow the polymer-
ization reaction. This process is often used for highly
exothermic reactions and produces polymers of low to
medium molecular weights.
Suspension A process in which monomer units are combined in the

polymerization presence of water and stabilizers to prevent the result-
ing polymer globules from aggregating to each other.
Emulsion A process in which monomer units are combined in the

polymerization presence of water and emulsifiers to create aggregates
or micelles of polymer particles. This process can cre-
ate high molecular weight polymers.
POLYMERS
1-4 Introduction to Polymers

Chapter 2
Using the Polymer Module with PRO/II
To create a simulation for a polymer system using PRO/II, follow

these six steps:
1. Select the input units of measure to be SI.
2. Enter the segment data and select the polymer components
(required).
3. Enter the polymer molecular weight distribution and moments
of distributions (optional).
4. Select the polymer thermodynamic method.
5. Create the flowsheet by selecting the desired polymer reactor(s)
and other pre- and/or post-processing units (such as flash,
mixer, wiped film evaporator) and completing the stream con-
nections between each unit.
6. Solve the flowsheet and generate the output to view the results
of the simulation.
This chapter includes a brief overview of the first five steps. The
following chapters give a more detailed descriptions.
Selecting the Units of Measure POLYMERS
The current version of the polymers module in PRO/II requires the

units of measure basis for input data to be SI. To set the input units
basis to be SI, do the following:
Click the Units of Measure button on the toolbar (or select
Input/Units of Measure from the menu bar) to display the
Default Units of Measure for Problem Data Input dialog box.

Figure 2-1: Default Units of Measure for Problem Data Input Dialog Box
BATCH
Click Initialize from UOM Library... to display the Initialize Units of

Measure from UOM Library dialog box (Figure 2-2).
Figure 2-2: Initialize Units of Measure from UOM Library
Select SI-SET1 from the drop-down list, and click OK. The units
of measure for all properties will now be in SI units; e.g., tem-
perature in degrees Kelvin, pressure in kilopascals, etc.
Entering Polymer Segment and Component Data

First, enter the information regarding the segments that make up the
polymers, and then enter the polymer components based on the
selected segments.
To enter the segment and polymer component data:
POLYMERS
Click the Component Selection button on the toolbar (or select

Input/Component Selection from the menu bar) to display the
Component Selection dialog box.
Click Polymer... to display the Definition of Polymer Compo-
nents dialog box (Figure 2-3).
2-2 Using the Polymer Module with PRO/II

Figure 2-3: Definition of Polymer Components Dialog Box
Complete all the segment data by entering the segment names

and their van Krevelen structures (required entry) and the
UNIFAC structures (optional entry).
After defining the segment data, enter the polymer components
by providing their names, average molecular weights, and the
segment compositions that make up each of the polymer com-
ponents.
All the polymer components selected in this dialog box will be dis-
played in the List of Selected Components in the Component Selec-
tion dialog box after you click OK.
To delete a polymer component:
Select the desired component from the List of Selected Compo-
nents in the Component Selection dialog box and click Delete.
A segment can be deleted by selecting the desired row in the Poly-
mer Segments section of the Definition of Polymer Components dia-
log box and clicking Cut.
Calculating Molecular Weight Distributions

POLYMERS
To calculate or input the molecular weight distributions, first enter

the molecular weight of the pseudocomponents that make up the
distribution. This can be achieved by entering the discrete molecular
weight range values for each of the polymer components. Also, you
can specify the number of moments of the molecular weight distri-
bution that need to be considered during calculations. Each moment
can be assigned a name, or a default name will be used.

To enter data for the molecular weight distribution:
Click the Component Properties button on the toolbar, or select
Input/Component Properties from the menu bar, to display the
BATCH
Component Properties dialog box.

Click Distribution Functions... under Polymer Properties to display
the Distribution Functions for Components dialog box
(Figure 2-4). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.
Figure 2-4: Distribution Function for Components Dialog Box
To enter the distribution data for a polymer component:

Select the desired polymer component from the drop-down list.
Select the appropriate kinetic type for the polymer (Free Radi-
cal, Ziegler-Natta, or Step Growth).
Click Enter Data... to display the Distribution Function Data dia-
log box for the selected component (Figure 2-5).
Figure 2-5: Distribution Function Data Dialog Box
POLYMERS
Select the desired distribution names from the list boxes in the
first column. If you select Discrete Mol. Wt. Cuts, enter the
molecular weight ranges by clicking Enter Data.... For the vari-
ous moments, specify the number of moments and optionally
enter the names of the moments by clicking Enter Data.... The

moment names default to M0, M1, M2, etc., and up to five
moments can be selected (M0 through M4).
Choosing Thermodynamic Methods

PRO/II currently supports five polymer thermodynamic methods
[Advanced Lattice Model (ALM), Flory-Huggins Model (Flory),
Unifac Free Volume Model (UNFV), Statistical Associating Fluid
Theory (SAFT), and Perturbed Hard-Sphere-Chain Theory
(PHSC)].
To select the method to be used in the simulation:
Click the Thermodynamic Data button on the toolbar, or select
Input/Thermodynamic Data from the menu bar, to display the
Thermodynamic Data dialog box (Figure 2-6).
Figure 2-6: Thermodynamic Data Dialog Box
From the Category list, select Polymers. All five polymer ther-
modynamic methods are displayed in the Primary Method list.
Select the desired method, and click Add > to include that
method in the simulation.
To change the thermodynamic method to be used for calculat-
ing various properties, click Modify... . The Modification dialog
box appears (Figure 2-7).
POLYMERS

Figure 2-7: Modification Dialog Box
BATCH
To enter the following, click Enter Data.... Detailed information

on entering these data can be found in Chapter 7, Specifying the
Thermodynamic Method.
Pure species parameters
Binary interaction parameters between two non-polymer
components
Binary interaction parameters between two segments
Binary interaction parameters between a non-polymer com-
ponent and a segment.
Building the Flowsheet and Selecting Polymer Reactors

Select the desired unit operations and the polymer reactors to be
used in the flowsheet from the unit operation palette by clicking on
the appropriate icons and placing them on the PFD.
To add a polymer reactor to the flowsheet:
Select the Polymer Reactors icon and click on the PFD. The
POLYMERS
Polymer Reactors dialog box (Figure 2-8) appears.

Select the desired polymer reactor type from the drop-down list
box. PRO/II supports seven types of CSTRs and seven types of
PFRs.

Figure 2-8: Polymer Reactors Dialog Box
Double-click on the polymer reactor icon on the PFD to display

the dialog box for the selected calculation model. Figure 2-9
shows the CSTR for Free Radical Homopolymerization dialog
box.
Figure 2-9: CSTR for Free Radical Homopolymerization Dialog Box
Enter reactor operating and kinetic data in the Real Data for
Unit (RPARM), Integer Data for Unit (IPARM), and Supple-
mental Data for Unit (SUPPLE) sections. See Chapter 8, Incor-
porating User-Added Polymer Reactor Models, for more
information on the data requirements for the polymer reactor.
POLYMERS

POLYMERS
Chapter 3
Estimating Polymer
Component Property Data
van Krevelen Group Contribution Method

PRO/II provides a segment approach to simulate polymer systems.
It requires you to input the van Krevelen structural groups for
defined segments. The segment approach is applicable to both
homopolymers and copolymers. The van Krevelen group contribu-
tion method is used to predict the properties of the segments that
make up the polymers on the basis of structural groups. This
method, based on the additivity principle, calculates the property of
a segment as the sum of the contribution of structural groups that
make up the segment. You provide information on the structure of
the segments in the form of group identifiers and counts. This
allows you to simulate processes that involve polymers for which
no experimental data are available, or for which no experimental
data are limited. The structure of a given segment is defined using a
unified set of groups. This unified set is a superset of a number of
group sets developed by van Krevelen for the prediction of various
properties of polymers.
Keyword Summary
POLYMERS
Segment Definition (required)
SEGMENT DATA
SEGMENT , name/, &
FILL= VANKREVELEN
STRUCTURE(VANKRE) , igroup(n)/

Component Definition (required)
COMPONENT DATA
BATCH
POLYMER i, name/
PCOMPOSITION(M or W) i, X,(), X(), /
MWAVG i, value/
PHASE VLS or LS or S = i, j
Input Description
SEGMENT DATA
SEGMENT , name/, &
FILL= VANKREVELEN
STRUCTURE(VANKRE) , igroup(n)/
All segments must be defined under SEGMENT DATA.
Segment type letter.
name Name of segment .
FILL This keyword is used to activate the van Krevelen
group contribution method.
The STRUCTURE statement with a VANKRE qualifier is required for

the van Krevelen group contribution method. The default VANKRE
qualifier distinguishes this statement from the UNIFAC structural
group statement (STRUCTURE(UNIFAC)).
Segment type letter.
igroup(n) The seven-digit identifier for an individual structural
group contained in the segment with n being used to
define the number of such groups.
COMPONENT DATA
POLYMER i, name/
MWAVG i, value/
POLYMERS
All polymer components must be defined as POLYMER components.
i Component number.
name Name of component i (polymer).
3-2 Estimating Polymer Component Property Data

MWAVG The molecular weight of each polymer component
must be supplied.
i Component number.
value Molecular weight of component i.
PCOMPOSITION The segment compositions in the polymer must be
supplied.
M Mole units.
W Weight units.
X() Composition of segment in the polymer.
PHASE The polymer phase type can be defined as VLS or LS or
S; default VLS.
i, j Component numbers continuously from
i to j.
van Krevelen Structural Groups

In van Krevelens original work, different group sets are used for
each individual property. Numerous auxiliary rules are used to
account for the location of a group within a main chain or a side
chain and to describe the proximity effects between a number of
groups. Thus, the logical structure of the van Krevelen group sets is
much more complex than the structure of the UNIFAC group sets; a
set of structural groups of over 700 is identified and used to predict
properties of segments that make up polymers in the van Krevelen
method (see Appendix A, van Krevelen Structural Groups).
The van Krevelen structural group codes are constructed through
three subcodes, CC, SS, and GGG, combined into an integer with a
maximum of seven digits, CCSSGGG. The subcodes have the fol-
lowing meanings:
CC An optional number of methylene (CH2) groups in a side chain;
this number can be entered only when the main chain unit con-
tains a methyl (CH3) group.
SS An optional code of the group system; it can equal 00 or 01. If
SS=00, the structure has to be constructed from only main chain
groups, which are marked by a plus (+) sign in the van Krevelen
Structural Groups Table. If SS=01, the structure can be con-
POLYMERS
structed from any combination of the van Krevelen structural

groups.
GGG A code from the van Krevelen Structural Groups Table; it is
required.
It is best to use the group system SS=00. This is due to the fact that
the van Krevelen group contributions have been developed prima-

rily for groups that can serve as main chain segments in a polymer.
It is anticipated that this group system will be used for the vast
majority of polymer segments of interest. However, it is possible
BATCH
that certain polymer segments cannot be constructed from the main

chain groups given in the van Krevelen Groups Table because of
their chemical complexity. For such cases, the SS=01 group system
is needed; it allows you to calculate the properties of polymer seg-
ments that are composed of any combination from the van Krevelen
Structural Groups Table.
When choosing the group codes GGG, it is recommended to start
with the most complex groups to construct the structural units of
polymer segments of interest. Select more elementary groups only
when an appropriate complex group is not found. While this is not
mandatory, it will maximize accuracy.
Example 3-1
The segment structure of polystyrene is constructed using the SS=00
system (the leading zeros are dropped):
SEGMENT DATA
SEGMENT A, STYRENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)
COMPONENT DATA
POLYMER 1, POLYSTRENE
PCOMPOSITION 1, 1(A)
Example 3-2
The segment structure of poly(1-pentene) (PP) is constructed using
the SS=00 system. The number of methylene groups in the side
chain (which is equal to 2) is specified using the CC subcode:
SEGMENT DATA
SEGMENT A, PENTENE1, FILL=VANKREVELEN
COMPONENT DATA
POLYMER 1, PP
POLYMERS
Example 3-3
The segment structure of poly(phenyl methacrylate) (PPMA) can-
not be constructed using the SS=00 system. Therefore, the SS=01
system is used:
SEGMENT DATA
SEGMENT A, PPMA1, FILL=VANKREVELEN

STRUCTURE(VANKRE) A, 01004(1),01001(1),01012(1),&
01110(1),01238(1),01710(2),01708(2)
COMPONENT DATA
POLYMER 1, PPMA
Example 3-4
The segment structure of poly(p-phenylene terephthalamide)
(Kevlar) is best defined by just one group (522), even though the
repeat unit of Kevlar is composed of two phenyl rings, two C=O
groups, and two N-H groups.
SEGMENT DATA
SEGMENT A, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 522(1)
COMPONENT DATA
POLYMER 1, KEVLAR
The van Krevelen group technique can be used to predict polymer

segment properties if structural information is available for the
polymer segments of interest. In PRO/II, over 700 structural groups
have been identified and may be used to define the polymer seg-
ments.
Table 3-1 shows the fixed and temperature-dependent properties of
polymer segments that are predicted by the van Krevelen group
method.
Table 3-1: Properties Predicted by the van Krevelen Method
Fixed Temperature-Dependent
Molecular weight Liquid density
Average segment number Liquid enthalpy
van der Waals volume Surface tension
Normal melting point (NMP) Solid density
Glass transition temperature Solid enthalpy
Specific gravity of liquid at 60 F
POLYMERS
Enthalpy of fusion at NMP

Standard enthalpy of formation at 298.15 K
Standard Gibbs energy of formation at 298.15 K
Solubility parameter
Liquid thermal conductivity at 298.15 K

Reference
[1] D.W. van Krevelen, 1990, Properties of Polymers. Their Corre-
lation with Chemical Structure; Their Numerical Estimation and
BATCH
Prediction from Additive Group Contributions, 3rd edition,

Elsevier. Amsterdam.
Example 3-5
This example uses the van Krevelen group contribution method to
predict properties of segments for polystyrene (PS),
poly(1-pentene) (PP), poly(phenyl methacrylate) (PPMA), and
poly(p-phenylene terephthalamide) (Kevlar). The polymer proper-
ties are generated from the calculated segment properties by the van
Krevelen method. Segment compositions are provided in the input.
TITLE PROB=HOMOPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, STYRENE1/B, PENTENE1/C,PPMA1/&
D, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)/&
B, 200015(1), 4(1)/&
C, 01004(1),01001(1),01012(1),&
01110(1),01238(1),01710(2),&
01708(2)/&
D, 522(1)
COMPONENT DATA
POLYMER 1, PS/&
2, PP/&
3, PPMA/&
4, KEVLAR
PCOMPOSITION 1,1(A)/2,1(B)/3,1(C)/4,1(D)
PHASE VLS = 1,4
MWAVG 1,10000/2,10000/3,10000/4,10000
$
LIBRARY 5, HEXANE
$
POLYMERS
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$

$
$
$
UNIT OPERATION
HCUR UID=HC1L
ISO STREAM=F1L, TEMP=200, 400, PRES=10, POIN=20
PROP THERMO
HCUR UID=HC1S
ISO STREAM=F1S, TEMP=200, 300, PRES=10, POIN=20
PROP THERMO
$
HCUR UID=HC2L
PROP THERMO
HCUR UID=HC2S
PROP THERMO
$
HCUR UID=HC3L
PROP THERMO
HCUR UID=HC3S
PROP THERMO
$
HCUR UID=HC4L
PROP THERMO
HCUR UID=HC4S
PROP THERMO
POLYMERS
Example 3-6
This example uses the van Krevelen group contribution method to
predict properties of segments for the copolymer poly(methyl meth-
acrylate-co-vinyl acetate) (PMMACcoVAC), which has 25% vinyl
acetate. The copolymer properties are generated using calculated
segment properties by the van Krevelen method. Segment composi-
tions are provided in the input.

TITLE PROB=COPOLYMER
DIMENSION SI
PRINT INPUT = FULL
BATCH
$
SEGMENT DATA
SEGMENT A, MMAC1/B, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),252(1),9(1)/B,5(1),250(1),9(1)
$
COMPONENT DATA
POLYMER 1, PMMACcoVAC
PCOMPOSITION 1, 0.75(A),0.25(B)
PHASE VLS = 1
MWAVG 1,10000
$
LIBRARY 2, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
$
UNIT OPERATION
HCUR UID=HC1L
PROP THERMO
HCUR UID=HC1S
PROP THERMO
$
Entering Polymer Segment and Component Data

To enter the segment and polymer component information:
Click the Component Selection button on the toolbar, or select
Input/Component Selection from the menu bar, to display the
Component Selection dialog box (Figure 3-1).
POLYMERS

Figure 3-1: Component Selection Dialog Box
Click Polymer... to display the Definition of Polymer Compo-

nents dialog box (Figure 3-2).
Figure 3-2: Definition of Polymer Components Dialog Box
Enter the names of the desired segments, and click Enter Data...
for each segment to display the Define van Krevelen Structures
dialog box (Figure 3-3). POLYMERS

Figure 3-3: Define van Krevelen Structures Dialog Box
BATCH
Enter the van Krevelen structure groups and counts by either

selecting from the lists at the top of the dialog box or by enter-
ing the group number directly into the table.
You can also enter the UNIFAC structures for the segments by
clicking Enter Data... under UNIFAC Structures. The Define UNIFAC
Structures dialog box appears (Figure 3-4). UNIFAC structures are
required if the selected polymer thermodynamic method is UNIFAC
Free Volume.
Figure 3-4: Define UNIFAC Structures Dialog Box
POLYMERS

After the segment information is complete, enter the compo-
nent names in the Polymer Components table. Supply an aver-
age molecular weight for each component.
To specify the segment composition for each component (in
either the mole or mass basis), click Enter Data... under Segment
Composition to display the Segment Composition Data dia-
log box (Figure 3-5).
Figure 3-5: Segment Composition Data Dialog Box
POLYMERS

POLYMERS
Chapter 4
Supplying Polymer Pure
Component Property Data
In PRO/II, component property data can be supplied for homopoly-

mers and copolymers. You can provide polymer segment composi-
tions, polymer phase types, and polymer molecular weights. You
can also provide the molecular weight distribution (MWD), moments
of the molecular weight distribution (MMWD), and other moment
distributions. You also supply values for a number of invariant prop-
erties (e.g., heat of fusion, crystallinity, and tacticity) and tempera-
ture-dependent properties (e.g., density, enthalpy, viscosity, and
thermal conductivity).
Keyword Summary
Polymer Definition (required)
POLYMER i, name/
MWAVG i, value/
Polymer Attributes (conditional)

ATTRIBUTE COMPONENT = i,j, KINETICS = FR or ZN or SG,
POLYMERS
MWD = mw1, mw2, , &

{MMWD = M0, M1, M2, M3, M4}, &
{MBCL = M0, M1, M2, M3, M4}, &
{MTTB = M0, M1, M2, M3, M4}, &
{MDSD(unit)= s0, s1, s2, }, &
{PSD(unit) = s0, s1, s0, }, &
GENERAL = 10, {GNAME = text1, text2, text3, }

Polymer Invariant Properties (optional)
NMP(unit) i, value
TGLASS(unit) i, value
BATCH
HFUSION(unit) i, value
SOLUPARA(unit) i, value
Polymer Temperature-Dependent Properties (optional)

DENSITY(L or S, propunit, tunit, WT or M) CORRELATION=icorr,
DATA = i, tmax, tmin, C1, , C8 /
or
TABULAR= t1, t2, /i, p1, p2, /
ENTHALPY(L or S, propunit, tunit, WT or M) CORRELATION=icorr,
or
SURFACE(L, propunit, tunit, WT or M) CORRELATION=icorr,
or
CONDUCTIVITY(L or S, propunit, tunit, WT or M)
CORRELATION=icorr,
or
VISCOSITY(L, propunit, tunit, WT or M) CORRELATION=icorr,
or
Input Description
POLYMERS
Polymer Definition (required)

POLYMER i, name/
PCOMPOSITION(W or M) i, X(), X(),/
MWAVG i, value/
4-2 Supplying Polymer Pure Component Property

POLYMER Defines the polymer component.
PCOMPOSITION Provides the composition (e.g. X, X, ) for each
segment in the polymer. The composition of segments
can be given in weight or mole units and will be nor-
malized before calculation.
MWAVG Supplies the polymer molecular weight.
PHASE Provides the phase assignments for the polymer com-
ponents as well as for the regular components. Because
most polymers at normal processing conditions can
exist only in L and/or S phases, phase designations of
VLS, LS, or S are appropriate for polymer compo-
nents.
Note: Polymer components by definition are non-library components

and will not have any data stored in the component library. All polymer
properties must be either input or calculated from properties of the con-
stituent segments predicted by the van Krevelen method, known struc-
ture-property relationships, and the input segment compositions.
Polymer Attributes (required for unit US21)

ATTRIBUTE COMPONENT = i,j, KINETICS = FR or ZN or SG,
MWD = mw1, mw2, , &
{MMWD = M0, M1, M2, M3, M4}, &
{MBCL = M0, M1, M2, M3, M4}, &
{MTTB = M0, M1, M2, M3, M4}, &
{MDSD(unit)= s0, s1, s2, }, &
{PSD(unit) = s0, s1, s0, }, &
GENERAL = 10, {GNAME = text1, text2, text3, }
Polymer component attributes consist of required defined attributes
(MWD) and optional defined attributes. General attributes may be
used by certain users for properties of interest to them, such as acid
number or special end-use properties. A PSD attribute must be
POLYMERS
defined for modeling the particle size distribution of crystalline

polymer solids. The defined attributes are:

KINETICS Specifies the kinetics type of polymerization as Free
Radical (FR) Polymerization, Ziegler-Natta (ZN)
Polymerization, or Step Growth (SG) Polymerization.
BATCH
MWD Specifies the molecular weight distribution (MWD) to

be used in the polymerization processes. If the poly-
mer component can be modeled as a distribution of
discrete pseudocomponents, then mw1 is the average
molecular weight of the first pseudocomponent, mw2
is the average molecular weight of the second
pseudocomponent, and so on.
Note: The MWD must be supplied for the polymer components if the
polymer reactor unit US21 is used.
MMWD Specifies the molecular weight distribution (MWD)

that will be used in the polymerization processes. M0 is
the zeroth order moment, M1 is the first order moment,
M2 is the second order moment, and so on.
MBCL Specifies the moments with respect to the branch chain
length, measured as the numbers of average monomer
units in the branches. It is called Moments of
Branching Length.
MTTB Specifies the moments with respect to the number of
trifunctional/tetrafunctional branches. It is called
Moments of Branching Density.
MDSD Specifies the distribution of monomer droplets in
emulsion and suspension polymerization. Monomer
droplets are dispersed in the liquid phase and may be
uniform in size (emulsion polymerization) or may fol-
low a size distribution (suspension polymerization).
The first range has particles with diameters ranging
from s0 to s1; the second range has particles from s1
to s2, and so on. The last range is sn-1 to sn, where n is
the size given for the component. It is called Droplet
Size Distribution.
PSD Specifies Particle Size Distribution, defaulting to prob-
lem fine length units. The first range has particles with
diameters ranging from s0 to s1; the second range has
POLYMERS
particles from s1 to s2, and so on. The last range is

sn-1 to sn, where n is the number of size given for the
component.
GENERAL Specifies the number of user-defined solid attributes.
The default is 10. The range extends to 100.

GNAME Specifies the user-defined names for each of the
GENERAL attributes. A maximum of four alphanu-
meric characters are allowed. If the number of GNAME
arguments is less than the GENERAL integer value,
PRO/II fills in the remaining names. The default
assigned names are AT01, AT02, etc.
Polymer Invariant Properties (optional)

NMP(unit) i, value
TGLASS(unit) i, value
HFUSION(unit) i, value
SOLUPARA(unit) i, value
Table 4-1: Pure Component Invariant Properties

Property Unit Description
NMP Temperature Normal melting point
TGLASS Temperature Glass temperature
HFUSION Energy/Mole (default) or Heat of fusion
Energy/Mass
SOLUPARA Fixed, (cal/cc)1/2 Solubility parameter
Polymer Temperature-Dependent Properties (optional)

DENSITY(L or S, propunit, tunit, WT or M) CORRELATION=icorr,
or
ENTHALPY(L or S, propunit, tunit, WT or M) CORRELATION=icorr,
or
SURFACE(L, propunit, tunit, WT or M) CORRELATION=icorr,
POLYMERS

or
CONDUCTIVITY(L or S, propunit, tunit, WT or M)
CORRELATION=icorr,

or
BATCH
VISCOSITY(L, propunit, tunit, WT or M) CORRELATION=icorr,

or
The defined attributes include:
allowable phase I-Ideal gas, V-Vapor, L-Liquid, S-Solid phase.
tunit Temperature units used in correlation or tabular data:
F, R, C, K. Defaults to problem units.
propunit Specific to each property. See Table 1.8-4 of the
SIMSCI Component and Thermodynamic Data Input
Manual.
allowable basis M-Mole, WT-Weight
CORRELATION The correlation form for equation-based data. See
Table 1.8-5 of the SIMSCI Component and Thermody-
namic Data Input Manual for the available equation
forms for each property.
DATA Data entry for equation-based correlations:
i Component number.
tmax, tmin Temperature limits for the data. Must
be entered for Chebychev equations,
optional for others.
C1, ,C8 Equation coefficients.
or
TABULAR Data entry for tabular based data.
t1, Temperatures at which tabular data are
entered. Correspond to data points p1,.
A minimum of two points must be given.
I Component number
POLYMERS
p1, Data values at temperatures t1,.... A minimum

of one value must be given. It is not necessary
to provide a value for every temperature
point. A place-holding comma must be sup-
plied for every value skipped. For vapor pres-
sures and viscosities, ln(p) vs. 1/t, where t is
absolute temperature, is used for interpola-
tion. For all others, linear p vs. t is used.

PRO/II also predicts the (pseudo) critical properties of polymers
based on the molecular weight only. This method is an extension of
a correlation originally developed by Tsonopoulos and Tan for nor-
mal alkanes (from methane to polyethylene).
Reference
C. Tsonopoulos and Z. Tan, 1993, The Critical Constants of Normal
Alkanes from Methane to Polyethylene II. Application of the Flory
Theory, Fluid Phase Equilibria, 83:127-138.
Example 4-1: WFE with Pseudocomponent Distribution

This example tests the wiped film evaporator (WFE) model with a
polymer pseudocomponent distribution. The WFE unit operation
model requires the transport properties.
TITLE PROJECT=WFE, PROBLEM=PS, USER=SIMSCI, DATE=DECEMBER/97
DESC TEST WFE WITH POLYMER PSEUDOCOMPONENT DISTRIBUTION
PRINT STREAM=ALL, RATE=WT, FRACTION=WT
DIMENSION SI
SEQUENCE PROCESS
SEGMENT DATA
SEGMENT A, STYR1, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)
COMPONENT DATA
LIBID 2, STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLY 1, PSTYR
PCOMPOSITION 1,1(A)
PHASE VLS=1
MWAVG 1,31000
ATTRIBUTE COMP=1, KINETICS=FR, MWD=1000,3000,5000, 7000,10000,

30000,40000,60000,80000,100000,120000,150000,200000,&
300000,400000,500000,600000, MMWD=MU0,MU1,MU2
VISCOSITY(V,K,PAS) TABULAR=300,500/1,0.001,0.001
VISCOSITY(L,C,PAS) TABULAR=30,100,500/1,500,450,300
CONDUCTIVITY(V,K,W/MK) TABULAR=300,500/1,1,1
POLYMERS
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE, DIFFUSIVITY=DATA,
KVAL(VLE)
ALME 3,A, 0.022,11.02
ALMC A,1.338
DIFFUSIVITY(L)
DIFDATA(K) 1,2,1E-8
DIFDATA(K) 1,3,5E-8
DIFDATA(K) 1,4,1E-9

STREAM DATA
PROPERTY STREAM=F1, TEMPERATURE=343, PRESSURE=1013.3, &
COMPOSITION(WT,KG/M)=2,10.4188/4,0.15
BATCH
UNIT OPERATIONS
PCSTR UID=REACTOR_1, NAME=1st PS REACTOR
FEED F1
PRODUCT P1
IPARM =1,1,1,0,79,0,1,1,1,3,1,2,0,3,4,0,0,0,0,0,0
RPARM =69900,200,0,0,0,355,0,0.5,0,0,0,0,1,0,0,0,0,0
SUPPLEMENTAL =1,1.58E15/128870/0/0/1.05E7/29540/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/1.05E7/29540/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/1.26E9/7030/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/&
0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0/0
FLASH UID=F2
FEED P1
PRODUCT V=V2, L=L2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
SPEC STREAM=L2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F2, TEMP
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED L2
PRODUCT L3,V3
IPARM =1,,,1,,2,4
RPARM =3,0.75,0.2,,,,,,,,500,,,,,,,,,0.0001,1E-5,400
END
Entering Molecular Weight Distributions

POLYMERS
To enter the molecular weight distribution:

Click the Component Properties button on the toolbar, or select
Input/Component Properties from the menu bar, to display the
Component Properties dialog box (Figure 4-1).

Figure 4-1: Component Properties Dialog Box
Click Distribution Functions... in the Polymer Properties section to

display the Distribution Functions for Components dialog box
(Figure 4-2). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.
Figure 4-2: Distribution Functions for Components Dialog Box
To enter the distribution data for a polymer component:

Select the desired component from the drop-down list.
Select the kinetic type of the component (Free Radical, Ziegler-
Natta, or Step Growth).
Click Enter Data... to display the Distribution Function Data
dialog box for the selected component (Figure 4-3).
POLYMERS

Figure 4-3: Distribution Function Data Dialog Box
BATCH
Select the desired distribution names from the list boxes in the
first column.
For Discrete Mol. Wt. Cuts, enter the molecular weight ranges
by clicking Enter Data.... The Molecular Weight Distribution
dialog box appears (Figure 4-4).
Figure 4-4: Molecular Weight Distribution Data Dialog Box
For the moments of various distributions, specify the number of

moments, and enter the names of the moments by selecting
them from the drop-down list box (optional task). The moment
names default to M0, M1, M2, etc., and up to five moments can
be selected (M0 through M4).
POLYMERS

Chapter 5
Supplying Polymer Stream Data
In addition to the composition of the polymer components, defined

streams containing polymers will also require input of MWD mole
fraction or weight fraction values to be interpreted in terms of
moments that might be submitted to a polymer reactor or other unit
operation process. You can also supply values of various moments,
size distributions, and general attributes that are defined in the poly-
mer component attributes. PRO/II will calculate the SCHULZ-
FLORY distribution from bulk moments generated from a polymer
reactor model or input by the user. PRO/II will also calculate the
number average molecular weight, weight average molecular
weight, and polydispersity index from the moments for various
chain types (e.g., live, dead, and bulk).
PRO/II provides the polymer characterization conversion utility to
establish a useful translation between the molecular weight distribu-
tion and the moments of the molecular weight distribution. You can
supply a molecular weight distribution to be interpreted in terms of
moments, or you can supply moments of a molecular weight distri-
bution to be converted to amounts of pseudocomponents that define
the molecular weight distribution.
Values of moments of distributions with respect to other parameters
of interest may also be input in the stream data section; e.g. moment
POLYMERS
attributes for branch chain length for a branched polymer. Moments

or properties defined as general attributes in the component data
section will also have their values entered here. Mole fraction and
weight fraction attributes for the different types of polymer chains
as fractions of the total chains can also be input for the polymer in
the stream. If there are polymer solids in the stream and PSD

attributes have been defined for the solid components, then PSD
weight fractions can be input for the solid polymers.
BATCH
Keyword Summary
Stream Polymers (optional)
MWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC or PBC or DA
or DB or DAA or DBB, L or S, M or WT), COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MMWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC or PBC or
DA or DB or DAA or DBB, L or S, unit), COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
PCFRAC(L or S, M or WT) COMPONENT = i, j, DATA = value1, value2,
value3, value4, value5, value6, value7, value8, value9, value10,
value11, value12, value13, {STREAM = sid}
MBCL(P or D, L or S, unit) COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
MTTB(P or D, L or S, unit) COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
MDSD COMPONENT = i, j, DATA = value1, value2, ..., {STREAM = sid}
PSD COMPONENT = i, j, DATA = value1, value2, ..., {STREAM = sid}
GENERAL COMPONENT = i, j, DATA = value1, value2, ...,
{STREAM = sid}
Polymer-specific data in the stream data section include composi-
tions of polymer components in the streams. This input is the same
as that for the regular components. Polymer solids in streams are
also specified using the same input as regular or low molecular
weight solids, i.e., using the SOLID and PSD statements.
Values of moments of distributions of polymer components with
respect to various parameters can be input as attributes. The
moments are defined in Chapter 4. For distributions that are func-
tions of the topology of the polymer, moments of live chains P and
dead chains D can be input for polymer components in the liquid (L)
and solid (S) phase in the stream.
You can provide data for either the molecular weight distribution
POLYMERS
through the MWD statement or for the moments of the molecular

weight distribution through the MMWD statement. Data input is not
allowed simultaneously for both of the MWD and MMWD statements.
The polymer characterization conversion utility will convert one
characterization into another. For instance, if mole or weight frac-
tion values are input for the MWD attributes, PRO/II will convert the
MWD attributes into the MMWD attributes (e.g., zero order, first order,
and second order). Conversely, if the moments are input for the
5-2 Supplying Polymer Stream Data

MMWD attributes, the MWD attribute values will be calculated and
then will be converted into the amounts of pseudocomponents that
define the molecular weight distribution.
The PCFRAC attribute refers to the mole or weight fraction compo-
sitions of the polymer chain types. These attributes can be input for
polymer components in the liquid (L) and solid phase (S) in the
stream. The PCFRAC attribute input is required for the MMWD
attributes and will be calculated for the MWD attributes.
For monomer emulsion/suspension in the stream, the distribution of
the monomer droplet size must be specified. Finally, values of gen-
eral attributes can also be entered here.
The moments or attributes of the polymer component in the stream
can be accessed and modified by the polymerization reactors and
unit operations in the flowsheet, although the type of the distribu-
tion function will continue to remain the same (or undefined)
throughout the flowsheet.
All data entered from POLYMER STREAM ATTRIBUTES affect all
components in sequence from component i through j. If j is not
given, only component i is activated. Separate statements are
allowed for each component having these attributes declared in
COMPONENT DATA. These attributes are listed below.
MWD or MMWD Attributes for Free Radical (FR) Polymerization

(Monomers are up to two, A and B)
PA refers to live chains terminating in single type A bond
PB refers to live chains terminating in single type B bond
PC not used for FR
PAA refers to live chains terminating in double type A bonds
PBB refers to live chains terminating in double type B bonds
PCC not used for FR
PAB not used for FR
POLYMERS
PAC not used for FR

PBC not used for FR
DA refers to dead chains terminating in single type A bond
DB refers to dead chains terminating in single type B bond
DAA refers to dead chains terminating in double type A bonds
DBB refers to dead chains terminating in double type B bonds

MWD or MMWD Attributes for Coordination Complex (ZN)
Polymerization
BATCH
(Monomers are up to two, A and B)

PA refers to live polymer chain bounded by monomer A at site 1
PB refers to live polymer chain bounded by monomer A at site 1
PC refers to dead polymer chain generated from site 1
PAA refers to live polymer chain bounded by monomer A at site 2
PBB refers to live polymer chain bounded by monomer A at site 2
PCC refers to dead polymer chain generated from site 2
PAB refers to live polymer chain bounded by monomer A at site 3
PAC refers to live polymer chain bounded by monomer A at site 3
PBC refers to dead polymer chain generated from site 3
DA refers to live polymer chain bounded by monomer A at site 4
DB refers to live polymer chain bounded by monomer A at site 4
DAA refers to dead polymer chain generated from site 4
DBB not used for ZN
MWD or MMWD Attributes for Step Growth (SG) Polymerization

(Monomers are up to three, A, B, and, C)
PA refers to monofunctional live chains terminating in A
PB refers to monofunctional live chains terminating in B
PC refers to monofunctional live chains terminating in C
PAA refers to bifunctional live chains terminating in A and A
PBB refers to bifunctional live chains terminating in B and B
PCC refers to bifunctional live chains terminating in C and C
PAB refers to bifunctional live chains terminating in A and B
PAC refers to bifunctional live chains terminating in A and C
PBC refers to bifunctional live chains terminating in B and C
DA refers to dead chains
POLYMERS
DB not used for SG

DAA not used for SG
DBB not used for SG

PCFRAC Attributes for Free Radical (FR) Polymerization
(Monomers A and B)
value1 fraction of live chains terminating in single type A bond
value2 fraction of live chains terminating in single type B bond
value3 zero, not used for FR
value4 fraction of live chains terminating in double type A bonds
value5 fraction of live chains terminating in double type B bonds
value10 fraction of dead chains terminating in single type A bond
value11 fraction of dead chains terminating in single type B bond
value12 fraction of live chains terminating in double type A bonds
value13 fraction of live chains terminating in double type B bonds
PCFRAC Attributes for Coordination Complex (ZN) Polymerization

Monomers A and B)
value1 fraction of live polymer chain bounded by monomer A at site 1
value2 fraction of live polymer chain bounded by monomer B at site 1
value3 fraction of dead polymer chain generated from site 1
POLYMERS
value13 not used for ZN

(PCFRAC Attributes for Step Growth (SG) Polymerization
(Monomers A, B, and C)
BATCH
value1 fraction of monofunctional live chains terminating in A

value2 fraction of monofunctional live chains terminating in B
value3 fraction of monofunctional live chains terminating in C
value4 fraction of bifunctional live chains terminating in A and A
value5 fraction of bifunctional live chains terminating in B and B
value6 fraction of bifunctional live chains terminating in C and C
value7 fraction of bifunctional live chains terminating in A and B
value8 fraction of bifunctional live chains terminating in A and C
value9 fraction of bifunctional live chains terminating in B and C
value10 fraction of dead chains
value11 zero, not used for SG
Example 5-1: Component and Stream Attribute Input

This example illustrates the input of the polymer component
attributes and the polymer stream attributes. This sequence converts
the input MWD attributes into the MMWD attributes for the kinetics of
free radical polymerization. The PCFRAC attributes will be calcu-
lated.
TITLE PROJ=MWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/B, 5(1), 252(1), 9(1)
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
POLYMERS
MWAVG 1, 8578.6
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR, &
MWD = 1000, 2000, 5000, 7000, 10000, 15000, 20000, &
MMWD = MU0, MU1, MU2, MU3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM
KVALUE
ALMC A, 1.338/B, 1.441
ALME 2,A, 0.022,11.02/2,B, 0.010, 16.36
STREAM DATA

PROP STRM=FEED, TEMP(K)=298.15, PRES(ATM)=1, &
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MWD(PA,L) COMP= 1, DATA = 25,10, 5,30,50,20,40, NORM, STREAM = FEED

MWD(PB,L) COMP= 1, DATA = 5,30,15,25,50,20,10, NORM, STREAM = FEED
MWD(PAA,L) COMP= 1, DATA = 35, 5,20,30,40,15,25, NORM, STREAM = FEED
MWD(PBB,L) COMP= 1, DATA = 15,40,30,20,10, 5,25, NORM, STREAM = FEED
MWD(DA,L) COMP= 1, DATA = 25,35,45,20,15,50,30, NORM, STREAM = FEED
MWD(DB,L) COMP= 1, DATA = 15,25,35,10, 5,40,20, NORM, STREAM = FEED
MWD(DAA,L) COMP= 1, DATA = 5,45,55,25,20,10,30, NORM, STREAM = FEED
MWD(DBB,L) COMP= 1, DATA = 25,30,20,40,10,50,15, NORM, STREAM = FEED
MBCL(P,L) COMP = 1, DATA = 1, 1000, 100000, STREAM=FEED

MTTB(P,L) COMP = 1, DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, DATA = 5, 5000, 500000, STREAM=FEED

MTTB(D,L) COMP = 1, DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, DATA = 30, 30, 40, STREAM=FEED

PSD COMP = 1, DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1, DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=298.15, PRES(ATM)=1
END
Example 5-2: Component and Stream Attribute Input

This example shows the input of the polymer component attributes
and the polymer stream attributes. This sequence converts the input
MMWD attributes into the amounts of the pseudocomponents that
define the molecular weight distribution. The input PCFRAC
attributes are required for the conversion.
TITLE PROJ=MMWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/B, 5(1), 252(1), 9(1)
POLYMERS
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
MWAVG 1, 11276
$ POLYMER COMPONENT ATTRIBUTES

ATTRIBUTE COMPONENT = 1, KINETICS = FR, &
MWD = 1000,2000, 5000, 6000,8000,10000,&
12000,15000,20000,50000,70000,100000,&
MMWD = MU0, MU1, MU2, MU3
BATCH
MBCL = BCL0, BCL1, BCL2, *

MTTB = TTB0, RHO1, RHO2, *
MDSD = 10, 100, 1000, *
PSD = 20, 200, 2000, *
GENERAL = 3, *
GNAME = ATT1, ATT2, ATT3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM

KVALUE
ALMC A, 1.338/B, 1.441
ALME 2,A, 0.022,11.02/2,B, 0.010, 16.36
STREAM DATA
PROP STRM=FEED, TEMP(K)=300, PRES(ATM)=1, &
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MMWD(PA,L) COMP = 1,DATA = 0.1,10,2500,1000000,STREAM = FEED
MMWD(PB,L) COMP = 1,DATA = 0.2,20,3500,2000000,STREAM = FEED
MMWD(PAA,L) COMP = 1,DATA = 0.3,30,4500,3000000,STREAM = FEED
MMWD(PBB,L) COMP = 1,DATA = 0.4,40,5500,4000000,STREAM = FEED
MMWD(DA,L) COMP = 1,DATA = 0.5,50,6500,5000000,STREAM = FEED
MMWD(DB,L) COMP = 1,DATA = 0.6,60,7500,6000000,STREAM = FEED
MMWD(DAA,L) COMP = 1,DATA = 0.7,70,8500,7000000,STREAM = FEED
MMWD(DBB,L) COMP = 1,DATA = 0.8,80,9500,8000000,STREAM = FEED
PCFRAC(L,WT)COMP=1,DATA= 0.1,0.2,0.0,0.05,0.05,0.0,0.0,0.0,&
0.0,0.1,0.1,0.1,0.1, NORM, STREAM=FEED
BCL(P,L) COMP = 1, DATA = 1, 1000, 100000, STREAM=FEED
MTTB(P,L) COMP = 1, DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, DATA = 5, 5000, 500000, STREAM=FEED
MTTB(D,L) COMP = 1, DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, DATA = 30, 30, 40, STREAM=FEED
PSD COMP = 1, DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1, DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=300, PRES(ATM)=1
POLYMERS
END

Entering Stream Polymer Data
Stream data for the polymer components can be supplied for the
various distributions that were selected previously in the Compo-
nent Property section in Chapter 4.
Double-click on the desired stream to display the Stream Data
dialog box (Figure 5-1).
Figure 5-1: Stream Data Dialog Box
Click Stream Polymer Data... to display the Polymer Distributions

dialog box (Figure 5-2). The distribution data must be supplied
on a component-by-component basis. Only those components
with distributions that were specified in the Component Proper-
ties section in Chapter 4 will be available in the drop-down
lists.
Figure 5-2: Polymer Distributions Dialog Box
POLYMERS

Select the desired component, and click Enter Data... under MW/
Moment Distributions to display the Polymer Component
Distributions dialog box (Figure 5-3), in which the various dis-
BATCH
tribution types can be selected. Only those distributions that

were selected for the current component in the Component
Properties section in Chapter 4 will be displayed in this dialog
box. Also, data for only one of Molecular Weight Distribution
or Moments of Molecular Weight Distribution can be supplied.
If one is selected, the other will not be available.
Figure 5-3: Polymer Component Distributions Dialog Box
After selecting the distributions, click Enter Data... under

Additional Data to supply data for various chain types of the
polymer component in the Polymer Distribution Data dialog
box (Figure 5-4). Note that the chain type available will depend
on the polymer type (homopolymer or copolymer) and the
selected kinetic type (free radical, Ziegler-Natta, or step
growth).
POLYMERS

Figure 5-4: Polymer Distribution Data Dialog Box
Click Enter Data... under Additional Data to supply the data for
that chain type. If Discrete Mol. Wt. Cuts (MWD) is selected,
supply the molecular weight fractions (Figure 5-5).
Figure 5-5: Discrete Mol. Wt. Cuts Dialog Box
If Moments of Mol. Wt. Distribution (MMWD) is selected, sup-

POLYMERS
ply the values for the moments for the selected chain type and
the chain type fraction (PCFRAC) (Figure 5-6). Data can be sup-
plied for liquid and/or solid phase.

Figure 5-6: Moments of Mol. Wt. Distribution Dialog Box
BATCH
POLYMERS

Chapter 6
Stream Output Report Options
By default, the weight rates of the individual polymer pseudocom-

ponents (which result from the MWD attributes given for the poly-
mer) are printed in the Stream Weight Component Rates section of
the Stream Summary output. By using the optional PWRATE key-
word on the PRINT statement in the General Data category of input,
the weight rate of the TOTAL polymer is printed instead.
Also by default, the polymer characterization conversion utility is
activated for a simulated system containing polymers, and the con-
verted results either for the MWD attributes or for the MMWD
attributes will be printed out in the stream output. By using the
optional PCONV keyword on the PRINT statement in the General
Data category of input, the polymer characterization conversion
utility is disabled.
Keyword Summary
PRINT , PWRATE, PCONV
PWRATE This optional keyword specifies that the rate (on a weight
basis) of the total polymer component be printed in the
Stream Component Rates section of the output report.
PCONV This optional keyword disables the polymer characterization
conversion utility that converts one characterization (e.g. the
POLYMERS
MWD attributes or the MMWD attributes) into another.
Typical Usage
TITLE
DIME METRIC
PRINT RATE=WT, INPUT=ALL,PWRATE,PCONV


Entering PWRATE and PCONV
To enter PWRATE:
BATCH
Select Output/Report Format from the menu bar, and then

select Stream Properties to display the Stream Property Report
Options dialog box (Figure 6-1). By default, the Include Poly-
mer Pseudocomponent Flowrates option is checked, indicating
that the output report will contain the pseudocomponent flow-
rates. Uncheck this box to obtain the total polymer component
rate (on a weight basis) in the Stream Component Rates section
of the output report.
Figure 6-1: Stream Property Report Options Dialog Box
To toggle PCONV, the polymer characterization conversion:

Select Input/Miscellaneous Data from the menu bar to display
the Input Miscellaneous Data dialog box (Figure 6-2). By
default, the Polymer Consistency Check option is set to Yes. To
turn off the polymer characterization conversion utility, select
No in the drop-down list.
Figure 6-2: Input Miscellaneous Data Dialog Box
POLYMERS
6-2 Stream Output Report Options

Chapter 7
Specifying the Thermodynamic Method
In addition to the van Krevelen group contribution method for pre-

dicting thermophysical properties of polymers from structures of
segments, PRO/II also provides a set of superior polymer-specific
thermodynamic methods for phase equilibrium calculations for the
system containing polymers. These methods include the classical
Flory-Huggins model (FLORY), the popular UNIFAC-Free Volume
model (UNFV), the Advanced Lattice Model (ALM) developed by
SIMSCI, and the two state-of-the-art polymer equations of state,
i.e., the Statistical Associating Fluid Theory (SAFT) and the
Perturbed Hard-Sphere-Chain (PHSC) Theory.
All these methods have been implemented in PRO/II using the seg-
ment approach. For the pure component parameters, data may be
input for non-polymer components (solvents) and for segments that
make up the polymers. The polymer component parameters will be
generated from the segment properties predicted by the van
Krevelen method and segment compositions through input. For the
binary parameters, data can be input for non-polymer component
pairs (solvent-solvent), solvent-segment pairs, and segment-
segment pairs.
PRO/II automatically uses a new polymer flash algorithm devel-
oped by SIMSCI when a polymer-specific method is specified in
POLYMERS
the input.

Advanced Lattice Model (ALM)
The advanced lattice model (ALM) is used to predict VLE and
VLLE phase behavior for mixtures containing polymers. ALM is a
BATCH
segment-based activity coefficient model and is especially useful

for polymer solutions and polymer blends. It gives much more
accurate VLE and LLE correlations than the commonly used Flory-
Huggins model.
Typical Usage

SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
COMPONENT DATA
LIBID 1,BENZENE
POLYMER 2, PIB
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=ALM

Table 7-1: Attributes of ALM Method

Properties predicted by ALM methods K-values
Required pure component properties* Molecular weight
Liquid molar volume
Two liquid phase behavior VLLE Supported
* Automatically supplied by PRO/II for library and petroleum components.
Must be supplied or estimated using the van Krevelen group contributions
method for polymer components.
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=ALM, PHI=IDEAL, {HENRY},
or
POLYMERS
METHOD KVALUE(VLE and/or LLE or VLLE)=ALM, PHI=IDEAL,

{HENRY},
SYSTEM Selects a combination of consistent thermodynamic

property generators. When SYSTEM=ALM is chosen,
ALM K-values, IDEAL enthalpies, IDEAL liquid den-
sities, and IDEAL vapor densities are the defaults.
7-2 Specifying the Thermodynamic Method

KVALUE Selects the method for K-value calculations. Both VLE
and LLE K-value calculations are available with the
ALM method. The VLLE option automatically selects
both. See Section 2.1.7 of the SIMSCI Component and
Thermodynamic Data Input Manual (CTDIM) for
more details on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (i). A
vapor fugacity method should generally be selected for
high pressure applications. The options are the equa-
tions of state methods SRK, PR, SRKM, PRM, SRKH,
PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and UNI-
WAAL (see Section 2.4 of the SIMSCI CTDIM and
HOCV (the Hayden-OConnell method), TVIRIAL
(the Truncated Virial method), and the IDIMER
method. See sections 2.5.12, 2.5.13, and 2.5.14, Hay-
den-OConnell, Vapor Fugacity, Truncated Virial
Vapor Fugacity, and IDIMER Vapor Fugacity, of the
SIMSCI CTDIM for details on these last three options.
The default is PHI=IDEAL.
HENRY Selects Henrys Law data (either user-supplied or from
databanks) to model dissolved gases in a liquid solu-
tion. See Section 2.5.11, Henrys Law for Non-
condensable Components, of the SIMSCI CTDIM for
details.
Note: A heat of mixing option, HMIX, is available for the enthalpy
method selected. See Section 2.5.15, Redlich-Kister, Gamma Heat of
Mixing, of the SIMSCI CTDIM for details on the use of this option.
K-Value Data (optional)

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
ALME , , e1, e2, e3/
ALMC , c/
POYNTING Selects whether to apply the Poynting correction to

fugacities of components in the liquid phase. The
default is OFF unless a PHI method is selected, in
which case the default is ON.
POLYMERS
ALME Used to introduce binary energetic parameters. The

default values are zero. The temperature-dependent
energy parameter is calculated as:
e
r = e 1 + ----2 + e 3 ln T
T
ALMC Used to introduce the size correction factor c. The
default value is 1.

or Non-polymer component (solvent) number or segment
type letter.
Table 7-2 lists values of c for ALMC, and e1, and e2 for ALME
BATCH
(e3 = 0) for homopolymer segment-solvent component pairs.

Table 7-2: ALM Parameters for Homopolymer Segment-Solvent Pairs
Segment Name Homopolymer Solvent ALM
Symbol
c e1 e2
Butadiene PBD Benzene 1.370 0.017 11.12
Carbon tetrachloride 2.506 0.081
Chloroform 1.117 0.008
Cyclohexane 1.479 0.031 4.851
Dichloromethane 2.528 0.140
Ethylbenzene 0.710 -0.180 67.10
n-Hexane 1.663 0.058
n-Nonane 0.310 -0.258 88.54
Ethylene LDPE n-Butane 1.119 -0.488 192.7
1-Butene 0.554 -0.613 214.6
n-Heptane 1.837 0.007 41.82
n-Hexane 0.856 -0.210 90.55
Isobutane 0.942 -0.302 127.2
Isobutylene 0.744 -0.575 209.2
n-Pentane 0.894 -0.103 68.69
Dimethylsiloxane PDMS Benzene 0.971 -0.039 30.21
Chloroform 1.086 0.078
Dichloromethane 0.986 0.113
n-Heptane 0.956 -0.041 86.27
n-Hexane 1.032 -0.015 13.29
n-Nonane 0.726 -0.011 8.890
n-Octane 2.022 -0.056 24.92
POLYMERS
n-Pentane 1.119 0.035

Toluene 1.022 -0.037 24.52
2,2,4-Trimethylpentane 1.986 0.048 -8.317
Isobutylene PIB Benzene 1.019 -0.116 56.28
Cyclohexane 0.903 0.032
n-Pentane 1.223 0.033 11.04

Table 7-2: ALM Parameters for Homopolymer Segment-Solvent Pairs (cont.)
Segment Name Homopolymer Solvent ALM
Symbol
c e1 e2
Methyl Methacrylate PMMA Toluene 1.559 0.066
i-Propylene i-PP Dichloromethane 0.229 0.160
Decene-1 PD Toluene 1.263 0.054
Dodecene-1 PDD Toluene 0.544 0.005
Heptene-1 PH Toluene 1.165 0.052
Octadecene-1 POD Toluene 0.387 0.006
p-Bromostyrene PpBrS Toluene 0.943 0.062
p-Chlorostyrene PpClS Toluene 1.172 0.065
p-Methylstyrene PpMS Toluene 1.187 0.050
Styrene PS Acetone 0.677 -0.001 27.48
Benzene 1.338 0.022 11.02
n-Butyl acetate 1.044 0.061
Carbon disulfide 0.990 -0.340 153.6
Carbon tetrachloride 1.053 -0.647 200.6
Chloroform 2.182 0.156 -22.52
Cyclohexane 0.711 0.141 -28.75
1,4-Dioxane 0.463 0.395 -120.9
Ethylbenzene 0.701 -0.062 26.38
Nitromethane 1.103 0.218
n-Nonane 0.760 -0.061 40.00
n-Propyl acetate 1.124 0.006 16.24
di-n-Propyl ether 0.816 0.053
Toluene 0.770 -0.135 45.70
1,2,4-Trimethylbenzene 0.809 -0.211 94.74
m-Xylene 2.272 0.071 -0.807
Tetrahydrofuran PTHF 1,4-Dioxane 1.283 0.052
Vinyl Acetate PVAC Benzene 1.441 0.010 16.36
POLYMERS
Vinyl acetate 1.861 0.071

Vinyl Chloride PVC 1,4-Dioxane 1.769 0.096
di-n-Propyl ether 2.231 0.088
Tetrahydrofuran 2.072 0.070
Toluene 2.648 0.095

Example 7-1: ALM with Polyvinylacetate and Benzene
This example uses the ALM model to calculate the flash and BVLE
for a binary mixture containing benzene and polyvinylacetate
BATCH
(PVAC). The van Krevelen group contribution method (VANKRE)

is used to predict the properties of the polymer segment, and the
properties of the polymer are calculated from the segment proper-
ties and the segment composition.
TITLE PROB=ALM
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
$
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PHASE VLS=2
MWAVG 2, 48200
$
THERMODYNAMIC DATA
METHOD SYSTEM = ALM
KVALUE
ALME 1,A, 0.010,16.36
ALMC A, 1.441
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 298.15, PRES =10.0, &
COMP = 1, 0.93166/2, 0.06834
$
UNIT OPERATION
FLASH UID=FL1
FEED F1
PRODUCT V=V1, L=L1
BUBBLE TEMP=298.15
BVLE UID=BVLE1
POLYMERS
EVAL COMP=1,2, TEMP(K)=298.15, &

XVALUES=0.95,1.0, POINTS=51, PLOT=GAMMA
END

UNIFAC Free Volume K-Value Method
The UNFV free volume data method is designed to model both
VLE and VLLE for polymer solutions. It should not be used for
non-polymer systems.
Typical Usage

SEGMENT DATA
STRUCTURE(VANKRE) A, 16(1),4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV

Note: When using the UNFV method for polymer systems, UNIFAC
structural groups must be defined for the polymer segments via a
STRUCTURE(UNIFAC) statement under SEGMENT DATA. For more
information on non-polymer components, see Section 1.9, UNIFAC
Structural Groups, of the SIMSCI Component and Thermodynamic Data
Input Manual.
Table 7-3: Attributes of the UNFV Method

Properties predicted by UNFV K-values
Liquid molar volume
van der Waals volume
Suggested application ranges Pressure up to 10 atm
Temperature 70 - 300 F
POLYMERS
Two liquid phase behavior Freewater decant not supported

VLLE supported
* Automatically supplied by PRO/II for library and petroleum components. Must be
supplied or estimated using the van Krevelen group contributions method for polymer
components.

METHOD Statement
METHOD SYSTEM(VLE or VLLE)=UNFV, PHI=IDEAL, {HENRY},
or
BATCH
METHOD KVALUE(VLE and/or LLE or VLLE)=UNFV, PHI=IDEAL,

{HENRY},
SYSTEM Selects a combination of compatible thermodynamic
property generators. The available option is:
UNFV When SYSTEM=UNFV is chosen, UNFV
K-values, IDEAL vapor enthalpies,
IDEAL liquid enthalpies, IDEAL liquid
densities, and IDEAL vapor densities are
the defaults.
UNFV method. The VLLE option automatically
selects both. See Section 2.1.7, Vapor Liquid-Liquid
Equilibrium Considerations, of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual for more
details on liquid-liquid equilibrium calculations.
and mixture vapor phase fugacity coefficients (fi). A
WAAL (see Section 2.4 of the SIMSCI Component and
Thermodynamic Data Input Manual) and HOCV (the
Hayden-OConnell method), TVIRIAL (the Trun-
cated Virial method), and the IDIMER method. See
Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-OConnell
Vapor Fugacity, Truncated Virial Vapor Fugacity, and
IDIMER Vapor Fugacity, of the SIMSCI Component
and Thermodynamic Data Input Manual for details on
the last three options. The default is PHI=IDEAL.
HENRY This option selects Henrys Law data (either user-sup-
plied or from databanks) to model dissolved gases in a
liquid solution. See Section 2.5.11, Henrys Law for
POLYMERS
Non-condensable Components, of the SIMSCI Compo-

nent and Thermodynamic Data Input Manual for fur-
ther details.

Mixing, of the SIMSCI Component and Thermodynamic Data Input
Manual for further information on using this option.

Example 7-2: UNIFAC with Polyisobutylene and Benzene
This example uses the UNIFAC free volume method to perform a
VLE flash calculation for a binary mixture containing benzene and
polyisobutylene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer segment,
and the UNIFAC-FV model (UNFV) is used as the thermodynamic
method for calculating activity coefficients of mixtures. You need to
provide information only on polymer molecular weight and seg-
ment structures for both the van Krevelen and UNIFAC group con-
tribution. The two methods are distinguished by different identifiers
VANKRE and UNIFAC, respectively, in the STRUCTURE statement.
TITLE PROB=UNFV
DIMENSION SI
PRINT INPUT=FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 400, PRES =10, &
COMP = 1, 0.9/2, 0.1
$
UNIT OPERATION
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 400, PRES = 10
POLYMERS
$
END
Flory-Huggins Liquid Activity Method

The Flory-Huggins liquid activity method is used to predict VLE
and VLLE phase behavior. This method does not support free water
decant.

The Flory-Huggins liquid activity method is generally useful for
mixtures of components that differ vastly in size, e.g., polymer solu-
tions. This method should be used only for modeling polymer sys-
BATCH
tems. See the PRO/II Reference Manual for additional information.
Typical Usage

SEGMENT DATA
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=FLORY
Table 7-4: Attributes of FLORY Methods

Properties predicted by FLORY methods K-values
Liquid molar volume
Solubility parameter
Two liquid phase behavior Freewater decant not
supported
VLLE supported
* Automatically supplied by PRO/II for library and petroleum components. Must be
supplied or estimated using the van Krevelen group contribution method for polymer
components.
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=FLORY, PHI=IDEAL,{HENRY},
or
METHOD KVALUE(VLE and/or LLE or VLLE)=FLORY,
PHI=IDEAL, {HENRY},
SYSTEM Selects a combination of compatible thermodynamic
POLYMERS
property generators. When SYSTEM=FLORY is cho-

sen, FLORY K-values, IDEAL vapor enthalpies,
IDEAL vapor densities, IDEAL liquid densities, and
IDEAL liquid enthalpies are the defaults.

Margules method. The VLLE option automatically
selects both. See Section 2.1.7, Vapor-Liquid-Liquid
Equilibrium Considerations, of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual for more
details on liquid-liquid equilibrium calculations.
and mixture vapor phase fugacity coefficients (i). A
WAAL (see Section 2.4 of the SIMSCI Component and
Thermodynamic Data Input Manual) and HOCV (the
Hayden-OConnell method), TVIRIAL (the Trun-
cated Virial method), and the IDIMER method. See
Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-OConnell
Vapor Fugacity, Truncated Virial Vapor Fugacity, and
IDIMER Vapor Fugacity, of the SIMSCI Component
and Thermodynamic Data Input Manual for details on
these last three options. The default is PHI=IDEAL.
HENRY This option selects Henrys Law data (either user-sup-
plied or from databanks) to model dissolved gases in a
liquid solution. See Section 2.5.11, Henrys Law for
Non-condensable Components, of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual for fur-
ther details.

Mixing, of the SIMSCI Component and Thermodynamic Data Input
Manual for further information on the use of this option.
K-Value Data (optional)

KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
CHI or FLORY , , a1, a2/
POYNTING Selects whether to apply the Poynting correction to
POLYMERS
fugacities of components in the liquid phase. The

default is OFF unless a PHI method is selected, in
which case the default is ON.

CHI or FLORY Allows entry of the binary temperature-dependent
parameters for the Flory-Huggins liquid activity coef-
ficient method.
BATCH
The parameter is calculated as:

a
= a 1 + ----2-
T
Missing parameters are estimated from solubility
parameters.
The binary parameters for polymer segment-solvent systems are given

in Table 7-5.
POLYMERS

Table 7-5: Binay Parameters for Homopolymer Segment-Solvent Pairs
Segment Name Homopolymer Solvent Flory-Huggins
Symbol
a1 a2
Butadiene PBD Benzene -0.115 124.3
Carbon Tetrachloride 0.101
Chloroform -0.004
Cyclohexane 0.109 41.23
Dichloromethane 0.295
Ethylbenzene -1.865 819.6
n-Hexane 0.419
n-Nonane -2.309 1124
Ethylene LDPE Butane -4.684 1892
1-Butene -4.609 1844
n-Heptane 0.087 507.4
n-Hexane -1.057 784.5
Isobutane -2.433 1168
Isobutylene -4.639 1849
n-Pentane -0.410 626.9
Dimethylsiloxane PDMS Benzene 0.151 143.5
Chloroform 0.646
Dichloromethane 0.878
n-Heptane -0.891 229.6
n-Hexane 0.345 13.57
n-Nonane 0.269 53.49
n-Octane -2.301 654.3
n-Pentane 0.356
Toluene -0.197 210.1
2,2,4- 0.535 -238.1
Trimethylpentane
Isobutylene PIB Benzene -0.884 474.1
POLYMERS
Cyclohexane 0.456
n-Pentane 0.683 30.58
Methyl PMMA Toluene 0.465
Methacrylate
i -Propylene i -PP Dichloromethane 2.182
Decene-1 PD Toluene 0.451

Table 7-5: Binay Parameters for Homopolymer Segment-Solvent Pairs
Segment Name Homopolymer Solvent Flory-Huggins
Symbol
a1 a2
BATCH
Dodecene-1 PDD Toluene 0.579

Heptene-1 PH Toluene 0.497
Octadecene-1 POD Toluene 0.802
p-Bromostyrene PpBrS Toluene 0.724
p-Chlorostyrene PpClS Toluene 0.649
p-Methylstyrene PpMS Toluene 0.463
Styrene PS Acetone 0.729 65.14
Benzene 0.187 52.13
n-Butyl acetate 0.820
Carbon disulfide 2.444 1134
Carbon tetrachloride -6.331 1960
Chloroform 1.792 -506.8
Cyclohexane 1.355 -185.9
1,4-Dioxane 3.120 -757.4
Ethylbenzene -0.185 223.8
Nitromethane 1.670
n-Nonane -0.166 476.7
n-Propyl acetate 0.274 118.9
Di-n-Propyl ether 0.869
Toluene 0.418
1,2,4- 0.323
Trimethylbenzene
m-Xylene 0.385 -26.35
Tetrahydrofuran PTHF 1,4-Dioxane 0.333
Vinyl Acetate PVAC Benzene 0.346 4.916
Vinyl acetate 0.261
Vinyl Chloride PVC 1,4-Dioxane 0.563
POLYMERS
Di-n-Propyl ether 0.759

Tetrahydrofuran 0.074
Toluene 0.390
Any parameters for homopolymer segment-solvent interactions

not given in Table 7-5 may be derived from Brandrup, J. and

Immergut, E.H., 1989. Polymer Handbook, 3rd Ed., Wiley-Inter-
science, New York.
Example 7-3: Flory-Huggins with Polystyrene and Acetone

This example uses the Flory-Huggins method to perform polymer
VLE flash calculations for a binary mixture containing acetone and
polystyrene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer component.
TITLE PROJ=FLORY-HUGGINS METHOD
DIMENSION SI
PRINT INPUT = FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
COMPONENT DATA
LIBID 1, ACETONE
POLYMER 2, POLYSTYRENE
PHASE LS = 2
MWAVG 2, 20000
$
THERMODYNAMIC DATA
METHOD SYSTEM = FLORY
KVALUE
CHI 1,A, 0.729, 65.14
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 400, PRES = 10., &
COMP(W) = 1, 0.9 / 2, 0.1
$
UNIT OP
FLASH UID = FL1, NAME = FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP=400., PRES=10
END
POLYMERS
SAFT and PHSC Equations of State

The statistical associating fluid theory equation of state (SAFT) and
the perturbed hard-sphere-chain equation of state (PHSC) are used
to predict VLE and VLLE phase behavior for mixtures containing
polymers. They predict K-values, enthalpies, entropies, and densi-
ties. Compared to commonly-used cubic equations of state, both of
the SAFT and PHSC equations of state are applicable to a wider

variety of systems, including small and medium molecules, as well
as large substances like polymers, and a wider range of fluid condi-
tions including vapor, liquids, and supercritical regions.
BATCH
The SAFT and PHSC equations of state are especially useful for
polymer solutions and polymer blends. They are also uniquely
applicable to high-pressure polymer-supercritical solvent systems.
They are characterized by a much higher accuracy of VLE and LLE
correlation than any of the existing thermodynamic models for
polymer systems.
Typical Usage

SEGMENT DATA
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=SAFT or PHSC
Table 7-6: Attributes of SAFT and PHSC Equations of State

Properties predicted by SAFT and PHSC EOS K-values, enthalpies, entropies,
vapor and liquid densities
Required pure component properties* Segment size, energy, and chain
length parameters
Non-polymer component size,
energy, and chain length
parameters
Two liquid phase behavior VLLE Supported
* All required pure parameters must be supplied.
POLYMERS

METHOD Statement
METHOD SYSTEM(VLE or VLLE)=SAFT or PHSC
or
METHOD KVALUE(VLE and/or LLE or VLLE)=SAFT or PHSC
SYSTEM When SYSTEM=SAFT or PHSC is chosen, K-values,
enthalpies, entropies, liquid densities, and vapor
densities are assumed.
K-Value Data (required)

KVALUE (VLE or LLE or VLLE)
EPSILON , value /
SIGMA , value /
RMW , value /
KIJ ,, value /
EPSILON Introduces the pure energy parameter .
SIGMA Introduces the pure size parameter .
RMW Introduces the pure chain length parameter. For non-
polymer components, it is the chain length r. For poly-
mer segments, it is the ratio of the chain length to the
molecular weight r/M.
KIJ Introduces the interaction binary parameters for seg-
ment-segment pairs, segment-solvent pairs, and non-
polymer component pairs. The default value is 0.
or Non-polymer component (solvent) number or segment
type letter.
Table 7-7 lists values of the SAFT and PHSC EOS parameters for
common solvents. Table 7-8 lists values of the SAFT and PHSC
EOS parameters for some homopolymer segments. Table 7-9 lists
values of the SAFT EOS binary parameter for some homopolymer
segment-solvent pairs.
Table 7-7: SAFT and PHSC EOS Parameters for Solvents
POLYMERS
Substance SAFT PHSC

r /kB(K) () r /kB(K) ()
Argon 1 150.9 3.370 1 143.2 3.757
Oxygen 1.235 126.7 3.480
Nitrogen 1 123.5 3.575 1.340 97.9 3.613
Carbon dioxide 1.417 216.1 3.171 2.859 153.7 2.774

Table 7-7: SAFT and PHSC EOS Parameters for Solvents (cont.)
Substance SAFT PHSC
r /kB(K) () r /kB(K) ()
BATCH
Normal Alkanes
Methane 1 190.3 3.700 1 182.1 4.126
Ethane 1.941 191.4 3.238 1.694 206.3 3.916
Propane 2.696 193.0 3.162 2.129 219.0 3.998
Butane 3.458 195.1 3.093 2.496 231.3 4.085
Pentane 4.091 200.0 3.088 3.149 226.0 3.995
Hexane 4.724 202.7 3.083 3.446 235.6 4.084
Heptane 5.391 204.6 3.067 4.255 225.9 3.947
Octane 6.045 206.0 3.063 5.055 219.6 3.850
Nonane 6.883 203.6 3.063 5.748 217.3 3.804
Decane 7.527 205.5 3.020 6.616 212.7 3.723
Undecane 7.057 215.4 3.754
Dodecane 8.921 205.9 3.032 7.712 214.8 3.733
Tridecane 7.986 218.3 3.794
Tetradecane 9.978 209.4 3.076 9.023 213.7 3.682
Pentadecane 9.851 211.3 3.662
Hexadecane 11.209 210.7 3.068 10.168 214.2 3.703
Heptadecane 10.834 213.7 3.680
Octadecane 11.110 216.5 3.698
Nonadecane 11.659 216.1 3.718
Eicosane 13.940 211.3 3.043 12.925 212.1 3.633
Branched and Cyclic Alkanes
Isobutane 2.397 226.2 4.155
Isopentane 2.777 236.7 4.182
Neopentane 2.526 233.7 4.351
2,2-Dimethylbutane 2.849 247.7 4.368
2,3-Dimethylbutane 2.998 247.1 4.278
POLYMERS
Cyclopentane 3.670 226.7 3.082 2.509 277.3 4.090

Methylcyclopentane 4.142 223.3 3.141 2.902 267.2 4.153
Ethylcyclopentane 4.578 229.0 3.186 3.277 269.4 4.181
Propylcyclopentane 5.037 232.2 3.223 3.823 262.7 4.130
Cyclohexane 3.970 236.4 3.165 2.723 286.7 4.215
Methylcyclohexane 3.954 248.4 3.325 2.968 283.7 4.336

Substance SAFT PHSC
r /kB(K) () r /kB(K) ()
Ethylcyclohexane 4.656 243.2 3.314 3.392 282.4 4.306
Propylcyclohexane 5.326 238.5 3.281 3.969 272.3 4.230
Butylcyclohexane 6.060 234.3 3.238 4.580 264.5 4.151
Alkenes
Ethylene 1.464 212.1 3.494 1.609 196.8 3.839
Propylene 2.223 213.9 3.325 2.029 221.9 3.951
1-Butene 3.162 202.5 3.138 2.677 218.3 3.882
trans-2-Butene 2.504 233.9 3.984
cis-2-Butene 2.530 235.7 3.941
1-Pentene 2.828 237.1 4.087
1-Hexene 4.508 204.7 3.125 3.395 234.5 4.042
trans-Decaline 3.160 333.8 4.657
Aromatics
Benzene 3.749 250.2 2.993 2.727 291.6 3.958
Toluene 4.373 245.3 3.025 3.138 287.0 4.019
Ethylbenzene 4.719 248.8 3.100 3.607 279.4 4.018
Propylbenzene 5.521 238.7 3.078 4.137 270.6 4.007
o-Xylene 3.620 285.4 3.998
m-Xylene 3.721 276.4 3.977
p-Xylene 3.455 287.9 4.104
Chlorobenzene 3.144 305.3 3.975
Fluorobenzene 3.012 276.9 3.883
Styrene 3.291 304.3 4.083
Acetates
Methyl acetate 3.804 224.8 3.338
Ethyl acetate 4.509 213.5 3.369
n-Propyl acetate 4.989 213.9 3.440
POLYMERS
i-Propyl acetate 4.779 210.6 3.484

n-Butyl acetate 5.413 216.3 3.514
i-Butyl acetate 5.574 207.4 3.461
t-Butyl acetate 4.485 220.2 3.743
n-Pentyl acetate 6.547 206.6 3.403
i-Pentyl acetate 5.568 220.5 3.628

Substance SAFT PHSC
r /kB(K) () r /kB(K) ()
BATCH
n-Hexyl acetate 6.720 212.9 3.514

Vinyl acetate 4.259 218.2 3.371
Ethers
Dimethyl ether 2.799 207.8 3.003 2.519 216.6 3.553
Diethyl ether 4.430 191.9 2.885 2.985 237.9 3.780
Ethylene oxide 2.242 277.5 3.390
1,3-Propylene oxide 2.381 295.4 3.729
Tetrahydrofuran 2.758 279.5 3.811
Ketones
Acetone 4.504 210.9 2.632 3.164 250.9 3.510
Methyl ethyl ketone 4.193 230.0 3.032 3.344 255.8 3.694
Diethyl ketone 4.644 230.4 3.014 3.931 245.4 3.684
2-Pentanone 4.041 241.2 3.661
2-Hexanone 5.151 224.5 3.506
Chlorinated Hydrocarbons
Methyl chloride 2.377 238.4 2.935 2.018 256.7 3.591
Dichloromethane 3.114 253.0 2.896 2.669 268.1 3.541
Carbon tetrachloride 2.507 301.7 4.187
Chloroform 2.878 268.1 3.726
Vinyl chloride 2.175 249.7 3.773
1,2-Dichlorethane 2.994 280.9 3.691
Table 7-8: SAFT and PHSC Equation-of-State Parameters for Homopolymer Segments
Segment Name Homopolymer SAFT PHSC
Name r /kB(K) () r /kB(K) ()
Ethylene HDPE 0.0510 216.2 3.043 0.04938 324.1 3.825
POLYMERS
Ethylene LDPE 0.05854 306.0 3.603

i-Propylene i-PP 0.02831 392.1 4.705
i-1-Butene i-PB 0.04024 353.2 4.120
4-Methyl-1-pentene PMP 0.02890 381.7 4.685
Styrene PS 0.0389 206.9 3.043 0.03834 385.4 3.899
o-Methyl styrene PoMS 0.03925 393.5 3.893

Table 7-8: SAFT and PHSC Equation-of-State Parameters for Homopolymer Segments (cont.)
Segment Name Homopolymer SAFT PHSC
Name r /kB(K) () r /kB(K) ()
Vinyl chloride PVC 0.03672 365.1 3.590
Ethylene glycol PEG 0.04778 316.6 3.532
Vinyl acetate PVAC 0.0394 275.1 3.043 0.05166 292.6 3.346
Methyl methacrylate PMMA 0.04222 373.5 3.608
i-Methyl methacrylate i-PMMA 0.05071 347.6 3.367
Butyl methacrylate PBMA 0.04764 323.4 3.604
Cyclohexyl methacrylate PCHMA 0.03742 379.3 3.856
Ethylene terephthalate PETP 0.04777 363.5 3.320
Carbonate PC 0.03885 393.0 3.707
Ether ether ketone PEEK 0.04424 375.0 3.429
Sulphone PSF 0.03720 425.7 3.721
Tetrafluoroethylene PTFE 0.02705 215.9 3.244
Isobutylene PIB 0.0484 220.6 3.043
Propylene PP 0.0361 110.9 3.043
Tetrahydrofuran PTHF 0.04277 327.6 3.833
POLYMERS

Table 7-9: SAFT EOS Binary Parameter kij for Homopolymer
Segment-Solvent Pairs
Segment Name Homopolymer Symbol Solvent SAFT kij
BATCH
Styrene PS Ethyl benzene 0.0259

Benzene 0.024
Cyclohexane 0.0447
Ethylene PE C6H14 0.0119
C7H16 0.0121
C8H18 0.0112
Isobutylene PIB C6H5CH3 0.0292
C6H14 0.0199
C6H12 0.0282
Propane 0.0324
Butane 0.0239
Pentane 0.0168
Propylene PP Diethyl ketone -0.0474
Hexane -0.0259
Vinyl acetate PVAC Benzene 0.0108
References
[1] S. H. Huang and M. Radosz, 1990, Equation of State for Small,
Large, Polydisperse, and Associating Molecules, Ind. Eng. Chem.
Res., 29:2284-2294.
[2] Y. Song, T. Hino, S. M. Lambert, and J. M. Prausnitz, 1996, Liq-
uid-Liquid Equilibria for Polymer Solutions and Blends, Including
Copolymers, Fluid Phase Equilibria, 117:69-76.
[3] C. S. Wu and Y. P. Chen, 1994, Calculation of Vapor-Liquid
Equilibria of Polymer Solution Using the SAFT Equation of State,
Fluid Phase Equilibria, 100:103-119.
Example 7-4: SAFT EOS with PVAC and Benzene

POLYMERS
This example uses the SAFT equation of state to perform a vapor-

liquid flash calculation. The system is a binary mixture of PVAC
and benzene.
TITLE=SAFT
DIMENSION SI
PRINT INPUT = ALL
$

SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1),9(1)
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PCOMPOSITION 2, 1.0(A)
MWAVG 2, 12000
PHASE VLS=2
THERMODYNAMIC DATA
METHOD SYSTEM = SAFT
KVALUE
EPSI 1, 250.2/A, 275.1
SIGM 1, 2.993/A, 3.043
RMW 1, 3.749/A, 0.0394
KIJ 1, A, 0.0108
STREAM DATA
PROPERTY STRM = F1, TEMP = 500, PRES = 300, *
COMP = 1, 0.95 /2, 0.05
UNIT OP
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 500, PRES = 300
END
Example 7-5: PHSC EOS with PVAC and Benzene

This example uses the PHSC equation of state to perform a liquid-
liquid equilibrium calculation. The system is a binary mixture of
PVAC and benzene. The binary parameter kij is set to zero.
TITLE PROJ=PHSC
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
COMPONENT DATA
POLYMERS
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PHASE VLS = 2
MWAVG 2, 48000
THERMODYNAMIC DATA
METHOD SYSTEM (VLLE) = PHSC
KVALUE
EPSI 1, 291.6/A, 292.6

SIGM 1, 3.958/A, 3.346
RMW 1, 2.727/A, 0.05166
STREAM DATA
BATCH
PROPERTY STRM = F1, TEMP = 298.15, PRES = 100., &

COMP = 1, 0.9996 / 2,0.0004
UNIT OP
FEED F1
PRODUCT V=V1, L=L1, W=W1
ISOT TEMP=298.15, PRES=100.
END
Selecting Polymer Thermodynamic Methods

To select the method and supply its parameters:
Click the Thermodynamic Data button, or select Input/Thermo-
dynamic Data from the menu bar, to display the Thermody-
namic Data dialog box (Figure 7-1).
Figure 7-1: Thermodynamic Data Dialog Box
Select Polymers in the Category list to display the five polymer

thermodynamic methods currently available in PRO/II. Select
the desired polymer method, and click Add > or double click on
the entry) to include the method in the simulation.
To modify data and to enter method parameters:
POLYMERS
Highlight the entry in the Defined Systems list, and click

to display the Modification dialog box (Figure 7-2).
Modify...

Figure 7-2: Modification Dialog Box
The method to calculate various properties can be changed in this

dialog box. Also, to enter the parameter data for the selected meth-
ods, click Enter Data... corresponding to the desired property. Nor-
mally, for the polymer methods, parameters are required only for
the K-value (VLE) method. The data supplied for this property are
used for all other properties that can be predicted for the selected
thermodynamic method.
The parameters are entered through a dialog box similar to that
shown in Figure 7-3. The available parameters will depend on the
property and the thermodynamic method category (equation of
state, liquid activity, etc.).
Figure 7-3: VLE K-Values Dialog Box
POLYMERS

To supply pure species parameters:
Click Enter Data... corresponding to the row. The Pure Species
Parameter dialog box (Figure 7-4) will contain the parameters
BATCH
applicable to the thermodynamic method.

Figure 7-4: Pure Species Parameters Dialog Box
For some thermodynamic methods (Flory, ALM, UNIFAC), PRO/II

supplies the default values; for others (PHSC, SAFT), the pure spe-
cies parameters are required information. Pure species parameters
can be supplied for non-polymer components and for segments.
Three types of binary interaction parameters can be supplied: (Non-
Polymer Component - Non-Polymer Component, Non-Polymer
Component - Segment, and Segment - Segment). To supply data for
the desired type:
Click Enter Data... to display the Binary Interaction Parameters
dialog box (Figure 7-5). Depending on the thermodynamic
method selected, the number of parameters will vary.
Figure 7-5: Binary Interaction Parameters Dialog Box
POLYMERS

Chapter 8
User-Added Polymer Reactor
The PRO/II features for handling polymers (e.g., van Krevelen

property prediction method, polymer moment attributes, polymer-
specific thermodynamic methods, and polymer flash) offer you the
ability to develop individual models for a wide variety of polymer
systems.
As outlined in previous chapters, polymers are formed through two
distinct atomistic mechanisms chain (or addition) polymerization
and step growth (or condensation) polymerization. However,
PRO/II also contains built-in CSTR and PFR units with the capabil-
ity of modeling a polymerization kinetics reactor operating under
the following, more specific conditions:
Free-radical homopolymerization to produce a linear
homopolymer
Free-radical copolymerization to produce a linear copolymer
Multi-site coordination complex polymerization to produce a
linear homopolymer
linear copolymer
Type I, Type II and Type III stepwise polymerization
POLYMERS

Ideal CSTR (steady-state, well mixed, constant volume reactor)

Ideal PFR (steady-state, plug flow, constant diameter reactor)
Single-phase kinetic reaction environment (effects of heat and
flow fields on the mass transport are not considered)

Bulk or solution polymerization.
This reactor unit has been modeled in PRO/II as user-added subrou-
tine US21 and is included as part of this release.
BATCH
Kinetic Rate Constants

The free-radical kinetic rate constants follow the Arrhenius form
given as:
E a V ( P P o )
k = A exp ------------------------------------------
RT
where A is the preexponential factor, Ea is the activation energy, V
is the volume coefficient, and Po is the reference pressure. These
four parameters are given sequentially as SUPPLE(i), SUPPLE(i+1),
SUPPLE(i+2), and SUPPLE(i+3) in the SUPPLE data for reaction step
i.
The stepwise kinetic rate constants follow the form given as:
+
k = ko + kc [ H ]
where ko is the intrinsic kinetic rate constant given by:

Ea
k o = A o exp --------o
RT
and kc is the acid catalyzed kinetic rate constant given by:

Ea
k c = A c exp --------c
RT
and the equilibrium rate constant is defined as:

H TS-
K = -------------------------
RT
and where Ao is the preexponential factor for the intrinsic reaction

rate, Eao is the activation energy for the intrinsic reaction rate, Ac is
the preexponential factor for the catalytic reaction rate, Eac is the
activation energy for the catalytic reaction rate, H is the enthalpy
change, and S is the entropy change. These six parameters are
POLYMERS
given sequentially as SUPPLE(i), SUPPLE(i+1), SUPPLE(i+2),

SUPPLE(i+3), SUPPLE(i+4), and SUPPLE(i+5) in the SUPPLE data for
reaction step i.
CSTR Mass and Energy Operating Equations

The ideal CSTR model is used to calculate steady state reactor per-
formance. The ideal CSTR assumption states that there are no tem-
8-2 User-Added Polymer Reactor

perature or concentration gradients in the reactor. Therefore, the
CSTR is operated at a single temperature with a uniform composi-
tion. Also, the reactor is characterized with a single residence time.
The CSTR mass and energy balances are written for a general
copolymerization reaction scheme below. Consequently, the gov-
erning mass and energy equations for the homopolymerization case
are a subset of the copolymerization case. Symbol definitions can
be found in the nomenclature. A general energy balance equation
for the copolymerization polymerization is given as:
dT dV
Vc ------- = Q f f c p T f Qc p T UA j ( T T j ) c p T -------
dt f dt
* *
+ ( H aa )Vk paa [ A ]P + ( H ba V )k pba [ A ]Q
+
* *
+ ( H ab )Vk pab [ A ]P + ( H bb )Vk pbb [ A ]Q
The CSTR is operated at steady state; therefore, the time-dependent

temperature and volume derivatives in this equation are zero. These
same derivatives are zero in the mass and moment equations that
follow. The heat of polymerization is generated from the polymer-
ization mechanisms such as those given in Steps (22), (23), (24),
and (25) of Table 9-1. The energy balance becomes:
0 = Q f f c p T f Qc p T UA j ( T Tj )
f
* *
+
* *
Mole balances are written for each chemical species according to

the general equation given by:
d[W]
V -------------- = Q f [ W f ] Q [ W ] VR W
dt
where [W] represents the concentration of each small molecule
chemical species present, [W] = {[A], [B], [S],}, and RW is the
POLYMERS
molar rate of production for species [W].

Moments are introduced below. The moment equations follow this
same hierarchy, and the moment balances describing moments of
identical order are written as:
d [ n, m ]
- = Q f [ n, m, f ] Q [ n, m ] VR
V -------------------
dt n, m

where [n,m] represents the moment of order n,m for the distribution
in question, and Rn,m is the molar rate of production for moment
[n,m]. For example, these moments could describe the variance in
BATCH
length of the live or growing polymer chains.
PFR Mass and Energy Operating Equations

The ideal PFR model is used to calculate steady state reactor perfor-
mance. The ideal PFR assumption states that there are no tempera-
ture or concentration gradients along the reactor radius. Therefore,
the PFR is characterized with gradients along the axial dimension
only.
The PFR mass and energy balances are written for a general copoly-
merization reaction scheme below. Consequently, the governing
mass and energy equations for the homopolymerization case are a
subset of the copolymerization case. Symbol definitions can be
found in the nomenclature. A general energy balance equation for
the copolymerization polymerization is given as:
dT U
c ------- = 4 ----- ( T T j )
dz Di
* *
+
* *
The PFR is operated at steady state; therefore, temperature, pres-

sure, and composition along the reactor length do not vary with
time. The heat of polymerization is generated from the polymeriza-
tion mechanisms such as those given in Steps (22), (23), (24), and
(25) of Table 9-1.
Mole balances are written for each chemical species according to
the general equation given by:
d[W]
u -------------- = QR W
dz
where [W] represents the concentration of each small molecule
POLYMERS
chemical species present, [W] = {[A], [B], [S],}, and RW is the

molar rate of production for species [W].
Moments are introduced below. The moment equations follow this
same hierarchy. The moment balances associated with moments of
the same order are written as:
d [ n, m ]
- = QR
u -------------------
dz n, m

where [n,m] represents the moment of order n,m for the distribution
in question, and Rn,m is the molar rate of production for moment
[n,m]. For example, these moments could describe the variance in
length of the live or growing polymer chains.
Heat Transfer Coefficient

In some reaction processes, the heat transfer coefficient is a critical
parameter in the operation. The reaction temperature, reaction pres-
sure, and polymer concentration will affect the heat transfer coeffi-
cient, perhaps to the point that polymer production is by the heat
transfer capabilities of the rector. The functional form used for the
overall heat transfer coefficient is:
1
U i = --------------------------------------------------------
1 A i ln ( r o / r i ) A i 1
---- + ------------------------- + ------ -----
hi 2 kL Ao ho
The overall heat transfer coefficient is specified in RPARM(5). Heat
transfer is then calculated from:
Qxfer = UATfm
Reactor Pressure Effects

In some cases, the kinetic reaction mechanisms are different in dif-
ferent pressure ranges. A change in pressure can change the reac-
tion mechanism, leading to a broadening in the molecular weight
distribution. The polymer broadening of the MWD function or dis-
persity is determined by the relative rates of the competing termina-
tion mechanisms. The termination mechanisms here are then
greatly influenced by the operating pressure. PRO/II supports pres-
sure coefficients for the intrinsic free-radical kinetic rate constants.
Reactor pressure may be a critical design variable.
For the CSTR, the pressure drop across the reactor is given in
RPARM(7). For the PFR, the pressure drop is calculated from a
mechanical energy balance parameterized with a Fanning friction
factor specified in RPARM(18). The mechanical energy balance takes
POLYMERS
the form:
2
dP u
------- = 4f ---------
dz 2D i

Population Balance
The rationale for introducing the population balance into polymer-
ization kinetics is that there exist an essentially infinite number of
BATCH
molecules of different length in a polymer sample. An essentially

infinite set of pseudocomponent balance equations must be solved
to obtain the individual polymer species concentration. To decrease
the computation time required to solve this large set of equations,
the method of moments is introduced to reduce the size of the equa-
tion set. For example, in reaction Step 22 of Table 9-1, the variable
n refers to the number of monomer units incorporated into the poly-
mer or degree of polymerization. The value of n can take on values
from 1 to very large numbers.
The population balance is very similar to the mass balance equa-
tions given above. From the kinetic mechanisms presented in
Table 9-1, a balance equation is written for the production and con-
sumption rates of a polymer molecule of length n. Samples of the
population balance can be seen in the review paper presented by
Ray (1972). An example population balance for the molar rate of
*
production of polymer species Pn, m, b, 1 is:
* *
R * = R As n-1, m, b + k paa [ A ] { P n-1, m, b, 1 P n, m, b, 1 }
P n-1, m, b, 1
* *
k pab [ B ] { P n, m, b, 1 } + k pba [ A ] { Q n-1, m, b, 1 }
*
* k tpaa P ( n + m )D n, m, b-1, 1
( A' 1, s + A' 0, s )P n, m, b, 1 +
k tpba Q * ( n + m )D n, m, b-1, 1

Reference
1. Ray, W. H. (1972), On the Mathematical Modeling of Poly-
merization Reactors, J. Macromol. Sci. Revs. Macromol.
Chem., C(8):1 56.
POLYMERS

Moment Expansions
Once the population balances have been generated, it remains to
solve these equations to predict the size and shape of the polymer
molecule. Rather than attempting to solve a very large set of cou-
pled population balance equations for individual polymer molecules
of length n, the method of moments is used to make the population
balance solution tractable. An example moment equation for the
molar rate of production of polymer moment k,l is:
k
k
R k, i = R As ( 1 ) + k paa [ A ] k, l
i i, l
i
k
k
k paa [ A ] [ k, l ] + k pba [ A ]
i i, l
i
l
l
( A' 1, s + A' 0, s ) [ k, l ] + l j
k + l, j
j
POLYMERS

POLYMERS
Chapter 9
User-Added Free Radical
Polymerization Model

systems.
homopolymer
linear homopolymer
POLYMERS
linear copolymer

BATCH

Polymerization via Free-Radical Kinetics

Chain polymerization can be accomplished via a number of chemis-
tries that include free-radical, ionic, and coordination catalysis.
Common to all these chemistries is the reactive center, which is at
the core of the chain polymerization process. The reactive center
can be identified as a free-radical center, an anionic or cationic spe-
cies, or the active center of a coordination catalyst. The reactions
associated with these polymerizations are very active and rapid.
In free-radical polymerization, the monomer is a small molecular
weight molecule (100 g/mol) that contains a double bond. When a
thermally active initiator molecule is added to the system, the initia-
tor fragments via thermal degradation into free-radical(s), and the
monomer double bond is then attacked by the free-radical. A bond
is created between the monomer and the initiator free-radical frag-
ment. This new radical is called the primary polymer radical. Poly-
mer is formed as more monomer is added to the primary polymer
radical. This process continues rapidly (0.1 second) until the poly-
mer radical is deactivated by a transfer or termination step. The
kinetic mechanisms are described later. Olefins are the most com-
mon monomers reacted through free-radical chemistry. Examples
are polyethylene, polypropylene, polyvinyl chloride, polybutadiene,
and polystyrene.
Free-Radical Kinetics Mechanisms

A free-radical bulk or solution polymerization process can be ade-
quately modeled by the kinetic mechanisms presented in Table 9-1.
Symbols A, I, P, etc., within the table indicate low molecular weight
POLYMERS
species that include monomer(s), a solvent, an initiator(s), a transfer

agent, and an inhibitor, live or growing polymer chain radicals that
contain the reactive center, and inactive or dead polymer chains in
which the reactive center is no longer present.
9-2 User-Added Free Radical Polymerization Model

Table 9-1: Free-Radical Polymerization Scheme
Decomposition and Initiation Reactions
* * f k
a da *
1 Decomposition of initiator A to form I a I a >2I a
* k *
* iaa
2 Initiation of monomer A by I a I a + A> P1, 0, 0, 1
* k *
* iab
3 Initiation of monomer B by I a I a + B> Q 0, 1, 0, 1
* * f k
b db *
4 Decomposition of initiator B to form I b I b > 2I b
* k *
* iba
5 Initiation of monomer A by I b I b + A> P1, 0, 0, 1
* k *
* ibb
6 Initiation of monomer B by I b I b + B> Q 0, 1, 0, 1
* * c dc
f k *
7 Decomposition of initiator C to form I c I c >2I c
* k *
* ica
8 Initiation of monomer A by I c I c + A> P1, 0, 0, 1
* k *
* icb
9 Initiation of monomer B by I c I c + B> Q 0, 1, 0, 1
k *
10 Spontaneous initiation of A to form A
* ra A>
spa
pa A (see note a at end of table) a
k *
11 Spontaneous initiation of B to form B
* rb B>
spb
pb B (see note a at end of table)
k *
12 Thermal decomposition of A to form R a
* pa A>
tha
pa R a (see note a at end of table)
k *
13 Thermal decomposition of B to form R b
* pb B>
thb
pb R b (see note a at end of table)
k *
* dOa
14 Initiation of monomer A by O2 to form R a O 2 + A>2R a
k *
* dOb
15 Initiation of monomer B by O2 to form R b O 2 + B>2R b
k *
*
POLYMERS
dpa
16 Peroxide decomposition to form R a RO 2 + A>2R a
k *
* dpb
17 Peroxide decomposition to form R b RO 2 + B>2R b
* k
* ra
18 Peroxide production by R a R a + O 2 >RO 2 + inert products
* k
* rb
19 Peroxide production by R b R b + O 2 >RO 2 + inert products

Table 9-1: Free-Radical Polymerization Scheme (cont.)
* k *
* raa
20 Reinitiation of monomer A by R a R a + A> P1, 0, 0, 1
BATCH
* k *
* rbb
21 Reinitiation of monomer B by R b R b + B> Q 0, 1, 0, 1
Propagation Reactions
* * k
paa *
22 Monomer A added to P P n, m, b, t + A> P n + 1, m, b, t
* * k
pba *
23 Monomer A added to Q Q n, m, b, t + A> P n + 1, m, b, t
* * k
pab *
24 Monomer B added to P P n, m, b, t + B> Q n, m + 1, b, t
* * k
pbb *
25 Monomer B added to Q Q n, m, b, t + B> Q n, m + 1 , b , t
Chain Transfer and Reinitiation Reactions
* * * k *
26 Transfer from P to solvent to form S
tsa
P n, m, b, t + S> D n, m, b, t + S
* * * k *
27 Transfer from Q to solvent to form S
tsb
Q n, m, b, t + S> D n, m, b, t + S
* k *
* rsa
28 Reinitiation of monomer A by S S + A> P1, 0, 0, 1
* k *
* rsb
29 Reinitiation of monomer B by S S + B> Q 0, 1, 0, 1
* * * k *
30 Transfer from P to modifier to form T
txa
P n, m, b, t + T x > D n, m, b, t + T x
* * * k *
31 Transfer from Q to solvent to form T
txb
Q n, m, b, t + T x > D n, m, b, t + T x
* k *
* rta
32 Reinitiation of monomer A by T T x + A> P1, 0, 0, 1
* k *
* rtb
33 Reinitiation of monomer B by T T x + B> Q 0, 1, 0, 1
* * * k *
34 Transfer from P to initiator A to form I a
tiaa
P n, m, b, t + I a > D n, m, b, t + I a
POLYMERS
* * * k *
35 Transfer from Q to initiator A to form I a
tiba
Q n, m, b, t + I a > D n, m , b, t + I a
* k *
* riaa
36 Reinitiation of monomer A by I a I a + A> P1, 0, 0, 1
* k *
* riab
37 Reinitiation of monomer B by I a I a + B> Q 0, 1, 0, 1

* * * k *
38 Transfer from P to initiator B to form I b
tiab
P n, m, b, t + I b > D n, m, b, t + I b
* * * k *
39 Transfer from Q to initiator B to form I b
tibb
Q n, m, b, t + I b > D n, m , b, t + I b
* k *
* riba
40 Reinitiation of monomer A by I b I b + A> P1, 0, 0, 1
* k *
* ribb
41 Reinitiation of monomer B by I b I b + B> Q 0, 1, 0, 1
* * * k *
42 Transfer from P to initiator C to form I c
tiac
P n, m, b, t + I c > D n, m, b, t + I c
* * * k *
43 Transfer from Q to initiator C to form I c
tibc
Q n, m, b, t + I c > D n, m, b, t + I c
* k *
* rica
44 Reinitiation of monomer A by I c I c + A> P1, 0, 0, 1
* k *
* ricb
45 Reinitiation of monomer B by I c I c + B> Q 0, 1, 0, 1
* * * k *
46 Transfer from P to monomer A to form A
maa
P n, m, b, t + A> D n, m, b, t + A
* * * k *
47 Transfer from Q to monomer A to form A
mba
Q n, m, b, t + A> D n, m , b, t + A
* k *
* rmaa
48 Reinitiation of monomer A by A A + A> P1, 0, 0, 2
* k *
* rmab
49 Reinitiation of monomer B by A A + B> Q 0, 1, 0, 2
* * * k *
50 Transfer from P to monomer B to form B
mab
P n, m, b, t + B> D n, m, b, t + B
* * * k *
51 Transfer from Q to monomer B to form B
mbb
Q n, m, b, t + B> D n, m , b, t + B
* k *
* rmba
52 Reinitiation of monomer A by B B + A> P1, 0, 0, 2
* k *
* rmbb
53 Reinitiation of monomer B by B B + B> Q 0, 1, 0, 2 POLYMERS
* * * k *
54 Transfer from polymer P to form P
tpaa
P n, m, b, t + D r, q, x, t > D n, m, b, t + P r, q, x + 1, t
with rate constant ktpaa
* * * k *
tpba
Q n, m, b, t + D r, q, x, t > D n, m, b, t + P r, q, x + 1, t
with rate constant ktpba

* * * k *
tpab
P n, m, b, t + D r, q, x, t > D n, m, b, t + Q r, q, x + 1, t
BATCH
with rate constant ktpab
* * * k *
tpbb
Q n, m, b, t + D r, q, x, t > D n, m, b, t + Q r, q, x + 1, t
with rate constant ktpbb
Termination Reactions
* * * * caa
k
58 Combination of P and P P n, m, b, s + P r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cba
k
59 Combination of Q and P Q n, m, b, s + P r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cab
k
60 Combination of P and Q P n, m, b, s + Q r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * cbb
k
61 Combination of Q and Q Q n, m, b, s + Q r, q, x, t > D n + r, m + q, b + x, max ( s, t )
* * * * k
daa D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
62 Disproportionation of P and P P n, m, b, s + P r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dba D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
63 Disproportionation of Q and P Q n, m, b, s + P r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dab D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
64 Disproportionation of P and Q P n, m, b, s + Q r, q, x, t > -------------------- + -------------------- + ----------------- + ------------------
2 2 2 2
* * * * k
dbb D n, m, b, s D n, m, b, 2 D r, q, x, t D r, q, x, 2
65 Disproportionation of Q and Q Q n, m, b, s + Q r, q, x, t > -------------------
- + -------------------- + ----------------- + ------------------
2 2 2 2
* * k
66 Termination of P by inhibitor
za
P n, m, b, t + I n > D n, m, b, t + Y
* * k
67 Termination of Q by inhibitor
zb
Q n, m, b, t + I n > D n, m, b, t + Y
*
+ R*
k
* * P n, m, b, 1 >D
bta
68 Beta-scission of P to form R n, m, b, t
*
+ R*
k
* * Q n, m, b, 1 >D
btb
69 Beta-scission of Q to form R n, m , b, t
POLYMERS
* k *
* rra
70 Reinitiation of monomer A by R R + A> P 1, 0, 0, 1
* k *
* rrb
71 Reinitiation of monomer B by R R + B> Q 0, 1, 0, 1
Side Reactions

*
+ H*
k
* * P n, m, b, t >D
tta
72 Thermal degradation of P to form H n, m, b, t
*
+ H*
k
* * Q n, m, b, t >D
ttb
73 Thermal degradation of Q to form H n, m, b , t
* k *
* kha
74 Reinitiation of monomer A by H H + A> P 1, 0, 1, 0
* k *
* khb
75 Reinitiation of monomer B by H H + B> Q 0, 1, 0, 1
* * * k
bnaa *
76 Terminal double bond from P and P P n, m, b, s + D r, q, x, 2 > P n + r, m + q, b + x + 1, 2
with rate constant kbnaa
* * * k
bnba *
with rate constant kbnba
* * * k bnab *
with rate constant kbnab
* * * k
bnbb *
with rate constant kbnbb
a. Values for and are currently fixed internally at 2.0 and 1.1, respectively. In future releases, and will accept
user-specified values.
Free-Radical Initiation
Some organic molecules contain unstable double bonds that can be
induced to undergo thermal disassociation to form free-radicals.
The radical center is an atom possessing an unpaired electron, and it
is this unpaired electron that attacks the double bond present in the
monomer. Because the parent organic initiator molecule is con-
sumed by the reaction, the term initiator rather than catalyst is
appropriate. Up to three initiators may be used in the free-radical
simulation. Each initiator is characterized by its molecular weight,
its decomposition kinetic rate data, and its recombination efficiency.
The activity of each initiator is set through its preexponential factor
POLYMERS
and activation energy kinetic constants. The initiator radical recom-

bination efficiency is also set through input. The mechanism for ini-
tiator decomposition is given in Table 9-1 through the following
reactions.
REACTION STEP(1): DECOMPOSITION OF INITIATOR A TO FORM IA* KDA
REACTION STEP(2): INITIATION OF MONOMER A BY IA* KIAA
REACTION STEP(3): INITIATION OF MONOMER B BY IA* KIAB

REACTION STEP(4): DECOMPOSITION OF INITIATOR B TO FORM IB* KDB
REACTION STEP(5): INITIATION OF MONOMER A BY IB* KIBA
REACTION STEP(6): INITIATION OF MONOMER B BY IB* KIBB
BATCH
REACTION STEP(7): DECOMPOSITION OF INITIATOR C TO FORM IC* KDC

REACTION STEP(8): INITIATION OF MONOMER A BY IC* KICA
REACTION STEP(9): INITIATION OF MONOMER B BY IC* KICB
REACTION STEP(10): SPONTANEOUS INITIATION OF A TO FORM A* KSPA
REACTION STEP(11): SPONTANEOUS INITIATION OF B TO FORM B* KSPB
REACTION STEP(12): THERMAL DECOMPOSITION OF A TO FORM RA* KTHA
REACTION STEP(13): THERMAL DECOMPOSITION OF B TO FORM RB* KTHB
REACTION STEP(14): INITIATION OF MONOMER A BY O2 TO FORM RA* KDOA
REACTION STEP(15): INITIATION OF MONOMER B BY O2 TO FORM RB* KDOB
REACTION STEP(16): RO2 DECOMPOSITION TO FORM RA* KDPA
REACTION STEP(17): RO2 DECOMPOSITION TO FORM RB* KDPB
REACTION STEP(18): PEROXIDE PRODUCTION BY RA* KRA
REACTION STEP(19): PEROXIDE PRODUCTION BY RB* KRB
Chain Propagation
The reactive center continues to add monomer to the growing or live
chain, thereby increasing the molecular weight of the polymer mol-
ecule. The mechanisms are given in the following steps:
REACTION STEP(22): PROPAGATION OF P* WITH MONOMER A KPAA
REACTION STEP(23): PROPAGATION OF Q* WITH MONOMER A KPBA
REACTION STEP(24): PROPAGATION OF P* WITH MONOMER KPAB
REACTION STEP(25): PROPAGATION OF Q* WITH MONOMER B KPBB
Chain Transfer
The reactive center is very active and, as such, can react with other
chemical species in the reaction mixture. The reactive center can be
transferred to other polymer, monomer, or solvent molecules. The
original live polymer chain is now inactive or dead, but the reactive
site remains active on some other molecule.
RNX STEP(26): TRANSFER FROM P* TO SOLVENT TO FORM S* KTSA
RNX STEP(27): TRANSFER FROM Q* TO SOLVENT TO FORM S* KTSB
POLYMERS
RNX STEP(30): TRANSFER FROM P* TO XFER AGENT TO FORM T* KTXA

RXN STEP(31): TRANSFER FROM Q* TO XFER AGENT TO FORM T* KTXB
RXN STEP(34): TRANSFER FROM P* TO INITIATOR A TO FORM IA** KTIAA
RXN STEP(35): TRANSFER FROM Q* TO INITIATOR A TO FORM IA** KTIBA
RXN STEP(38): TRANSFER FROM P* TO INITIATOR B TO FORM IB** KTIAB
RXN STEP(39): TRANSFER FROM Q* TO INITIATOR B TO FORM IB** KTIBB
RXN STEP(42): TRANSFER FROM P* TO INITIATOR C TO FORM IC** KTIAC
RXN STEP(43): TRANSFER FROM Q* TO INITIATOR C TO FORM IC** KTIBC

RXN STEP(46): TRANSFER FROM P* TO MONOMER A TO FORM A* KMAA
RXN STEP(47): TRANSFER FROM Q* TO MONOMER A TO FORM A* KMBA
RXN STEP(50): TRANSFER FROM P* TO MONOMER B TO FORM B* KMAB
RXN STEP(51): TRANSFER FROM Q* TO MONOMER B TO FORM B* KMBB
RXN STEP(54): TRANSFER FROM POLYMER P* TO FORM P* KTPAA
RXN STEP(55): TRANSFER FROM POLYMER Q* TO FORM P* KTPBA
RXN STEP(56): TRANSFER FROM POLYMER P* TO FORM Q* KTPAB
RXN STEP(57): TRANSFER FROM POLYMER Q* TO FORM Q* KTPBB
Free-Radical Recombination
These radicals recombine with the monomer to form new primary
polymer radicals, which then generate a new polymer. Some kinetic
models assume that the active radical recombines instantaneously
so that it is the radical formation step that is rate limiting. This
assumption is not made here. Kinetic data for each free-radical
resulting from a transfer reaction must be input in the order in
which the radical participates in the polymerization.
The following recombination steps are present in the kinetic
scheme:
RXN STEP(20): REINITIATION OF MONOMER A BY RA* KRAA
RXN STEP(21): REINITIATION OF MONOMER B BY RB* KRBB
RXN STEP(28): REINITIATION OF MONOMER A BY S* KRSA
RXN STEP(29): REINITIATION OF MONOMER B BY S* KRSB
RXN STEP(32): REINITIATION OF MONOMER A BY T* KRTA
RXN STEP(33): REINITIATION OF MONOMER B BY T* KRTB
RXN STEP(36): REINITIATION OF MONOMER A BY IA** KRIAA
RXN STEP(37): REINITIATION OF MONOMER B BY IA** KRIAB
RXN STEP(40): REINITIATION OF MONOMER A BY IB** KRIBA
RXN STEP(41): REINITIATION OF MONOMER B BY IB** KRIBB
RXN STEP(44): REINITIATION OF MONOMER A BY IC** KRICA
RXN STEP(45): REINITIATION OF MONOMER B BY IC** KRICB
RXN STEP(48): REINITIATION OF MONOMER A BY A* KRMAA
RXN STEP(49): REINITIATION OF MONOMER B BY A* KRMAB
RXN STEP(52): REINITIATION OF MONOMER A BY B* KRMBA
RXN STEP(53): REINITIATION OF MONOMER B BY B* KRMBB
POLYMERS
RXN STEP(70): REINITIATION OF MONOMER A BY R* KRRA

RXN STEP(71): REINITIATION OF MONOMER B BY R* KRRB
RXN STEP(74): REINITIATION OF MONOMER A BY H* KRHA
RXN STEP(75): REINITIATION OF MONOMER B BY H* KRHB

Chain Termination
An obvious termination method, whereby the polymerization pro-
cess is stopped, is for two kinetic chain ends to combine and pro-
BATCH
duce a dead chain. This process is called combination. A less

apparent termination mechanism is for one live chain to abstract an
alpha hydrogen with respect to the reactive center on a second live
chain. This process is called disproportionation and results in two
stable chains. Inhibitors are organic molecules that are added to
chemically react with the reactive center and to terminate the
growth mechanism, thereby lowering the polymer molecular
weight.
RXN STEP(58): TERMINATION BY COMBINATION OF P* AND P* KCAA
RXN STEP(59): TERMINATION BY COMBINATION OF Q* AND P* KCBA
RXN STEP(60): TERMINATION BY COMBINATION OF P* AND Q* KCAB
RXN STEP(61): TERMINATION BY COMBINATION OF Q* AND Q* KCBB
RXN STEP(62): TERMINATION BY DISPROPORTIONATION P* & P* KDAA
RXN STEP(63): TERMINATION BY DISPROPORTIONATION Q* & P* KDBA
RXN STEP(64): TERMINATION BY DISPROPORTIONATION P* & Q* KDAB
RXN STEP(65): TERMINATION BY DISPROPORTIONATION Q* & Q* KDBB
RXN STEP(66): TERMINATION OF P* BY INHIBITOR KZA
RXN STEP(67): TERMINATION OF Q* BY INHIBITOR KZB
RXN STEP(68): BETA-SCISSION OF P* CHAIN TO FORM R* KBTA
RXN STEP(69): BETA-SCISSION OF Q* CHAIN TO FORM R* KBTB
RXN STEP(72): THERMAL DEGRADATION OF P* TO FORM H* KTTA
RXN STEP(73): THERMAL DEGRADATION OF Q* TO FORM H* KTTB
RXN STEP(76): TERMINAL DOUBLE BOND FROM P* TO P* KBNAA
RXN STEP(77): TERMINAL DOUBLE BOND FROM Q* TO P* KBNBA
RXN STEP(78): TERMINAL DOUBLE BOND FROM P* TO Q* KBNAB
RXN STEP(79): TERMINAL DOUBLE BOND FROM Q* TO Q* KBNBB
Gel and Glass Effects

As the polymerization reactions proceed, the concentration of poly-
mer and size of the average polymer molecule increases. Accompa-
nying this increased monomer conversion is a substantial increase
in the viscosity of the reacting mixture. The increased viscosity
POLYMERS
introduces adverse effects of diffusion on the propagation and ter-

mination kinetic rate constants. The gel and glass effects have been
implemented for free-radical homopolymerization only.
The polymer product composition consists of mostly dead polymer
chains accompanied by a few live or kinetic chains; however, both
dead polymer and kinetic chains contribute to the viscosity of the
reacting solution. Increased solution viscosity leads to a substantial

decrease in the diffusion of kinetic chains such that the bimolecular
chain termination reactions presented in Reaction Steps (58)
through (65) of Table 9-1 are effectively stopped. At this point, the
reacting solution undergoes autoacceleration. This is the gel effect.
At low monomer conversion, intrinsic values of the propagation and
termination kinetic rate constants are used. As conversion increases
and solution viscosity increases (which is typical of the gel effect),
modified or hindered termination rate constants are obtained from
empirical or experimentally obtained functions. For the polymer
propagation step to continue, unreacted monomer must be trans-
ported to the reactive center. Eventually, the solution viscosity
increases acceptably to hinder the transport of the small molecule
monomer, and hence the propagation reactions listed in Reaction
Steps (22) through (25) of Table 9-1 is decreased. The polymeriza-
tion rate decreases and the glass effect is encountered.
The modification of the propagation and termination kinetic rate
constants to account for gel and glass effects is accomplished
through the use of empirical and semi-empirical correlation func-
tions. These correlation functions are important because they are
used to curtail the polymerization reaction at medium to high mono-
mer conversions.
In the input file for the user-added polymer CSTR, IPARM(10) is
used to specify the correlation for gel effect and glass effect. The
options shown in Table 9-2 are available.
Table 9-2: Gel Effect and Glass Effect Correlation
Input Value of IPARM(10) Gel Effect and Glass Effect Correlation
0 No Gel Effect or Glass Effect
1 Reference 1 for PMMA
3 Reference 3 for PS, PMMA
4 Reference 4 for PVA, PMMA
POLYMERS
References
1. Kumar, V.R. and S.K. Gupta, Optimal Parameter Estimation
for Methyl Methacrylate Polymerization, Polymer, 32:3233-
3243 (1991).
2. Baillagou, P.E. and D.S. Soong, Molecular Weight Distribu-
tion of Products of Free-Radical Nonisothermal Polymerization

with Gel Effect Simulation for Polymerization of Poly(Methyl
Methacrylate, Chem. Eng. Sci., 40:87-104 (1985).
3. Jaisinghani, J. and W.H. Ray, On the Dynamic Behavior of a
BATCH
Class of Homogeneous Continuous Stirred Tank Polymeriza-

tion Reactors, Chem. Eng. Sci., 32:811-825 (1977).
4. Hamer, J.W., T.A. Akramov, and W.H. Ray, The Dynamic
Behaviour of Continuous Polymerization Reactors - II, Chem.
Eng. Sci., 36:1897-1914 (1981).
5. Schmidt, A.D. and W.H. Ray, The Dynamic Behaviour of
Continuous Polymerization Reactors - I, Chem. Eng. Sci.,
36:1401-1410 (1981).
Required Data for the Polymer Reactor Unit

The polymer reactor unit requires the following data:
Component data
Components Monomer(s), polymer, solvent, initiator
(required), transfer agent (optional), inhibitor (optional)
van Krevelen structural group data (required)
Average MW and MW distribution of polymer
Names of moments (will be calculated by US21)
Thermodynamics data (required)
ALM (recommended), Flory-Huggins, UNIFAC Free Volume,
SAFT, or PHSC
Unit data (US21)
Heat of polymerization (required)
CSTR volume or PFR diameter and length (required)
Temperature (required for isothermal reactor) or temperature
estimate (for non-isothermal reactor)
POLYMERS
Jacket temperature and heat transfer area (for non-isothermal

reactor)
Overall heat transfer coefficient (for non-isothermal reactor)
CSTR pressure drop or PFR friction factor
Free-radical kinetic data

Free-radical initiator efficiency factor
Required free-radical reactions (initiation, propagation, termi-
nation)
Optional reactions.
User-Added Subroutines
An outline of the keyword input syntax for user-added unit opera-
tions such as the polymer reactor unit US21 is given below. IPARM
and RPARM arrays are used to pass information on the component
and reactor configuration from the keyword file to the user-added
subroutine. The SUPPLE array is used to supply kinetics data.
Note: Details of user-added subroutines may be found in the

PRO/II Data Transfer System and User-Added Subroutines Users
Guide.
Communicating with PRO/II for Free-Radical Kinetics

The keyword headers that contain the descriptions of IPARM,
RPARM, and SUPPLE are quite lengthy. These headers are given here
and do not appear in the example problems:
US21 UID=uid {NAME=text}
IPARM integer, (up to 21 values)
RPARM real no, (up to 18 values)
SUPPLEMENTAL i,Ri/Ri+1//j,Rj/Rj+1 (up to 316 values)
Integer IPARM Data:

$ IPARM( 1) = REACTOR Type REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 2) = REACTOR THERMAL CONDITION FLAG REQ
$ = 0 FOR NONISOTHERMAL REACTOR
$ = 1 FOR ISOTHERMAL REACTOR
$ IPARM( 3) = KINETICS TYPE REQ
$ = 1 FOR FREE RADICAL HOMOPOLYMERIZATION
$ = 2 FOR FREE RADICAL COPOLYMERIZATION
POLYMERS
$ = 3 FOR TYPE I STEP GROWTH POLYMERIZATION
$ = 4 FOR TYPE II STEP GROWTH POLYMERIZATION
$ = 5 FOR TYPE III STEP GROWTH POLYMERIZATION
$ IPARM( 4) = NUMBER OF REVERSIBLE POLYMERIZATION REACTION STEPS N/A
$ IPARM( 5) = NUMBER OF IRREVERSIBLE POLYMERIZATION REACTION STEPS REQ
$ IPARM( 6) = NUMBER OF RINGS N/A
$ IPARM( 7) = BASIS FOR KINETIC RATE CONSTANTS REQ
$ = 1 FOR VOLUME BASIS
$ = 2 FOR WEIGHT BASIS
$ IPARM( 8) = REVERSIBLE KINETICS FLAG N/A
$ = 1 FORWARD KINETIC RATE CONSTANTS ONLY

$ = 2 INCLUDE REVERSE KINETIC RATE CONSTANTS
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANTS FLAG REQ
$ = 0 NO COEFFICIENTS
$ = 1 INCLUDE COEFFICIENTS
BATCH
$ IPARM(10) = FLAG FOR TYPE OF GEL AND GLASS EFFECT OPT

$ CORRELATION ( DEFAULT = 0 )
$ IPARM(11) = POLYMER COMPONENT
$ IPARM(12) = MONOMER A COMPONENT
$ IPARM(13) = MONOMER B COMPONENT (OR 0)
$ IPARM(14) = SOLVENT COMPONENT (OR 0)
$ IPARM(15) = INITIATOR A COMPONENT
$ IPARM(16) = INITIATOR B COMPONENT (OR 0)
$ IPARM(17) = INITIATOR C COMPONENT (OR 0)
$ IPARM(18) = TRANSFER AGENT COMPONENT (OR 0)
$ IPARM(19) = INHIBITOR COMPONENT (OR 0)
$ IPARM(20) = O2 COMPONENT (OR 0)
$ IPARM(21) = PEROXIDE COMPONENT (OR 0)
$
$
Real RPARM Data:

$ RPARM( 1) = HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2) = CSTR REACTOR VOLUME, LITER
$ RPARM( 3) = JACKET TEMPERATURE, K, FOR NONISOTHERMAL REACTOR
$ RPARM( 4) = JACKET AREA, M2, FOR NONISOTHERMAL REACTOR
$ RPARM( 5) = OVERALL HTC, J/SEC/M2/K, FOR NONISOTHERMAL REACTOR
$ RPARM( 6) = REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE FOR ISOTHERMAL CSTR/PFR
$ = TEMPERATURE ESTIMATE FOR NONISOTHERMAL CSTR
$ RPARM( 7) = CSTR REACTOR PRESSURE DROP (kPa) ; DEFAULT=0.0
$ RPARM( 8) = DECOMPOSITION EFFICIENCY FACTOR FOR 1ST INITIATOR
$ RPARM( 9) = DECOMPOSITION EFFICIENCY FACTOR FOR 2ND INITIATOR (OR 0)
$ RPARM(10) = DECOMPOSITION EFFICIENCY FACTOR FOR 3RD INITIATOR (OR 0)
$ RPARM(11) = PFR LENGTH, M
$ RPARM(12) = PFR DIAMETER, CM
$ RPARM(13) = FEED STREAM LIVE CHAIN A FRACTION
$ RPARM(14) = FEED STREAM LIVE CHAIN B FRACTION
$ RPARM(15) = HEAT OF POLYMERIZATION (Hba) , J/GMOL
$ RPARM(16) = HEAT OF POLYMERIZATION (Hab) , J/GMOL
$ RPARM(17) = HEAT OF POLYMERIZATION (Hbb) , J/GMOL
$ RPARM(18) = PFR FANNING FRICTION FACTOR
$
Real SUPPLE Data:

REACTION STEP( 1): DECOMPOSITION OF INITIATOR A TO FORM IA* KDA
$ SUPPLE( 1) = PREEXPONENTIAL FACTOR (SEC-1)
$ SUPPLE( 2) = ACTIVATION ENERGY (J/GMOL)
POLYMERS
$ SUPPLE( 3) = VOLUME COEFFICIENT (J/GMOL/ATM)

$ SUPPLE( 4) = REFERENCE PRESSURE (ATM)
$
REACTION STEP( 2): INITIATION OF MONOMER A BY IA* KIAA
$ SUPPLE( 5) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$
REACTION STEP( 3): INITIATION OF MONOMER B BY IA* KIAB

$
REACTION STEP( 4): DECOMPOSITION OF INITIATOR B TO FORM IB* KDB
$
REACTION STEP( 5): INITIATION OF MONOMER A BY IB* KIBA
$
REACTION STEP( 6): INITIATION OF MONOMER B BY IB* KIBB
$
REACTION STEP( 7): DECOMPOSITION OF INITIATOR C TO FORM IC* KDC
$
REACTION STEP( 8): INITIATION OF MONOMER A BY IC* KICA
$
REACTION STEP( 9): INITIATION OF MONOMER B BY IC* KICB
$
REACTION STEP(10): SPONTANEOUS INITIATION OF A TO FORM A* KSPA
$
REACTION STEP(11): SPONTANEOUS INITIATION OF B TO FORM B* KSPB
POLYMERS

$
REACTION STEP(12): THERMAL DECOMPOSITION OF A TO FORM RA* KTHA

$
REACTION STEP(13): THERMAL DECOMPOSITION OF B TO FORM RB* KTHB
BATCH

$
REACTION STEP(14): INITIATION OF MONOMER A BY O2 TO FORM RA* KDOA
$
REACTION STEP(15): INITIATION OF MONOMER B BY O2 TO FORM RB* KDOB
$
REACTION STEP(16): RO2 DECOMPOSITION TO FORM RA* KDPA
$
REACTION STEP(17): RO2 DECOMPOSITION TO FORM RB* KDPB
$
REACTION STEP(18): PEROXIDE PRODUCTION BY RA* KRA
$
REACTION STEP(19): PEROXIDE PRODUCTION BY RB* KRB
$
REACTION STEP(20): REINITIATION OF MONOMER A BY RA* KRAA
POLYMERS

$
REACTION STEP(21): REINITIATION OF MONOMER B BY RB*
$
REACTION STEP(22): PROPAGATION OF P* WITH MONOMER A KPAA

$
REACTION STEP(23): PROPAGATION OF Q* WITH MONOMER A KPBA
$
REACTION STEP(24): PROPAGATION OF P* WITH MONOMER B KPAB
$
REACTION STEP(25): PROPAGATION OF Q* WITH MONOMER B KPBB
$ SUPPLE(100) = REFERENCE PRESSURE (ATM)
$
REACTION STEP(26): TRANSFER FROM P* TO SOLVENT TO FORM S* KTSA
$ SUPPLE(101) = PREEXPONENTIAL FACTOR (L/GMOL/SEC)
$ SUPPLE(102) = ACTIVATION ENERGY (J/GMOL)
$ SUPPLE(103) = VOLUME COEFFICIENT (J/GMOL/ATM)
$
REACTION STEP(27): TRANSFER FROM Q* TO SOLVENT TO FORM S* KTSB
$
REACTION STEP(28): REINITIATION OF MONOMER A BY S* KRSA
$
REACTION STEP(29): REINITIATION OF MONOMER B BY S* KRSB
$
REACTION STEP(30): TRANSFER FROM P* TO XFER AGENT TO FORM T* KTXA
POLYMERS

$
REACTION STEP(31): TRANSFER FROM Q* TO XFER AGENT TO FORM T* KTXB
$
REACTION STEP(32): REINITIATION OF MONOMER A BY T* KRTA

BATCH
$
REACTION STEP(33): REINITIATION OF MONOMER B BY T* KRTB
$
REACTION STEP(34): TRANSFER FROM P* TO INITIATOR A TO FORM IA** KTIAA
$
REACTION STEP(35): TRANSFER FROM Q* TO INITIATOR A TO FORM IA** KTIBA
$
REACTION STEP(36): REINITIATION OF MONOMER A BY IA** KRIAA
$
REACTION STEP(37): REINITIATION OF MONOMER B BY IA** KRIAB
$
REACTION STEP(38): TRANSFER FROM P* TO INITIATOR B TO FORM IB** KTIAB
$
REACTION STEP(39): TRANSFER FROM Q* TO INITIATOR B TO FORM IB** KTIBB
$
POLYMERS
REACTION STEP(40): REINITIATION OF MONOMER A BY IB** KRIBA

$
REACTION STEP(41): REINITIATION OF MONOMER B BY IB** KRIBB

$
REACTION STEP(42): TRANSFER FROM P* TO INITIATOR C TO FORM IC** KTIAC
$
REACTION STEP(43): TRANSFER FROM Q* TO INITIATOR C TO FORM IC** KTIBC
$
REACTION STEP(44): REINITIATION OF MONOMER A BY IC** KRICA
$
REACTION STEP(45): REINITIATION OF MONOMER B BY IC** KRICB
$
REACTION STEP(46): TRANSFER FROM P* TO MONOMER A TO FORM A* KMAA
$
REACTION STEP(47): TRANSFER FROM Q* TO MONOMER A TO FORM A* KMBA
$
REACTION STEP(48): REINITIATION OF MONOMER A BY A* KRMAA
$
REACTION STEP(49): REINITIATION OF MONOMER B BY A* KRMAB
POLYMERS
$
REACTION STEP(50): TRANSFER FROM P* TO MONOMER B TO FORM B* KMAB
$

REACTION STEP(51): TRANSFER FROM Q* TO MONOMER B TO FORM B* KMBB
BATCH

$
REACTION STEP(52): REINITIATION OF MONOMER A BY B* KRMBA
$
REACTION STEP(53): REINITIATION OF MONOMER B BY B* KRMBB
$
REACTION STEP(54): TRANSFER FROM POLYMER P* TO FORM P* KTPAA
$
REACTION STEP(55): TRANSFER FROM POLYMER Q* TO FORM P* KTPBA
$
REACTION STEP(56): TRANSFER FROM POLYMER P* TO FORM Q* KTPAB
$
REACTION STEP(57): TRANSFER FROM POLYMER Q* TO FORM Q* KTPBB
$
REACTION STEP(58): TERMINATION BY COMBINATION OF P* AND P* KCAA
POLYMERS
$
REACTION STEP(59): TERMINATION BY COMBINATION OF Q* AND P* KCBA
$

REACTION STEP(60): TERMINATION BY COMBINATION OF P* AND Q* KCAB
$
REACTION STEP(61): TERMINATION BY COMBINATION OF Q* AND Q* KCBB
$
REACTION STEP(62): TERMINATION BY DISPROPORTIONATION P* AND P* KDAA
$
REACTION STEP(63): TERMINATION BY DISPROPORTIONATION Q* AND P* KDBA
$
REACTION STEP(64): TERMINATION BY DISPROPORTIONATION P* AND Q* KDAB
$
REACTION STEP(65): TERMINATION BY DISPROPORTIONATION Q* AND Q* KDBB
$
REACTION STEP(66): TERMINATION OF P* BY INHIBITOR KZA
$
REACTION STEP(67): TERMINATION OF Q* BY INHIBITOR KZB
$
POLYMERS
REACTION STEP(68): BETA-SCISSION OF P* CHAIN TO FORM R* KBTA

$ SUPPLE(269) = PREEXPONENTIAL FACTOR (SEC-1)
$
REACTION STEP(69): BETA-SCISSION OF Q* CHAIN TO FORM R* KBTB

$
REACTION STEP(70): REINITIATION OF MONOMER A BY R* KRRA
BATCH

$
REACTION STEP(71): REINITIATION OF MONOMER B BY R* KRRB
$
REACTION STEP(72): THERMAL DEGRADATION OF P* TO FORM H* KTTA
$
REACTION STEP(73): THERMAL DEGRADATION OF Q* TO FORM H* KTTB
$
REACTION STEP(74): REINITIATION OF MONOMER A BY H* KRHA
$
REACTION STEP(75): REINITIATION OF MONOMER B BY H* KRHB
$
REACTION STEP(76): TERMINAL DOUBLE BOND FROM P* TO P* KBNAA
$
REACTION STEP(77): TERMINAL DOUBLE BOND FROM Q* TO P* KBNBA
POLYMERS

$
REACTION STEP(78): TERMINAL DOUBLE BOND FROM P* TO Q* KBNAB
$
REACTION STEP(79): TERMINAL DOUBLE BOND FROM Q* TO Q* KBNBB

$
Using Reactor Unit US21 to Model Free-Radical Systems

Polymer systems that may be modeled with unit US21 are solution
and bulk polymerizations:
Homopolymer: Polystyrene (PS), Polymethymethacrylate
(PMMA)
Copolymer: Polymethymethacrylate Polyvinylacetate
(PMMA-PVAC), HDPE , LDPE.
Example 9-1: Free-Radical Homopolymerization in a CSTR

In this example problem, the built-in polymer CSTR unit US21 is
used to model the bulk polymerization of styrene to polystyrene
with n-butyl benzoate as the initiator. If solution polymerization is
of interest, this problem can be modified easily to add the input
component ethylbenzene to the reactor feed for use as a solvent. It
is important to note:
1. Van Krevelen structural groups (from Appendix A) are given
for the polymer polystyrene. The FILL=VANKREVELEN keyword
is used to specify that van Krevelen prediction methods be used
for polymer properties.
2. Advanced Lattice Model (ALM) binary interaction parameters
for the ethyl benzene-polystyrene pair are taken from Table 7-2
and are provided with the ALME and ALMC statements.
3. The kinetics type and the molecular weight distribution are pro-
vided on the ATTRIBUTE statement. The distribution given will
result in the creation of 19 polymer pseudocomponents
(1MW500 through 1MW500000).
4. Names are defined for the first three moments of molecular
weight distribution (MMWD) on the ATTRIBUTE statement.
These moments will be calculated by the US21 unit, but will be
printed in the stream report output only if the names are given
POLYMERS
on this statement.
5. The polymer CSTR is modeled as two US21 units in series.
6. Data on the reaction component types involved in the reaction
and the isothermal reactor operating conditions are provided on
the IPARM and RPARM statements.

7. Data for the free-radical kinetics for the polymerization reac-
tion are taken from Table 9-5 and are provided in the US21
units via the SUPPLE data statement.
BATCH
8. The product from the second reactor unit is flashed isother-

mally in unit FLASHDEV to remove volatiles.
9. A stream calculator, WFE, is used to model a wiped film evap-
orator. This unit separates the polymer component into product
stream POLYMER.The heat of polymerization (-Haa) for the
POLYMERS

Table 9-3: Kinetic Rate Parameters for Styrene Polymerization
Reaction Rate Constant Activation Energy
Step ko Prefactor Prefactor Units (J/gmol)
1 KDA 1.5800e15 1/sec 128870

2 KIAA 1.0500e7 m3/kmol/sec 29540
3
22 KPAA 1.0500e7 m /kmol/sec 29540
3
58 KCAA 1.2600e7 m /kmol/sec 7030
Note: The heat of polymerization (-Haa) for styrene is 69900 joule/gmol, and the initiator
efficiency is 0.7.
Polystyrene CSTR Input File

TITLE PROJ=POLYSTYRENE, PROB=PSTYR, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, STYR, FILL=VANKREVELEN
STRUCTURE A, 144(1), 4(1)
COMPONENT DATA
LIBID 2,STYRENE/3,EBZN/4,BOBZ , BANK=SIMSCI
POLYMER 1,PSTYR
MWAVG 1, 25000
PHASE VLS=1
ATTRIBUTE COMP=1, *
KINETICS=FR, MWD= 500, 1000, 3000, 5000, 7000,*
10000, 15000, 20000, 25000, 30000,*
50000, 60000, 70000, 80000,100000,*
200000,300000,400000,500000, *
MMWD= MU0, MU1, MU2
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,3, -.062, 26.38
ALMC A, 0.701
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=363, PRES(ATM)=1.0, *
COMP(WT, KG/MIN)=0.0/10.4188/0.0/4,0.150
UNIT OPERATION
MIXER UID=MIXER_1
FEED FEED_0,RECYCLE
PRODUCT M=FEED_1
OPERATION PRES(ATM)=1.75
POLYMERS
US21 UID=REACTOR_1, NAME=1st PS REACTOR
FEED FEED_1
PROD PROD_1
$------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE REQ
$ = 1 FOR CSTR
$ = 2 FOR PFR

$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
BATCH
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = HIGH PRESSURE KINETIC RATE CONSTANT REQ
$ = 0 NO PRESSURE COEFFICIENTS
$ = 1 INCLUDE PRESSURE COEFFICIENTS
$ IPARM(10) = GEL AND GLASS EFFECT CORRELATION OPT
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 1,1,1,0,0, 0,1,0,1,3, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ RPARM( 2) = CSTR VOLUME, LITER
$ RPARM( 3) = NONISOTHERMAL REACTOR JACKET TEMPERATURE, K
$ RPARM( 4) = NONISOTHERMAL CSTR JACKET AREA, M2
$ RPARM( 5) = NONISOTHERMAL REACTOR OVERALL HTC, J/SEC/M2/K
$ = OPERATING TEMPERATURE OF ISOTHERMAL CSTR/PFR
$ RPARM( 7) = CSTR PRESSURE DROP (kPa), (DEFAULT=0.0)
$ RPARM( 8) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 1ST INITIATOR
$ FOR 2ND INITIATOR (OR 0)
$ RPARM(10) = DECOMPOSITION EFFICIENCY FACTOR
$ FOR 3RD INITIATOR (OR 0)
POLYMERS

$------------------------------------------------------------
RPARM 69900., 200.0, 0.0, 0.0, 0.0, 350.0, 0.0, &
0.7, 0.0, 0.0, 0.0, 0.0, 1.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$------------------------------------------------------------
SUPPLE 1,1.580E15/ 128870/ 0.0/ 0.0/ 1.050E07/ 29540/ 0.0/ 0.0/ &

0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 1.050E07/ 29540/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 1.26E09/ 7030/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0
$------------------------------------------------------------
US21 UID=REACTOR_2, NAME=2nd PS REACTOR
FEED PROD_1
PROD PROD_2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
POLYMERS

$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A

$ IPARM( 8) = N/A
BATCH

$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 1,1,1,0,0, 0,1,0,1,3, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ FOR 1ST INITIATOR
$------------------------------------------------------------
RPARM 69900., 250.0, 0.0, 0.0, 0.0, 350.0, 0.0, &
POLYMERS
0.5, 0.0, 0.0, 0.0, 0.0, 1.0, 0.0, &

0.0, 0.0, 0.0, 0.0
$------------------------------------------------------------
SUPPLE 1,1.580E15/ 128870/0.0/0.0/ 1.050E07/ 29540/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &

0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 1.050E07/ 29540/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 1.26E09/ 7030/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/0.0/ 0.0
$ FIRST STAGE - FLASH DEVOLATILIZER
FLASH UID=FLASHDEV
FEED PROD_2
PRODUCT V=MON_RECYCLE, L=POLYMER_MELT
ISOT TEMP(K)=440, PRES(ATM)=1
$ SECOND STAGE - SPLITTER
SPLITTER UID=SPLITTER_1
FEED MON_RECYCLE
PRODUCT L=RECYCLE, V=WASTE
SPEC STREAM=RECYCLE, RATE, RATIO, &
STREAM=MON_RECYCLE, RATE, VALUE=0.40
$ THIRD STAGE - WIPED FILM EVAPORATOR
STCALC UID=WFE
FEED POLYMER_MELT
OVHD V=OFF-GAS, TEMP(K)=440, PRES(ATM)=1
FOVHD 1,4,1.0
POLYMERS
BTMS M=POLYMER, TEMP(K)=440, PRES(ATM)=1

FBTMS 5,24,1.0
$
Example 9-2: Free-Radical Homopolymerization in a PFR

In this example problem, the built-in polymer PFR unit US21 is
used to model the solution polymerization of ethylene to polyethyl-

ene with benzoyl peroxide as the initiator. If bulk polymerization is
of interest, this problem can be modified easily to remove the input
solvent component ethyl acetate from the reactor feed. It is impor-
BATCH
tant to note:
for the polymer polystyrene, and the FILL=VANKREVELEN key-
word is used to specify that van Krevelen prediction methods
be used for polymer properties.
(1MW10 through 1MW500000).
on this statement.
4. The polymer PFR is initially heated by the reactor jacket up to
an initiation temperature, after which the PFR is cooled by the
reactor jacket.
and the nonisothermal reactor operating conditions are pro-
vided on the IPARM and RPARM statements.
7. The product from the reactor unit is flashed isothermally in unit
PRODUCT to remove volatiles.
Table 9-4: Kinetic Rate Parameters for Ethylene Polymerization
Step Rate Prefactor Prefactor Activation Volume Reference
Constant ko Units Energy Coefficient Pressure
(J/gmol) (J/gmol/atm) (atm)
1 KDA 2.5000e14 1/sec 125520 0.6276 1.0
2 KIAA 2.5000e14 m3/kmol/sec 125520 0.6276 1.0
POLYMERS
4 KDB 5.9300e18 1/sec 195210 - -

5 KIBA 5.9300e18 m3/kmol/sec 195210 - -
22 KPAA 1.2500e8 m3/kmol/sec 31045 -2.0920 1301.
26 KTSA 2.7500e7 m3/kmol/sec 43390 -2.1171 0.0
28 KRSA 2.7500e7 m3/kmol/sec 43390 -2.1171 0.0
Note: The heat of polymerization (-Haa) for ethylene is 89540 joule/gmol, and the initiator efficiency
is 0.98.

Table 9-4: Kinetic Rate Parameters for Ethylene Polymerization (cont.)
Step Rate Prefactor Prefactor Activation Volume Reference
Constant ko Units Energy Coefficient Pressure
(J/gmol) (J/gmol/atm) (atm)
46 KMAA 1.2500e5 m3/kmol/sec 45355 - -
3
48 KRMAA 1.2500e5 m /kmol/sec 45355 - -
3
54 KTPAA 1.2400e6 m /kmol/sec 30335 - -
58 KCAA 2.5000e9 m3/kmol/sec 4184 - -
3
62 KDAA 2.5000e9 m /kmol/sec 4184 - -
3
68 KBTA 6.0700e7 m /kmol/sec 45185 - -
Note: The heat of polymerization (-Haa) for ethylene is 89540 joule/gmol, and the initiator efficiency
is 0.98.
Polyethylene PFR Input File

TITLE PROJ=POLYMER, PROB=HDPE, USER=RAS, DATE=12/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, PE1, FILL=VANKREVELEN
STRUCTURE A, 4(2)
COMPONENT DATA
LIBID 2,ETHYLENE/3,EOAC/4,BZPOX
POLYMER 1,HDPE
MWAVG 1, 16000
PHASE VLS = 1
ENTHALPY(L,K,J/G,WT) CORRELATION= 1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY(L,K,G/LIT,WT) CORRELATION=1,DATA=1,400,200,524/*
2,400,200,524/*
3,400,200,524/*
4,400,200,524
ATTRIBUTE COMP=1, KINE = FR, MWD = 10,50,100,300,500,1000,*
2000,3000,5000,7000,8000,9000,*
10000,15000,20000,30000,50000,70000,*
100000,300000,500000*
MMWD = psi0, psi1, psi2
THERMO DATA
METHOD SYSTEM=FLORY
POLYMERS
KVALUE
CHI A,3 ,0.5
STREAM DATA
PROP STRM=Feed_1, TEMP(K)=363.15, PRES(ATM)=2400.0, *
COMP(WT,KG/MIN)=0.0/1244.7/12.45/1.12
UNIT OPERATION
US21 UID=REACTOR_1, NAME=HDPE PFReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------

$ = 1 FOR CSTR
$ = 2 FOR PFR
BATCH

$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 2,0,1,0,0, 0,1,0,1,0, 1,2,0,3,4, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ FOR 1ST INITIATOR
POLYMERS


$-------------------------------------------------------------
RPARM 89540., 0.0, 393.15, 1.0, 1255.2, 363.15, 0.0, &
0.98, 0.0, 0.0, 1097.28, 5.25018, 1.0, 0.0, &
0.0, 0.0, 0.0, 0.015
$-------------------------------------------------------------
$ SUPPLE( ) KINETIC DATA
$-------------------------------------------------------------
SUPPLE 1,2.50E14/125520/0.6276/1.0/ 2.50E14/125520/ 0.6276/ 1.0/ &
0.0/ 0.0/ 0.0/0.0/ 5.93E18/195210/ 0.0/ 0.0/ &
5.93E18/195210/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E08/ 31045/-2.0920/1301.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.75E07/ 43390/-2.1171/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.75E07/ 43390/-2.1171/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E06/ 45355/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.25E06/ 45355/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 1.24E06/ 30335/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.50E09/ 4184/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 2.50E09/ 4184/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 6.07E07/ 45185/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/0.0
POLYMERS
FLASH UID=PRODUCT
FEED PROD_1
PRODUCT V=VAPOR, L=POLYMER_MELT
Example 9-3: Free-Radical Copolymerization in a CSTR

used to model the solution copolymerization of methyl methacry-

late (MMAC) and vinyl acetate (VAC) with n-butyl benzoate as the
initiator. If bulk polymerization is of interest, this problem can be
modified easily to remove the input solvent component benzene
BATCH
from the reactor feed. It is important to note:

for the polymer polystyrene, and the FILL=VANK keyword is
used to specify that van Krevelen prediction methods be used
(1MW500 through 1MW1000000).
3. The solution density and heat capacity have been set with the
ENTHALPY and DENSITY CORRELATION statements.
on this statement.
units via the SUPPLE data statement.The product is flashed iso-
thermally in unit PRODUCT to remove volatiles.
Table 9-5: Rate Parameters for MMAC and VAC Polymerization
Step Rate Prefactor ko Prefactor Activation Energy
Constant Units (J/gmol)
1 KDA 4.5000e14 1/sec 125000
2 KIAA 4.5000e14 m3/kmol/sec 125000
3 KIAB 4.5000e14 m3/kmol/sec 125000
22 KPAA 3.2070e6 m3/kmol/sec 24200
23 KPBA 2.1030e8 m3/kmol/sec 18000
POLYMERS
24 KPAB 1.2330e5 m3/kmol/sec 24200

25 KPBB 6.3080e6 m3/kmol/sec 24200
26 KTSA 8.6600e1 m3/kmol/sec 24200
27 KTSB 1.5140e3 m3/kmol/sec 18000
Note: The heats of polymerization for this system (- Haa), (-Hba), (-Hab), and
(-Hbb) are 54000, 54000, 86000, and 86000 joule/gmol, respectively; the initiator
efficiency is 1.0.

Table 9-5: Rate Parameters for MMAC and VAC Polymerization (cont.)
Step Rate Prefactor ko Prefactor Activation Energy
Constant Units (J/gmol)
28 KRSA 8.6600e1 m3/kmol/sec 24200
3
29 KRSB 1.5140e3 m /kmol/sec 18000
3
30 KTXA 2.0850e3 m /kmol/sec 24200
3
31 KTXB 4.1630e5 m /kmol/sec 24200
32 KRTA 2.0850e3 m3/kmol/sec 24200
33 KRTB 4.1630e5 m3/kmol/sec 24200
46 KMAA 3.2080e1 m3/kmol/sec 24200
47 KMBA 5.2570e4 m3/kmol/sec 18000
48 KRMAA 3.2080e1 m3/kmol/sec 24200
3
50 KRMAB 1.2340e0 m /kmol/sec 24200
3
51 KMAB 1.2340e0 m /kmol/sec 24200
52 KMBB 1.5770e3 m3/kmol/sec 18000
53 KRMBA 5.2570e4 m3/kmol/sec 18000
54 KRMBB 1.5770e3 m3/kmol/sec 18000
58 KCAA 4.2090e14 m3/kmol/sec 26900
61 KCBB 1.6100e9 m3/kmol/sec 4000
66 KZA 2.2000e0 m3/kmol/sec 0
67 KKZB 1.1300e5 m3/kmol/sec 0
(-Hbb) are 54000, 54000, 86000, and 86000 joule/gmol, respectively; the initiator
efficiency is 1.0.
Polymethylmethacrylate - Polyvinylacetate CSTR Input File

TITLE PROJ=COPOLYMER, PROB=PMMAC-VAC, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
STRUCTURE A, 252(1),4(1)/B, 250(1),4(1)
POLYMERS
COMPONENT DATA
LIBID 2,MMAC/3,VACT/4,BNZN/5,BOBZ, BANK=SIMSCI
POLYMER 1,PMMAC-VAC
MWAVG 1, 54300
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676/*

5,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, DATA= *
1, 400, 200, 1000/*
2, 400, 200, 1000/*
BATCH
3, 400, 200, 1000/*

4, 400, 200, 1000/*
5, 400, 200, 1000
ATTRIBUTE COMP=1,KINE = FR, *
MWD = 500,700,1000,3000,5000,7000,10000,*
30000,40000,50000,60000,80000,*
100000,300000,500000,700000,*
1000000,*
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4, 0.5/ B,4, 0.5
STREAM DATA
PROP STRM=S1, TEMP(K)=333.13, PRES(ATM)=5.0, *
COMP(WT,KG/MIN)=0.0/0.30/1.5/0.60/0.003
UNIT OPERATION
US21 UID=REACTOR, NAME=1st PMMAC-VAC CSTReactor
FEED S1
PROD S2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ ( DEFAULT = 0 )
$------------------------------------------------------------
POLYMERS
IPARM 1,1,2,0,0, 0,1,0,1,0, 1,2,3,4,5, 0,0,0,0,0,0

$------------------------------------------------------------

$------------------------------------------------------------
$ FOR 1ST INITIATOR
$-----------------------------------------------------------------
RPARM 54000., 1000.0, 333.15, 4.6, 60., 333.15, 405.3, &
1.0, 0.0, 0.0, 0.0, 0.0, 1.0, 1.0, &
54000., 86000., 86000.
$-----------------------------------------------------------------
$-----------------------------------------------------------------
SUPPLE 1,4.500E14/ 125000/ 0.0/ 0.0/ 4.500E14/ 125000/ 0.0/ 0.0/ &
4.500E14/ 125000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.207E06/ 24200/ 0.0/ 0.0/ &
2.103E08/ 18000/ 0.0/ 0.0/ 1.233E05/ 24200/ 0.0/ 0.0/ &
6.308E06/ 24200/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
POLYMERS
4.163E05/ 24200/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &

4.163E05/ 24200/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
5.257E04/ 18000/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
1.234E00/ 24200/ 0.0/ 0.0/ 1.234E00/ 24200/ 0.0/ 0.0/ &

1.577E03/ 18000/ 0.0/ 0.0/ 5.257E04/ 18000/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 4.209E11/ 26900/ 0.0/ 0.0/ &
BATCH
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &

1.610E09/ 4000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 2.2/ 0.0/ 0.0/ 0.0/ &
1.130E05/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0
FLASH UID=PRODUCT
FEED S2
Example 9-4: Free-Radical Copolymerization in a PFR

used to model the solution copolymerization of methyl methacry-
late and vinyl acetate with n-butyl benzoate as the initiator. If bulk
polymerization is of interest, this problem can be modified easily to
remove the input solvent component benzene from the reactor feed.
It is important to note:
(1MW500 through 1MW1000000).
POLYMERS
on this statement.

7. The product is flashed isothermally in unit PRODUCT to remove
volatiles.
Polymethylmethacrylate - Polyvinylacetate PFR Input File
TITLE PROJ=COPOLYMER, PROB=PMMAC-VAC, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
STRUCTURE A, 5(1),252(1),9(1)/B, 5(1),252(1),9(1)
COMPONENT DATA
LIBID 2,MMAC/3,VACT/4,BNZN/5,BOBZ, BANK=SIMSCI
POLYMER 1,PMMAC-VAC
MWAVG 1, 63950
PHASE VLS=1
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676/*
5,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, DATA= *
1, 400, 200, 1000/*
2, 400, 200, 1000/*
3, 400, 200, 1000/*
4, 400, 200, 1000/*
5, 400, 200, 1000
ATTRIBUTE COMP=1,KINE = FR, *
MWD = 500,1000,2000,3000,5000,7000,*
10000,30000,50000,60000,70000,*
80000,100000,300000,500000,*
700000,1000000,*
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4, 0.5/ B,4, 0.5
STREAM DATA
PROP STRM=S1, TEMP(K)=358.15, PRES(ATM)=5.0, *
COMP(WT,KG/MIN)=0.0/0.60/1.5/0.60/0.010
UNIT OPERATION
POLYMERS
US21 UID=REACTOR, NAME=1st PMMAC-VAC PFReactor
FEED S1
PROD S2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR

$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
BATCH
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ ( DEFAULT = 0 )
$------------------------------------------------------------
IPARM 2,0,2,0,0, 0,1,0,1,0, 1,2,3,4,5, 0,0,0,0,0,0
$------------------------------------------------------------
$------------------------------------------------------------
$ FOR 1ST INITIATOR
POLYMERS

$------------------------------------------------------------
RPARM 54000., 0.0, 358.15, 0.0, 60., 0.0, 0.0, &
1.0, 0.0, 0.0, 500.0, 5.0, 1.0, 1.0, &
54000., 86000., 86000., 0.0045
$------------------------------------------------------------

$------------------------------------------------------------
SUPPLE 1,4.500E14/ 125000/ 0.0/ 0.0/ 4.500E14/ 125000/ 0.0/ 0.0/ &
4.500E14/ 125000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.207E06/ 24200/ 0.0/ 0.0/ &
2.103E08/ 18000/ 0.0/ 0.0/ 1.233E05/ 24200/ 0.0/ 0.0/ &
6.308E06/ 24200/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 8.660E01/ 24200/ 0.0/ 0.0/ &
1.514E03/ 18000/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 2.085E03/ 24200/ 0.0/ 0.0/ &
4.163E05/ 24200/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
5.257E04/ 18000/ 0.0/ 0.0/ 3.208E01/ 24200/ 0.0/ 0.0/ &
1.234E00/ 24200/ 0.0/ 0.0/ 1.234E00/ 24200/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 5.257E04/ 18000/ 0.0/ 0.0/ &
1.577E03/ 18000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 4.209E11/ 26900/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
1.610E09/ 4000/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 2.2/ 0.0/ 0.0/ 0.0/ &
1.130E05/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ 0.0/ &
0.0/ 0.0/ 0.0/ 0.0
FLASH UID=PRODUCT
FEED S2
POLYMERS

POLYMERS
Chapter 10
User-Added Coordination Complex
Polymerization Model

systems.
homopolymer
linear homopolymer
POLYMERS
linear copolymer

BATCH

Polymerization via Coordination Complex Kinetics

A large percentage of commercial olefin and diene polymerization
reactions fit in the category of stereospecific, coordination complex,
or coordination polymerization. Here, active polymerization centers
(sites) are generated from a special initiator called a catalyst. The
catalyst may be a single compound or a system of compounds
whose synergistic effects lead to the creation of robust and highly
selective active polymerization centers.
There are two distinct paths to generate polymer with a given
molecular architecture. The first path is to use cascade reactor tech-
nology where polymer of a given characteristic is produced in an
upstream reactor. Polymerization with a different catalyst is then
performed in a downstream reactor to produce the desired charac-
teristics of the polymer product. It is now becoming possible to
combine two or more catalysts in a single reactor to obtain similar
results. The multi-site catalyst has been engineered to perform both
polymerizations in a single reactor.
Ultimately, bulk physiochemical properties, and consequently, the
final application of the product, are determined by the polymer
microstructure formed by the catalyst complex during the polymer-
ization process. Distributions such as the molecular weight distri-
bution, MWD, the chemical composition distribution (CCD), and
the long chain branching distribution (LCB) determine mechanical
and rheological properties. These properties must meet a wide
range of performance and processing criteria, and it is then desir-
able to tailor-make more molecularly homogeneous homopolymers
and copolymers.
POLYMERS
The catalyst performs two major functions in coordination polymer-

ization reactions, the first function is to provide a more accessible
energetic pathway from monomer reactant(s) to polymer product,
and secondly, the catalyst complex controls molecular architecture
via molecular selectivity. Selectivity here includes chemoselectiv-
ity, regioselectivity, and stereoselectivity. Of primary importance in
olefin polymerization is stereoselectivity where the head to tail
10-2 User-Added Coordination Complex Polymerization Model

bonding facilitated by the catalyst structure influences the tacticity,
and hence, the bulk properties of the polymer product. The degree
of stereoregulation is controlled by the degree of exposure of the
active site, the more exposure to the reacting medium, the less ste-
reospecific the reaction that will occur.
Numerous catalysts and catalyst systems have been developed that
promote highly reactive and specific polymerization. The catalysts
available to facilitate a coordination polymerization include organic
catalysts, the newly developed metallocene catalysts, and the classi-
cal Ziegler-Natta catalysts. Although soluble (homogeneous)
Ziegler-Natta catalysts are used in industry, currently the most
widely used coordination polymerization is via a supported (hete-
reogeneous) Ziegler-Natta catalyst polymerization. The Ziegler-
Natta catalyst consists of a mixture of a
transition metal compound (normally a halide) from groups IV
to VIII of the periodic table, and
an organometallic compound (hydrides, alkyls, or aryls) of a
metal from groups I to III of the periodic table.
By convention the transition metal compound is labeled the catalyst
and includes compounds such as TiCl3, TiCl4, TiCl2, Ti(OR)4,
TiI4, (C2H5)2,TiCl2, VCl4, VoCl3, vacetyl-acetonate, ZrCl4, Zr
tetrabenzyl, and (C2H5)2ZrCl2. The organometallic compound is
labeled the cocatalyst and includes compounds such as Al(C2H5)3,
Al(i-C4H9)3, Al(n-C6H13)3, Al(C2H5)2Cl, Al(i-C4H9)2Cl,
Al(C2H5)Cl2, and Al2(C2H5)3Cl.
Traditional Ziegler-Natta catalysts consist of multiple active cata-
lytic sites, all of which are chemically related, but each site can have
its own reactivity ratio for monomer and/or comonomer. This type
of catalyst can lead to a broad and unacceptable MWD function.
A well-known example is the coordination polymerization of
polypropylene that is carried out in the presence of a stereoselective
catalyst. This Ziegler-Natta catalyst-cocatalyst system is a mixture
POLYMERS
of TiCl3 and AlEt3 supported on an inert silica substrate. It is pos-

sible for propylene to form in various ways leading to either atactic,
syndiotactic, or isotactic configurations.
The single site metallocene or constrained geometry catalyst (CGC)
is a relatively new system to tailor make polymer molecules. The
ligand environment around the central metal atom is optimized to
generate polymer with certain characteristics. The selectivity of the

catalyst is given by the steric hindrance of the substituted ligands
with respect to bulk monomer. An added feature of the CGC is the
large area for reinsertion of polymer moieties into a polymer chain.
BATCH
This allows for the addition of branches. The advantages of the

metallocene catalyst system are:
a variety of comonomer choices,
a narrow to broad MWD,
an ability to control crystallinity,
incorporation of long chain branching, and
a clean reaction environment with high catalyst efficiency.
Coordination Complex Kinetic Mechanisms

A homogeneous coordination complex (Ziegler-Natta) bulk or solu-
tion polymerization process can be adequately modeled by the
kinetic mechanisms presented in Table 10-1. Symbols A, B, S, C, Z,
H, P, etc., within the table indicates low molecular weight species
that include monomer(s), a solvent, catalyst(s), cocatalyst(s), a
transfer agent, live or growing polymer chains that contain the
active center, and inactive or dead polymer chains in which the
active center is no longer present.
Table 10-1: Multi-site Homogeneous Coordination Complex Polymerization Scheme

Activation and Initiation Reactions
1 activation of site j on catalyst
k
C + Z C ,
act, j
j j
2 monomer A initiation at site j on catalyst
k
C , + A P
ica, j
j 1,0, j
POLYMERS
3 monomer B initiation at site j on catalyst
k
C , + B Q
icb, j
j 0,1, j

Propagation Reactions
4 monomer A propagation at site j on catalyst
k
P +AP
paa,j
n,m,j n+1,m,j
5 monomer B propagation at site j on catalyst
k
P +BQ
pab,j
n,m,j n,m+1,j
6 monomer A propagation at site j on catalyst
k
Q + A P
pba, j
n,m, j n+1,m, j
7 monomer B propagation at site j on catalyst
k
Q + BQ
pbb, j
n,m, j n,m+1, j
Chain Transfer Reactions
8 transfer to monomer A at site j on catalyst
k
P +AD +P
maa,j
n,m, j n,m 1,0,j
9 transfer to monomer B at site j on catalyst
k
P + BD +Q
mab, j
n,m, j n,m 0,1, j
10 transfer to monomer A at site j on catalyst
k
Q + P
mba, j
+ A D
n,m, j n,m 1,0, j
11 transfer to monomer B at site j on catalyst
k
Q + BD +Q
mbb,j
n,m,j n,m 0,1,j
POLYMERS
12 transfer to solvent at site j on catalyst
k
P +S D +P
tsa, j
n,m, j n,m 1,0, j

13 transfer to solvent at site j on catalyst
k
Q +Q
tsb, j
BATCH
+ S D
n,m, j n,m 0,1, j
14 transfer to modifier at site j on catalyst
k
P (a)
+H
tha,j
D +P
n,m,j n,m 1,0,j
15 transfer to modifier at site j on catalyst
k
Q +H (b) thb, j
D +Q
n,m, j n,m 0,1, j
16 transfer to cocatalyst at site j on catalyst
k
P D +C,
tac, j
+ Z
n,m, j n,m j
17 transfer to cocatalyst at site j on catalyst
k
Q +C,
tbc, j
+ Z D
n,m, j n,m j
18 spontaneous transfer at site j on catalyst
k
P + C,
za, j
D
n,m, j n,m j
19 spontaneous transfer at site j on catalyst
k
Q + C,
zb, j
D
n, m, j n, m j
Termination Reactions
20 spontaneous termination of site j on catalyst
k
C , D
spt, j
j j
POLYMERS
21 termination of activated site j on catalyst

k
P + D
tda, j
D
n, m, j n, m j
22 termination of activated site j on catalyst
k
Q + D
tdb, j
D
n, m , j n, m j

Catalyst Initiation
Mechanisms 1, 2, and 3 from Table 10-1 describe the catalyst initia-
tion steps, the catalyst being activated by the cocatalyst, required to
produce active polymerization sites. If from a practical standpoint,
the catalyst is preactivated before entering the reactor, then set the
pre-exponential factors of these mechanism to a large value, such as
five orders of magnitude greater than the polymerization steps 4
through 7.
RXN STEP (1): CATALYST SITE ACTIVATION BY COCATALYST KACT
RXN STEP (2): INITIATION OF MONOMER A BY C* KICA
RXN STEP (3): INITIATION OF MONOMER B BY C* KICB
Chain Propagation at Catalyst Site

The insertion reaction at the active center continues to add mono-
mer to the growing or live chain, thereby increasing the molecular
weight of the polymer molecule. The insertion mechanisms are
modeled with the following steps:
RXN STEP (4): PROPAGATION OF P* WITH MONOMER A KPAA
RXN STEP (5): PROPAGATION OF Q* WITH MONOMER A KPBA
RXN STEP (6): PROPAGATION OF P* WITH MONOMER B KPAB
RXN STEP (7): PROPAGATION OF Q* WITH MONOMER B KPBB
Chain Transfer at Catalyst Site

The active center is very reactive and, as such, can react with other
chemical species in the reaction mixture. The reactive center can be
transferred to monomer, solvent, or modifier molecules. The origi-
nal live polymer chain is now inactive or dead, but the reactive site
remains active on a different molecule.
RXN STEP (8): TRANSFER FROM P* TO MONOMER A TO FORM RP* KPAB
RXN STEP (9): TRANSFER FROM Q* TO MONOMER A TO FORM RP* KPBA
RXN STEP (10): TRANSFER FROM P* TO MONOMER B TO FORM RQ*KMAB
RXN STEP (11): TRANSFER FROM Q* TO MONOMER B TO FORM RQ*KMBB
RXN STEP (12): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTSA
RXN STEP (13): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTSB
RXN STEP (14): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTHA
RXN STEP (15): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTHB
RXN STEP (16): TRANSFER FROM P* TO COCATALYST TO FORM C* KTAC
POLYMERS
RXN STEP (17): TRANSFER FROM Q* TO COCATALYST TO FORM C* KTBC
Chain Termination
The current model presented in Table 10-1 provides for spontane-
ous and thermal termination of the active site. Once a site has been
market dead through these reactions, the mechanism does not allow
the site to be regenerated, rather that site is carried around as dead
catalyst.

RXN STEP (18): SPONTANEOUS TERMINATION OF P* TO FORM C* KZA
RXN STEP (19): SPONTANEOUS TERMINATION OF Q* TO FORM C* KZB
RXN STEP (20): SPONTANEOUS TERMINATION OF C* TO FORM D* KSPT
RXN STEP (21): THERMAL DEGRADATION OF P* TO FORM D* KTDA
BATCH
RXN STEP (22): THERMAL DEGRADATION OF Q* TO FORM D* KTDB
Figure 10-1: Pictorial Representation of Coordination Complex

Polymerization Scheme
C
j
k
act
k k
ica icb
P
1,0 C* Q
0,1
j
k
spt
k k
paa pbb
D
j
k k
za zb
k k
tac tbc
k k
pab k k pba
tda tdb
Pn, m D n, m Q n, m
k k
maa mbb
k k k k
paa tsa tsb pbb
k k
tha thb
k k
mab mba
The coordination complex polymerization scheme given in Table

10-1 is presented in pictorial form in Figure 10-1. Reaction path-
ways are represented with arrows and rate constants are indicated.
Inactive, active, and dead catalyst at site (j) are given by C(j), C*(j),
and D(j), respectively. Live polymer is represented by P(n,m) and
Q(n,m). Product polymer is represented by D(n,m). A sample
polymer reaction scheme occurring at site (j) is indicated with the
dotted arrows in this figure. Inactive catalyst, C(j), is converted to
active catalyst C*(j) at a rate given by the rate constant Kact.
Monomer A is inserted at the site at a rate given by the rate constant
Kica after which the propagation reaction given by the rate constant
Kpaa proceeds. A termination reaction given by Ktda produces
polymer product, D(n,m) and dead catalyst, D(j).
POLYMERS

Component data

Components Monomer(s), polymer, solvent, catalyst(s)
(required), cocatalyst(s) (optional), transfer agent (optional),
inhibitor (optional)
SAFT, or PHSC
Unit data (US21)
reactor)
Coordination Complex kinetic data
Required Coordination Complex reactions (initiation, propaga-
tion)
Optional reactions.
POLYMERS


Guide.

Communicating with PRO/II for Coordination Complex
Kinetics
BATCH
RPARM, and SUPPLE are quite lengthy. These headers are given on
the next page and do not appear in the example problems.
The homogeneous multi-site catalyst model developed here allows
for a maximum of four (N=4) distinct reaction sites generated from
a maximum of 2 catalysts or 2 catalyst-cocatalyst pairs. Each type
of reaction site is assumed to be unique kinetically; therefore, each
type of site has a unique set of kinetic rate parameters assigned to it
through the SUPPLE data vector.
The catalyst(s) or catalyst-cocatalyst pair(s) flow rate is set in the
STREAM DATA section. The first catalyst contains N types of
sites, and the second catalyst (if present) contains up to 4 N types
of sites. The relative amount and state of each type of reaction site
is described by a set of 3 numbers given sequentially in the RPARM
vector.
The site fraction gives the relative portion of that type of site to all
of the types of sites present on that particular catalyst. Since the
possible states for each type of site can be activated, inactive, or
dead, the second and third entries convey what portion of the type
of site is activated and inactive, respectively. The fraction of dead
sites is then calculated internally by difference.
From a processing standpoint, it is preferable to have a single cata-
lyst exhibiting polymerization characteristics of a single type of cat-
alyst site throughout the reaction process. In this case IPARM(4)
and IPARM(5) would be set to 1 and 0, respectively. The site frac-
tion defined in RPARM(22) would then be set to 1.0, there is only
one type of site. Now if the catalyst was pre-activated upstream of
the reactor inlet such that 95% of the available sites were reactive,
RPARM(23) and RPARM(24) would be 0.05 and 0.95, respectively.
POLYMERS

Figure 10-2: An example of two catalysts with four types of sites.
TypeISites
- inactive
- activated
- dead TypeIISites
- inactive TypeIVSites
TypeIIISites - activated - inactive
- inactive - dead - activated
- activated - dead
dead
Additional types of reaction sites can be introduced in the simula-

tion as needed. Figure 10-2 represents two catalysts, the 1st catalyst
with 3 types of sites, and the 2nd catalyst with one type of site. In
this case IPARM(4) and IPARM(5) would be set to 3 and 1, respec-
tively. Assuming that the concentrations of types of sites on the 1st
catalyst are equal in value, RPARM(22), RPARM(25), and
RPARM(28) are set close to 1/3 (site fractions will be normalized
internally). Assuming the catalyst has not been pre-activated
upstream of the reactor, the inactive fractions RPARM(23),
RPARM(26), and RPARM(29) are set to 1.0s and the activated
fractions RPARM(24), RPARM(27), and RPARM(30) are set to
0.0s, respectively. For the 2nd catalyst, the site fraction for the 4th
type of site is 1.0, there is only one type of site on the 2nd catalyst
and RPARM(31) is set to 1.0. Assuming the Type IV sites have not
been activated, RPARM(32) and RPARM(33) are 1.0 and 0.0,
respectively.
IPARM integer,. (up to 21 values)
RPARM real no,. (up to 18 values)
Integer IPARM Data:

POLYMERS
$
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ = 6 FOR HOMOGENEOUS ZN HOMOPOLYMERIZATION

$ = 7 FOR HOMOGENEOUS ZN COPOLYMERIZATION
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=n) REQ
$ IPARM( 5) = SITES (4-n MAX) ON 2ND CATALYST (=m OR 0)
$
BATCH
$ IPARM( 6) -> IPARM(10) N/A

$
$ IPARM(11) = POLYMER COMPONENT REQ
$
$ IPARM(12) = MONOMER A COMPONENT REQ
$ IPARM(15) = MODIFIER COMPONENT (OR 0)
$
$ IPARM(16) = 1ST CATALYST COMPONENT REQ
$ IPARM(17) = 1ST COCATALYST COMPONENT (OR 0)
$
$ IPARM(18) = 2ND CATALYST COMPONENT (OR 0)
$ IPARM(19) = 2ND COCATALYST COMPONENT (OR 0)
$
$
Real RPARM Data:

$
$ RPARM( 1)
= HEAT OF POLYMERIZATION (Haa) , J/GMOL
$ RPARM( 2)
= CSTR REACTOR VOLUME, LITER
$ RPARM( 3)
= JACKET TEMPERATURE, K, FOR NONISOTHERMAL REACTOR
$ RPARM( 4)
= JACKET AREA, M2, FOR NONISOTHERMAL REACTOR
$ RPARM( 5)
= OVERALL HTC, J/SEC/M2/K, FOR NONISOTHERMAL REACTOR
$ RPARM( 6)
= REACTOR TEMPERATURE, K,
$ = OPERATING TEMPERATURE FOR ISOTHERMAL CSTR/PFR
$ RPARM( 7) = CSTR REACTOR PRESSURE DROP (kPa) ; DEFAULT=0.0
$
$ RPARM( 8) -> RPARM(10) N/A
$
$ RPARM(14) = FEED STREAM LIVE CHAIN B FRACTION (COPOLYMER)
$ RPARM(19) = N/A
$
$ RPARM(20) = INTERACTION ORDER FOR TRANSFER AGENT TO P*
POLYMERS
$ RPARM(21) = INTERACTION ORDER FOR TRANSFER AGENT TO Q*

$
$ RPARM(22) = TYPE I SITE FRACTION
$ RPARM(23) = FRACTION OF TYPE I SITES WHICH ARE INACTIVE
$ RPARM(24) = FRACTION OF TYPE I SITES WHICH ARE ACTIVE
$
$ RPARM(25) = TYPE II SITE FRACTION
$ RPARM(26) = FRACTION OF TYPE II SITES WHICH ARE INACTIVE
$ RPARM(27) = FRACTION OF TYPE II SITES WHICH ARE ACTIVE
$
$ RPARM(28) = TYPE III SITE FRACTION

$ RPARM(29) = FRACTION OF TYPE III SITES WHICH ARE INACTIVE
$ RPARM(30) = FRACTION OF TYPE III SITES WHICH ARE ACTIVE
$
$ RPARM(31) = TYPE IV SITE FRACTION
$ RPARM(32) = FRACTION OF TYPE IV SITES WHICH ARE INACTIVE
$ RPARM(33) = FRACTION OF TYPE IV SITES WHICH ARE ACTIVE
$
$
Real SUPPLE Data:

$$
$ CATALYST - FIRST SITE
$
$REACTION STEP( 1): CATALYST SITE ACTIVATION BY COCATALYST KACT
$
$REACTION STEP( 2): INITIATION OF MONOMER A BY C* KICA
$
$REACTION STEP( 3): INITIATION OF MONOMER B BY C* KICB
$
$REACTION STEP( 4): PROPAGATION OF P* WITH MONOMER A KPAA
$
$REACTION STEP( 5): PROPAGATION OF Q* WITH MONOMER A KPBA
$
$REACTION STEP( 6): PROPAGATION OF P* WITH MONOMER B KPAB
$
$REACTION STEP( 7): PROPAGATION OF Q* WITH MONOMER B KPBB
$
$REACTION STEP( 8): TRANSFER FROM P* TO MONOMER A TO FORM RP* KMAA
$
$REACTION STEP( 9): TRANSFER FROM Q* TO MONOMER A TO FORM RP* KMBA
POLYMERS
$
$REACTION STEP(10): TRANSFER FROM P* TO MONOMER B TO FORM RQ* KMAB
$
$REACTION STEP(11): TRANSFER FROM Q* TO MONOMER B TO FORM RQ* KMBB
$
$REACTION STEP(12): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTSA

$
$REACTION STEP(13): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTSB
BATCH

$
$REACTION STEP(14): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTHA
$
$REACTION STEP(15): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTHB
$
$REACTION STEP(16): TRANSFER FROM P* TO COCATALYST TO FORM C* KTAC
$
$REACTION STEP(17): TRANSFER FROM Q* TO COCATALYST TO FORM C* KTBC
$
$REACTION STEP(18): SPONTANEOUS TERMINATION OF P* TO FORM C* KZA
$
$REACTION STEP(19): SPONTANEOUS TERMINATION OF Q* TO FORM C* KZB
$
$REACTION STEP(20): SPONTANEOUS TERMINATION OF C* TO FORM D* KSPT
$
$REACTION STEP(21): THERMAL DEGRADATION OF P* TO FORM D* KTDA
$
$REACTION STEP(22): THERMAL DEGRADATION OF Q* TO FORM D* KTDB
$
$ CATALYST - SECOND SITE ( IF USED )
$ REACTION(23) -> REACTION(44)
$ SUPPLE(45) -> SUPPLE(88)
$
POLYMERS
$ CATALYST - THIRD SITE ( IF USED )

$
$ CATALYST - FOURTH SITE ( IF USED )
$

Using Reactor Unit US21 to Model Coordination Polymeriza-
tion Systems
Polymer systems that may be modeled with unit US21 are:
Polyolefin Homopolymers and Copolymers
Example 10-1: Single-Site Coordination Homopolymerization

in a CSTR
used to model the solution polymerization of polyethylene. It is
important to note:
for the polymer polyethylene, and the FILL=VANK keyword is
2. The molecular weight distribution is provided on the
ATTRIBUTE statement. The distribution given will result in
the creation of 10 polymer pseudocomponents (1MW50000
through 1MW600000).
on this statement.
5. NONLIB components MSZ and MAO represent the zir-
conocene dichloride ([C2H5]2ZrCl2) catalyst and methylalu-
minoxane ([MeAlO]x) activator system. Here the molecular
weight given for MAO is consistent for a value of x=3.
and the non-isothermal reactor operating conditions are pro-
7. Data for the coordination complex kinetics for the polymeriza-
tion reaction are taken from Table 10-2 and are provided in the
POLYMERS
US21 units via the SUPPLE data statement.

Table 10-2: Kinetic Rate Parameters for Ethylene - Butene
Step Rate Prefactor k0 Prefactor Units Activation Energy
BATCH
Constant (J/gmol)
1 kact 9.999E09 (L/gmol/sec) 20000.
2 kica 1.611E10 (L/gmol/sec) 20502.
3 kicb 1.056E09 (L/gmol/sec) 25940.
4 kpaa 1.611E10 (L/gmol/sec) 20502.
5 kpba 4.722E10 (L/gmol/sec) 25940.
6 kpab 7.222E08 (L/gmol/sec) 20502.
7 kpbb 1.056E09 (L/gmol/sec) 25940.
8 kmaa 5.833E04 (L/gmol/sec) 14540.
9 kmba 8.167E02 (L/gmol/sec) 19986.
10 kmab 9.917E02 (L/gmol/sec) 14540.
11 kmbb 2.722E04 (L/gmol/sec) 19986.
12 ktsa 0.000E00 (L/gmol/sec) 0.
13 ktsb 0.000E00 (L/gmol/sec) 0.
14 ktha 0.000E00 (L/gmol/sec) 0.
15 kthb 0.000E00 (L/gmol/sec) 0.
16 ktac 5.833E05 (L/gmol/sec) 14540.
17 ktbc 9.917E03 (L/gmol/sec) 14540.
18 kza 5.000E10 (sec^-1) 46420.
19 kzb 1.361E12 (sec^-1) 51860.
20 kspt 4.722E04 (sec^-1) 25104.
21 ktda 4.722E04 (sec^-1) 25104.
22 ktdb 4.722E04 (sec^-1) 25104.
(-Hbb) are 94800, 89650, 89650, and 84750 joule/gmol, respectively.
References
1. Kim, Kee Jeong and Kyu Yong Choi, Continuous Olefin
POLYMERS
Copolymerization with Soluble Ziegler-Natta Catalysts,

AICHE Journal, August 1991, Vol. 37, No. 8 pp. 1255-1260.
Polyethylene Input CSTR File
TITLE PROJ=HOMOPOLYMER, PROB=ETH, USER=SIM, DATE=12/30/98
$
DIME SI
$
$ DIMENSION METRIC, STDTEMP=0, STDPRES=1.03323

$ DIMENSION ENGLISH, STDTEMP=60.0008, STDPRES=14.6959
$
OUTDIME REPLACE, SI, TIME=MIN
$
PRINT INPUT=ALL, STREAM=ALL, RATE=WT, PWRATE
$
SEGMENT DATA
STRUCTURE A, 4(2)
$
$ (1)Polymer
$ (2)Monomer A (3)Monomer B (4)Solvent
$ (5)Modifier (6)1st Catalyst (7)1st CoCatalyst
$ (8)2nd Catalyst (9)2nd CoCatalyst
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,HEXANE , BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1, HPE
MWAVG 1, 100000/ 4, 292.2 / 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, *
DATA=1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, *
DATA=1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
4, 400, 200, 915/*
5, 400, 200, 920
$
VP(Pa) CORRELATION= 20, DATA=4, 400, 200, 0.0, 1.0 /*
5, 400, 200, 0.0, 1.0
$
LATENT (KCAL/K,WT) CORRELATION= 15, *
DATA=4, 400, 200, 8730800., 0.3526000/*
5, 400, 200, 8730800., 0.3526000
POLYMERS
$
ATTRIBUTE COMP= 1, KINE= ZN, *
MWD= 50000, 100000, 150000, 200000, 250000,*
300000, 350000, 400000, 500000, 600000,*
MMWD= psi0, psi1, psi2
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,3, 0.5 $MONOMER-SOLVENT INTERACTIONS

$
STREAM DATA
$
BATCH
COMP(WT,KG/MIN)=0.0/0.8/0.2/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=PE CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = SITES ( 4 MAX ) ON 1ST CATALYST (=N) REQ
$ IPARM( 5) = SITES (4-N MAX) ON 2ND CATALYST (=M OR 0)
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,0,6,1,0, 0,0,0,0,0, 1,2,0,3,0, 4,5,0,0
$------------------------------------------------------------
$
POLYMERS

$ RPARM( 8) -> RPARM(19) N/A

$------------------------------------------------------------
RPARM 74800., 1000.0, 180.15, 100.0, 3.66, 150.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &

0.0, 0.0, 0.0, 0.0, 0.0, 0.5, 0.5, &
$
1.00, 1.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6
$------------------------------------------------------------
$ RPARM(22) = Type I Site Fraction
$ RPARM(23) = Fraction of Type I Sites which are Inactive
$ RPARM(24) = Fraction of Type I Sites which are Active
$
$ RPARM(25) = Type II Site Fraction
$ RPARM(26) = Fraction of Type II Sites which are Inactive
$ RPARM(27) = Fraction of Type II Sites which are Active
$
$ RPARM(28) = Type III Site Fraction
$ RPARM(29) = Fraction of Type III Sites which are Inactive
$ RPARM(30) = Fraction of Type III Sites which are Active
$
$ RPARM(31) = Type IV Site Fraction
$ RPARM(32) = Fraction of Type IV Sites which are Inactive
$ RPARM(33) = Fraction of Type IV Sites which are Active
$
$
$
$------------------------------------------------------------
SUPPLE 1, &
$ CATALYST / 1ST (ONLY) SITE
9.999E09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$
Example 10-2: Multi-Site Coordination Copolymerization in a

CSTR
used to model the bulk copolymerization of ethylene and butene. It
POLYMERS
is important to note:
ATTRIBUTE statement. The distribution given will result in the

creation of 10 polymer pseudocomponents (1MW50000
through 1MW600000).
BATCH

on this statement.
weight given for MAO is consistent for a value of x=3. Data
describing the NONLIB components MSZP and MAOP are
identical with that of the NONLIB components MSZ and
MAO. NONLIB components MSZP and MAOP have been
introduced here to indicate how a second catalyst-activator sys-
tem is addressed.
and the non-isothermal reactor operating conditions are pro-
Polyethylene-butene Input CSTR File
TITLE PROJ=COPOLYMER, PROB=Eth:But-1, USER=SIM, DATE=12/30/98
$
DIME SI
$
$
$
PRINT RATE=WT
$ PRINT RATE=WT, PWRATE
$
SEGMENT DATA
SEGMENT A, PE1/B, BUT1, FILL=VANKREVELEN
POLYMERS
STRUCTURE A, 4(2)/B, 60(1),4(1)

$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,BUT1/ 4,HEXANE/ 5,DPRK, BANK=SIMSCI
NONLIB 6,MSZ/ 7,MAO/ 8,MSZP/ 9,MAOP

$
POLYMER 1,PE-BUTENE
MWAVG 1, 100000/ 6, 292.2/ 7, 580.0/ 8, 292.2/ 9, 580.0
PHASE VLS=1
$
SPGR 6, 1.6 / 7, 1.4 / 8, 1.6 / 9, 1.4
NBP(K) 6, 450.0 / 7, 450.0 / 8, 450.0 / 9, 450.0
SOLUPARA 6, 10.0 / 7, 10.0 / 8, 10.0 / 9, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, DATA= *
1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76/*
6, 400, 200,-457.7994, 1.76/*
7, 400, 200,-457.7994, 1.76/*
8, 400, 200,-457.7994, 1.76/*
9, 400, 200,-457.7994, 1.76
$
DENSITY (L,K,G/LIT,WT) CORRELATION= 1, DATA= *
1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
4, 400, 200, 915/*
5, 400, 200, 920/*
6, 400, 200, 925/*
7, 400, 200, 930/*
8, 400, 200, 935/*
9, 400, 200, 940
$
VP(Pa) CORRELATION= 20, DATA=6, 400, 200, 0.0, 1.0/*
7, 400, 200, 0.0, 1.0/*
8, 400, 200, 0.0, 1.0/*
9, 400, 200, 0.0, 1.0
$
DATA=6, 400, 200, 8730800., 0.3526000/*
7, 400, 200, 8730800., 0.3526000/*
8, 400, 200, 8730800., 0.3526000/*
9, 400, 200, 8730800., 0.3526000
$
MWD= 50000, 100000, 150000, 200000, 250000,*
300000, 350000, 400000, 500000, 600000,*
POLYMERS
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4,0.5 / B,4,0.5 $MONOMER-SOLVENT INTERACTION
$
STREAM DATA
$
COMP(WT,KG/MIN)= 0.0/0.2/0.8/0.1/0.1/ *

1.0E-7/0.01/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE-BUT CSTReactor
BATCH
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,0,7,2,2, 0,0,0,0,0, 1,2,3,4,5, 6,7,8,9
$------------------------------------------------------------
$
$ RPARM( 8) = N/A
POLYMERS
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A

$------------------------------------------------------------
RPARM 94800., 100.0, 180.15, 100.0, 36.6, 148.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
$
0.20, 1.0E-0, 0.0E-6, &
0.30, 1.0E-0, 0.0E-6, &
0.40, 1.0E-0, 0.0E-6, &
0.10, 1.0E-0, 0.0E-6
$------------------------------------------------------------
$
$
$
$
$
$
$
$ CATALYST - THIRD SITE ( IF USED )
$
$ CATALYST - FOURTH SITE ( IF USED )
$------------------------------------------------------------
$
SUPPLE 1, &
$
$ CATALYST / 1ST SITE
9.999e18/ 20000./ 1.611E10/ 20502./ &
POLYMERS
1.056E09/ 25940./ 1.611E10/ 20502./ &

4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &

$
$ CATALYST / 2ND SITE
9.999e18/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
BATCH
4.722E10/ 25940./ 7.222E08/ 20502./ &

1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$
$ CATALYST / 3RD SITE
9.999e18/ 20000./ 1.611E09/ 20502./ &
1.056E09/ 25940./ 1.611E09/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$
$ CATALYST / 4TH SITE
9.999e18/ 20000./ 1.611E09/ 20502./ &
1.056E09/ 25940./ 1.611E09/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$
Example 10-3: Single-Site Coordination Polymerization in a

CSTR
used to model the bulk polymerization of ethylene and butene. If
POLYMERS
solution polymerization is of interest, this problem can be modified

easily to add an input solvent component to the reactor feed. It is
important to note:
for the polymer polyethylene and polyvinylacetate. The
FILL=VANK keyword is used to specify that van Krevelen predic-
tion methods be used for polymer properties.

creation of 10 polymer pseudocomponents (1MW50000 through
1MW200000).
on this statement.
POLYMERS

Polyethylene-Butene CSTR Input File
TITLE PROJ=COPOLYMER, PROB=Eth:But-1, USER=SIM, DATE=12/30/98
$
BATCH
DIME SI
$
$
$
PRINT RATE=WT
$
SEGMENT DATA
SEGMENT A, PE1 /B, BUT1, FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 60(1),4(1)
$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,BUT1, BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PE-BUT
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, DATA= *
1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DATA=1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
4, 400, 200, 915/*
POLYMERS
5, 400, 200, 920

$
5, 400, 200, 0.0, 1.0
$
DATA=4, 400, 200, 8730800., 0.3526000/*
5, 400, 200, 8730800., 0.3526000
$

MWD= 50000, 60000, 70000, 80000, 90000,*
110000, 130000, 150000, 170000, 200000,*
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,4, 0.5/ B,4, 0.5 $MONOMER-SOLVENT INTERACTIONS
$
STREAM DATA
$
COMP(WT,KG/MIN)=0.0/0.2/0.8/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE-BUT CSTReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,1,7,1,0, 0,0,0,0,0, 1,2,3,0,0, 4,5,0,0
$------------------------------------------------------------
POLYMERS
$

$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
BATCH

$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$------------------------------------------------------------
RPARM 94800., 100.0, 180.15, 100.0, 36.6, 140.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
$
1.00, 1.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6
$------------------------------------------------------------
$
$
$
$
$------------------------------------------------------------
$
SUPPLE 1, &
$
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
POLYMERS
4.722E10/ 25940./ 7.222E08/ 20502./ &

1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$
$

US21 UID=REACTOR2, NAME=2nd PE-BUT CSTReactor
FEED Prod_1
PROD Prod_2
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 1,1,7,1,0, 0,0,0,0,0, 1,2,3,0,0, 4,5,0,0
$------------------------------------------------------------
$
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
POLYMERS
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$------------------------------------------------------------

RPARM 94800., 100.0, 180.15, 100.0, 36.6, 160.00, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
89650., 89650., 84750., 0.0, 0.0, 0.5, 0.5, &
$
BATCH
1.00, 1.0E-0, 0.0E-6, &

0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6, &
0.00, 0.0E-0, 0.0E-6
$
DEFINE RPARM(22) AS US21=REACTOR1 RPARM(22)



$
$------------------------------------------------------------
$
$
$
$
$----------------------------------------------------------------------
-
$
SUPPLE 1, &
$
POLYMERS
9.999e09/ 20000./ 1.611E10/ 20502./ &

1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &

4.722E04/ 25104./ 4.722E04/ 25104.
$
Example 10-4: Multi-Site Coordination Polymerization in a

PFR
used to model the solution polymerization of ethylene. It is impor-
tant to note:
1MW200000).
on this statement.
and the nonisothermal reactor operating conditions are pro-
POLYMERS

Polyethylene PFR Input File
TITLE PROJ=HOMOPOLYMER, PROB=Eth, USER=SIM, DATE=12/30/98
$
BATCH
DIME SI
$
$
$
PRINT RATE=WT
$
SEGMENT DATA
STRUCTURE A, 4(2)
$
$ (1)Polymer
$
COMPONENT DATA
LIBID 2,ETHYLENE/ 3,HEXANE , BANK=SIMSCI
NONLIB 4,MSZ/ 5,MAO
$
POLYMER 1,PETH
MWAVG 1, 100000/ 4, 292.2/ 5, 580.0
PHASE VLS=1
$
SPGR 4, 1.6 / 5, 1.4
NBP(K) 4, 450.0 / 5, 450.0
SOLUPARA 4, 10.0 / 5, 10.0
$
ENTHALPY (L,K,J/G,WT) CORRELATION= 1, *
DATA=1, 400, 200,-457.7994, 1.76/*
2, 400, 200,-457.7994, 1.76/*
3, 400, 200,-457.7994, 1.76/*
4, 400, 200,-457.7994, 1.76/*
5, 400, 200,-457.7994, 1.76
$
DATA=1, 400, 200, 900/*
2, 400, 200, 905/*
3, 400, 200, 910/*
POLYMERS
4, 400, 200, 915/*

5, 400, 200, 920
$
5, 400, 200, 0.0, 1.0
$
DATA=4, 400, 200, 8730800., 0.3526000/*
5, 400, 200, 8730800., 0.3526000
$

MWD= 50000, 60000, 70000, 80000, 90000,*
110000, 130000, 150000, 170000, 200000,*
$
THERMO DATA
METHOD SYSTEM=FLORY
KVALUE
CHI A,2 ,0.5 $MONOMER-SOLVENT INTERACTION
$
STREAM DATA
$
COMP(WT,KG/MIN)=0.0/2.0/2.0/ 1.0E-7/0.01
$
UNIT OPERATION
US21 UID=REACTOR1, NAME=1st PE PFReactor
FEED Feed_1
PROD Prod_1
$------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 6) = N/A
$ IPARM( 7) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$------------------------------------------------------------
IPARM 2,0,6,2,0, 0,0,0,0,0, 1,2,0,3,0, 4,5,0,0
$------------------------------------------------------------
POLYMERS
$

$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
BATCH

$ RPARM(13) = N/A
$ RPARM(14) = N/A
$ RPARM(19) = N/A
$------------------------------------------------------------
RPARM 94800., 0.0, 140.15, 0.0, 36.6, 140.00, 0.0, &
0.0, 0.0, 0.0, 500.0, 4.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.9, 0.0, 0.5, 0.5, &
$
0.25, 1.0E-0, 0.0E-6, &
0.75, 1.0E-0, 0.0E-6, &
0.0, 0.0E-0, 0.0E-6, &
0.0, 0.0E-0, 0.0E-6
$------------------------------------------------------------
$
$
$
$
$
$
$RXN STEP( 1): CATALYST SITE ACTIVATION BY COCATALYST KACT
$RXN STEP( 2): INITIATION OF MONOMER A BY C* KICA
$RXN STEP( 3): INITIATION OF MONOMER B BY C* KICB
$RXN STEP( 4): PROPAGATION OF P* WITH MONOMER A KPAA
POLYMERS
$RXN STEP( 5): PROPAGATION OF Q* WITH MONOMER A KPBA

$RXN STEP( 6): PROPAGATION OF P* WITH MONOMER B KPAB
$RXN STEP( 7): PROPAGATION OF Q* WITH MONOMER B KPBB
$RXN STEP( 8): TRANSFER FROM P* TO MONOMER A TO FORM RP* KMAA
$RXN STEP( 9): TRANSFER FROM Q* TO MONOMER A TO FORM RP* KMBA
$RXN STEP(10): TRANSFER FROM P* TO MONOMER B TO FORM RQ* KMAB
$RXN STEP(11): TRANSFER FROM Q* TO MONOMER B TO FORM RQ* KMBB
$RXN STEP(12): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTSA
$RXN STEP(13): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTSB
$RXN STEP(14): TRANSFER FROM P* TO SOLVENT TO FORM RP* KTHA
$RXN STEP(15): TRANSFER FROM Q* TO SOLVENT TO FORM RQ* KTHB

$RXN STEP(16): TRANSFER FROM P* TO COCATALYST TO FORM C* KTAC
$RXN STEP(17): TRANSFER FROM Q* TO COCATALYST TO FORM C* KTBC
$RXN STEP(18): SPONTANEOUS TERMINATION OF P* TO FORM C* KZA
$RXN STEP(19): SPONTANEOUS TERMINATION OF Q* TO FORM C* KZB
$RXN STEP(20): SPONTANEOUS TERMINATION OF C* TO FORM D* KSPT
$RXN STEP(21): THERMAL DEGRADATION OF P* TO FORM D* KTDA
$RXN STEP(22): THERMAL DEGRADATION OF Q* TO FORM D* KTDB
$
$
$----------------------------------------------------------------------
-
$
SUPPLE 1, &
$
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104./ &
$
$ CATALYST / 2ND SITE
9.999e09/ 20000./ 1.611E10/ 20502./ &
1.056E09/ 25940./ 1.611E10/ 20502./ &
4.722E10/ 25940./ 7.222E08/ 20502./ &
1.056E09/ 25940./ 5.833E04/ 14540./ &
8.167E02/ 19986./ 9.917E02/ 14540./ &
2.722E04/ 19986./ 0.000E00/ 0./ &
0.000E00/ 0./ 0.000E00/ 0./ &
0.000E00/ 0./ 5.833E05/ 14540./ &
9.917E03/ 14540./ 5.000E10/ 46420./ &
1.361E12/ 51860./ 4.722E04/ 25104./ &
4.722E04/ 25104./ 4.722E04/ 25104.
$
POLYMERS

POLYMERS
Chapter 11
User-Added Step Growth
Polymerization Reactor Model

systems.
homopolymer
linear homopolymer
POLYMERS
linear copolymer

BATCH

Polymerization via Stepwise Kinetics

Stepwise or step growth polymerization refers to a kinetic mecha-
nism in which the polymer molecular weight increases in a slow
and steplike manner as the reaction time increases. The stepwise
polymerization mechanism involves a chemical reaction between
monomer functional groups. All stepwise polymerizations fall into
two groups, depending on the structure and number of monomers
taking part in the reaction.
The first monomer group describes the reaction between the func-
tional groups of one bifunctional or polyfunctional monomer that
contains different functional groups. The monomers of this group
are labeled as ARB. A general stepwise ARB polymerization can be
represented as:
( n )XAR 1 BY + ( n )XAR 1 BY<> X ( AR 1 BAR 1 B ) n Y + ( 2n 1 )X:Y
in which A'X represents functional groups may include:

NH 2 SH CONH 2 OH NOH
and B'Y represents functional groups that may include:

COOH COCl PORCl SOOCl
The second monomer group describes the reaction between two dif-
ferent bifunctional or polyfunctional monomers in which each of
the reacting monomers contains only one unique functional group.
The monomers of this group are labeled as ARA and BRB. A general
stepwise ARA and BRB polymerization can be represented as:
POLYMERS
( n )XAR 1 AX + ( n )YBR 2 BY<> X ( AR 1 BAR 2 B ) n Y + ( 2n 1 )X:Y
The reacting functional groups contain the atoms X and Y and it is

these moieties that form the condensate X:Y. To simplify the step-
wise nomenclature, the following definitions have been used:
*
A = XA B = YB R = R 1 ABR 1 R = R 1 ABR 2
11-2 User-Added Step Growth Polymerization Reactor Model

Note that the groups R* and R do not take place explicitly in the
polymerization, because the condensation reactions occur at the ter-
minal functional groups. The general reactions for ARB and ARA and
BRB polymerization are then greatly simplified.
ARB polymerization:
*
( n )AR 1 B<>A ( R ) n + ( 2n 1 )X:Y
ARA + BRB polymerization:

( n )AR 1 A + ( n )BR 2 B<>A ( R n ) + ( 2n 1 )X:Y
The step growth polymerization reactions are usually slow and take
on the order of 10 - 20 hours to complete. The polymerization reac-
tions may be reversible, and, if so, they are dominated by equilib-
rium considerations. Consequently, it is important to accurately
simulate a flash in which any condensate or residual monomer is
driven off. The reaction kinetics are then shifted such that increased
yield is obtained. The monomers used in the step growth polymer-
izations include esters, ethers, amines, and amides. Polymer exam-
ples are polyesters, polyethers, nylons (Nylon 6, Nylon 6,6), and
polyimides (Kevlar).
Stepwise Polymerization Chain Types

Three categories of stepwise polymer chains can be identified from
the functionality of the reacting monomers and the structure of the
polymer chain formed.
If a single monomer is involved in the reaction, and the monomer is
of the bifunctional form A-B (actually A-R-B), the polymer formed
has the structure given by A-BA-BA-B. This is a Type I stepwise poly-
merization.
Type I:
ARB + ARB<> ARRB + C

X 1 ARBY 1 + X 1 ARBY 1 <> X 1 ABARBY 1 + X 1 Y 1
POLYMERS
The kinetic data for this reaction require the definition of a single
monomer along with the rate constants for the reaction between X1
and Y1.
If two monomers are involved in the reaction, and the monomers are
of the monofunctional form A-A and B-B (actually A-R-B and B-R-B),

the polymer formed has the structure given by A-BA-BA-B. This is a
Type II stepwise polymerization.
Type II:
BATCH
AR 1 A + BR 2 B<> AR 1 R 2 B + C
X 1 A 1 R 1 A 1 X 1 + Y 1 B 1 R 2 B 1 Y 1 <> X 1 A 1 R 1 A 1 B 1 R 2 B 1 Y 1 + X 1 Y 1
The kinetic data for this reaction require the definition of two
monomers along with the rate constants for a reaction between X1
and Y1.
If a single monomer is involved in the reaction and the monomer is
of the monofunctional form A-A (actually A-R-A), the polymer
formed has the structure given by A-R-R-A. This is a Type III step-
wise polymerization.
Type III:
ARA + ARA<> ARRA + C

X 1 ARAY 1 + X 1 ARAY 1 <> X 1 ARAY 1 + X 1 Y 1
The kinetic data for this reaction requires the definition of a single
monomer along with the rate constants for a reaction between X1
and Y1.
Ultimately, it is required that a value for the number of monomer
units be incorporated into the average stepwise polymer and that
the number of active functional groups (X and Y) on the average
polymer chain be available. This characterization begins with the
population balance. The term Pm,a,b is introduced to indicate a linear
polymer molecule containing m repeat units terminated on one end
by an a functional group and the other end by a b functional group.
The vectors m, a, and b are defined by:
m1 X1 Y1

m m2 a X2 b Y2
POLYMERS

M M M
in which the vector components are mi = Ri, ai = XiAi', and

bi = YiBi'. The population balance is then written consistent with
these vectors and the kinetic mechanisms given in Table 11-1.

Stepwise Polymerization Kinetic Mechanisms
A stepwise polymerization can be adequately modeled by the
kinetic mechanisms presented in Table 11-1. The stepwise polymer-
ization mechanisms are reversible and therefore are ultimately
determined by chemical equilibrium. Also, some mechanisms are
acid catalyzed. The kinetic constants ki, kir and Ki, which are the
forward, reverse, and equilibrium rate constants, respectively, for
reaction (i), are based on the reaction of functional groups.
Table 11-1: Step Growth Polymerization Mechanisms
Reaction Constant Type
1 k1 Polycondensation I
P n, a, b + P m, x, y >P n + m, a + x ( i ), b + y d ( j ) + C i, j
2 k2 Polymer addition
P n, a, b + P m, x, y >P n + m, a + x ( i ), b + y d ( j )
3 k3 Polycondensation II
P n, a, b + P m, x, y >P n + m, a + x ( i ), b + y d ( j ) + P ( k ), 2 ( i ) ( j ), 0
4 k4 Polymer-monomer unequal reactivity

P n, a, b + P ( k ), m ( i ), 0 >P n + ( k ), a + ( m 1 ) ( c ), b d ( j ) + C i:j
5 k5 Scission degradation
P n, a, b >P n r, a x, b y + ( j ) + P r ( r1 ) + ( r2 ), x, y
6 k6 Monomer salting
S ( i ) + S ( j ) >P ( i ) + ( j ), a, b + C i:j
7 k7 Two-chain reformation
P n, a, b + P m, x, y >P n ( r1 ), a ( i ), b + ( b1 ) +
P m ( r2 ) + ( r3 ), x ( j ) ( a1 ), y
8 k8 Deactivation of A group
P n, a, b + Z k >P n, a ( i ), b + ( C i:k )
9 k9 Deactivation of B group
P n, a, b + Z k >P n, a, b ( j ) + ( C i:k )
10 k10 Ultimate monomer degradation

P n, a, b >P n ( k ), a ( i ), b + ( j ) + C i:j
POLYMERS
11 k11 Ring opening

R n + C i:j >P n, ( i ), ( j )
12 k12 Ring addition
P n, a, b + R m >P n + m, a ( k ) + d ( i ), b added to Ak
A brief description of each mechanism is presented below.

1. Polycondensation I: This reaction is between two non-ring lin-
ear polymer chains and involves the reaction between an Ai end
group and Bj end group. The kinetic rate constant is based on
the reaction between the end groups Ai and Bj.
BATCH
2. Polymer Addition: This reaction is identical to the polycon-

densation I reaction except that no condensate is formed.
Non-ring linear chains are involved, and the reaction is between
the Ai and Bj end groups.
3. Polycondensation II: This mechanism describes the reaction
between two end groups of the same type, which are Ai with Bj.
A condensate labeled P(k), 2(i)-(j),0 is formed. The rate constant
is based on the rate of reaction of an Ai group reacting with an
Aj group.
4. Polymer Monomer Unequal Reactivity: This mechanism
describes the reaction of two non-ring polymer chains to form
monomer end groups that have different reactivities from the
identical end groups already on the polymer chain. This reac-
tion is similar to the polycondensation I reaction, except that
the end group of the ultimate monomer unit transforms. The
kinetic rate constant is based on the rate of reaction for an Ai
end group with a Bj end group.
5. Scission Degradation: This mechanism describes the degrada-
tion of a chain linkage to form two polymer chains. The ulti-
mate monomer unit on the first chain is chemically altered
(made inactive), and an active Bj end group is created on the
second chain. The rate constant is based on the rate of reaction
of an ij linkage with a polymer chain.
6. Monomer Salting: This mechanism describes the reaction of
two salting compounds to form polymer and a condensate. The
polymer salt formed is treated as polymer dimer.
7. Two Chain Reformation: This reaction is between two A end
groups. It creates two new chain ends. The first chain has its
ultimate monomer unit stripped away, which leads to the
penultimate monomer unit and its corresponding Bi end group
being exposed. The second chain receives the stripped mono-
mer unit. The kinetic rate constant is based on reacting with the
Ai end group.
POLYMERS
8. Deactivation of A Group: This mechanism describes the reac-

tion of a deactivating species with the polymer chain. The result
is that the polymer chain has one less active end group. Here it
is assumed no condensate is formed. This reaction deactivates
an Ai group. The rate constant is based on the rate of reaction of
the Ai functional group and the Zk deactivation species.
9. Deactivation of B Group: This mechanism describes the reac-
tion of a deactivating species with the polymer chain. The result

is that the polymer chain has one less active end group. Here it
is assumed no condensate is formed. This reaction deactivates a
Bj group. The rate constant is based on the rate of reaction of
the Bj functional group and the Zk deactivation species.
10. Ultimate Monomer Degradation: This mechanism describes
the degradation of the ultimate monomer unit, (Rk). The result
is that the chain has one less monomer unit. The rate constant is
based on the rate of reaction of the ij linkage made by the ulti-
mate monomer unit (Rk) and the penultimate monomer unit.
11. Ring Opening: This reaction is between the condensate i:j and
the ring h-mer where the symbol h indicates the equivalent num-
ber of linear monomers n in the ring. The reaction product is
therefore an n-mer, and it has Ai and Bj end groups. The kinetic
rate constant is based on the reaction rate between condensate i:j
and ring h.
12. Ring Addition: This reaction is between the ring h-mer of the
previous mechanism and the polymer chain. The ring h-mer is
added to the polymer chain end group. The kinetic rate constant
is based on the rate of reaction of the ring h-mer and the func-
tional group.

Component data
Components Monomer(s), polymer, solvent, transfer agent
(optional), inhibitor (optional)
SAFT, or PHSC
POLYMERS
Unit data (US21)


reactor)
BATCH

Step growth kinetic data
Required stepwise reactions (polycondensation reaction)
Optional reactions.

Guide.
Communicating with PRO/II for Stepwise Kinetics

RPARM, and SUPPLE are quite lengthy. These headers are given on
the next page and do not appear in any example problem.
IPARM integer,. (up to 24 values)
RPARM real no,. (up to 18 values)
Integer IPARM Data:

$ = 1 FOR CSTR
$ = 2 FOR PFR
POLYMERS

$ = 3 FOR STEP GROWTH POLYMERIZATION ( TYPE I )
$ = 4 FOR STEP GROWTH POLYMERIZATION ( TYPE II )
$ = 5 FOR STEP GROWTH POLYMERIZATION ( TYPE III )
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = NUMBER OF RINGS REQ

$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$
$ IPARM(12) = MONOMER 1 ( A1-R1-B1 ) COMPONENT
$ IPARM(13) = MONOMER 2 ( A2-R2-B2 ) COMPONENT (OR 0)
$ IPARM(14) = MONOMER 1 - RING 1 ( A-R[1]-B ) COMPONENT
$ IPARM(15) = MONOMER 1 - RING 2 ( A-R[2]-B ) COMPONENT (OR 0)
$ IPARM(17) = P1 COMPONENT (OR 0)
$ IPARM(20) = CONDENSATE COMPONENT (OR 0)
$ IPARM(21) = CATALYST COMPONENT (OR 0)
$ IPARM(22) = DEACTIVATION AGENT COMPONENT (OR 0)
$ IPARM(23) = SALTING AGENT COMPONENT (OR 0)
$ IPARM(24) = INERT COMPONENT, N2 (OR 0)
$
Real RPARM Data:

$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$
Real SUPPLE Data:

POLYMERS
$
$ NON RING REVERSIBLE KINETIC DATA
$
$ REACTION 1 POLYCONDENSATION I
$ SUPPLE( 1) = PREEXPONENTIAL FACTOR FOR INTRINSIC REACTION
$ SUPPLE( 2) = ACTIVATION ENERGY
$ SUPPLE( 3) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$ SUPPLE( 5) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE( 6) = DEL(S)

$
$ REACTION 2 POLYMER ADDITION
$ SUPPLE( 7) = PREEXPONENTIAL FACTOR FOR INTRINSIC RXN
BATCH
$ SUPPLE( 9) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN

$ SUPPLE(10) = ACTIVATION ENERGY
$ SUPPLE(11) = DEL(H) FOR EQUILIBRIUM RXN
$ SUPPLE(12) = DEL(S)
$
$ REACTION 3 POLYCONDENSATION II
$ SUPPLE(13) = PREEXPONENTIAL FACTOR FOR INTRINSIC RXN
$ SUPPLE(15) = PREEXPONENTIAL FACTOR FOR CATALYZED RXN
$
$ REACTION 4 POLYMER-MONOMER U. R.
$
$ REACTION 5 SCISSION DEGRADATION
$
$ NON RING IRREVERSIBLE KINETIC DATA
$
$ REACTION 6 MONOMER SALTING
$
$ REACTION 7 TWO CHAIN REFORMATION
$
POLYMERS
$ REACTION 8 DEACTIVATION
$
$ REACTION 9 DEACTIVATION

$
$ REACTION 10 ULTIMATE MONOMER DEGRADATION
$
$ RING REVERSIBLE KINETIC DATA
$
$ REACTION 11a RING OPENING OF MONOMER
$
$ REACTION 11b RING OPENING OF DIMER
$
$ REACTION 11c RING OPENING OF TRIMER
$
$ REACTION 12a POLYADDITION OF MONOMER
$
$ REACTION 12b POLYADDITION OF DIMER
POLYMERS
$
$ REACTION 12c POLYADDITION OF TRIMER
$

Using Reactor Unit US21 to Model Step Growth Systems
Polymer systems that may be modeled with unit US21 are:
BATCH
Type I Nylon 6
Type II Ethylene Glycol and Adipic Acid, Nylon 6,6
Type III BHET homopolymerization
Example 11-1: Type I Step Growth Polymerization in a CSTR

used to model the bulk polymerization of caprolactum to Nylon 6.
If solution polymerization is of interest, this problem can be modi-
fied easily to add an input component to the reactor feed for use as a
solvent. It is important to note:
1MW200000).
on this statement.
6. Data for the step growth kinetics for the polymerization reac-
tion are taken from Table 11-2 and Table 11-3 and are provided
in the US21 units via the SUPPLE data statement.
POLYMERS
Table 11-2: Kinetic Rate Parameters for Caprolactum Polymerization

Rxn Rate Prefactor Prefactor Prefactor Ea0 Eac
Step Const. Ao Ac Units
1 k1 1.8942e10 1.2114e10 kg/kmol/hr 9.7389e4 8.6504e4
11a k11a 5.9874e5 4.3075e7 kg/kmol/hr 8.3198e4 7.8703e4
12a k12a 2.8558e9 1.6377e10 kg/kmol/hr 9.5606e4 8.4148e4
Note: The heat of polymerization (-Haa) for caprolactum is 16900 joule/gmol.

Table 11-3: Equilibrium Constants for Nylon 6
Reaction Step Rate Constant Enthalpy Entropy
H (J/kg) S (J/kg/K)
1 K1 -2.4883e4 3.9496e0
11a K11a 8.0268e3 -3.2997e1
12a K12a -1.6923e4 -2.9068e1
Nylon 6 Input CSTR File

TITLE PROJ=POLYMER, PROB=NYLON6, USER=SIM, DATE=12/01/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, NYLON1, FILL=VANKREVELEN
STRUCTURE A, 4(5), 231(1), 403(1)
COMPONENT DATA
LIBID 2,CPLC/3,NPHT/4,H20
POLYMER 1, NYLON6
MWAVG 1, 5900
PHASE VLS = 1
ENTHALPY (L,K,J/G,WT) CORRELATION=1, *
DATA=1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
DENSITY (L,K,G/LIT,WT) CORRELATION = 1, *
DATA=1, 400, 200, 910/*
2, 400, 200, 910/*
3, 400, 200, 910/*
4, 400, 200, 910
ATTRIBUTE COMP=1, KINE= SG, *
MWD = 50,100,200,500,800,1000,3000,4000,*
5000,6000,8000,10000,30000,50000,*
70000,80000,100000,200000,*
MMWD = PSI0, PSI1, PSI2
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,2, 0.00681127
ALMC A, 0.475503
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=494.15, PRES(ATM)=5, *
COMP(WT, KG/MIN)=0.0/9.650/0.000/0.0430
UNIT OPERATION
POLYMERS
US21 UID=REACTOR_1, NAME=NYLON6 CSTReactor

FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR

BATCH
$ IPARM( 4) = NUMBER OF REVERSIBLE REACTION STEPS REQ

$ IPARM( 5) = NUMBER OF IRREVERSIBLE REACTION STEPS REQ
$ IPARM( 8) = REVERSIBLE KINETICS FLAG REQ
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 1,1,3,5,5, 1,2,2,0,0, 1,0,0,2,0, 0,3,0,0,4, 0,0,0,0
$---------------------------------------------------------------
$---------------------------------------------------------------
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
POLYMERS
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$---------------------------------------------------------------
RPARM 16900., 6400.0, 350., 2.5, 60., 494.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$---------------------------------------------------------------

$---------------------------------------------------------------
SUPPLE 1,1.8942D+10/ 9.7389D+04/ 1.2114D+10/ 8.6504D+04/ &
-2.4883D+04/ 3.9496D+00/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
5.9874D+05/ 8.3198D+04/ 4.3075D+07/ 7.8703D+04/ &
8.0268D+03/ -3.2997D+01/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
2.8558D+09/ 9.5606D+04/ 1.6377D+10/ 8.4148D+04/ &
-1.6923D+04/ -2.9068D+01/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
Example 11-2: Type I Step Growth Polymerization in a PFR

used to model the bulk polymerization of caprolactum to Nylon 6.
If solution polymerization is of interest, this problem can be modi-
fied easily to add an input component to the reactor feed for use as a
solvent. It is important to note:
1MW50000).
on this statement.
POLYMERS


Nylon 6 Input PFR File
$TITLE PROJ=POLYMER, PROB=NYLON6, USER=SIM, DATE=12/01/97
DIME SI
BATCH
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, NYLON1, FILL=VANKREVELEN
STRUCTURE A, 4(5), 231(1), 403(1)
COMPONENT DATA
LIBID 2,CPLC/3,NPHT/4,H20
POLYMER 1, NYLON6
MWAVG 1, 8400
PHASE VLS = 1
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
1, 400, 200, 897/*
2, 400, 200, 897/*
3, 400, 200, 897/*
4, 400, 200, 897
ATTRIBUTE COMP=1, KINE= SG, *
MWD = 1000,2000,3000,5000,6000,7000, *
8000,9000,10000,15000,20000, *
30000,40000,50000,*
THERMO DATA
METHODS SYSTEM=ALM
KVALUE
ALME A,2, 0.00681127
ALMC A, 0.475503
STREAM DATA
COMP(WT, KG/MIN)=0.0/9.650/0.000/0.0830
UNIT OPERATION
US21 UID=REACTOR_1, NAME=NYLON6 PFReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
POLYMERS

$ IPARM( 4) = NUMBER OF REVERSIBLE REACTION STEPS REQ
$ IPARM( 5) = NUMBER OF IRREVERSIBLE REACTION STEPS REQ

$ IPARM( 8) = REVERSIBLE KINETICS FLAG REQ
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$---------------------------------------------------------------
2,1,3,5,5, 1,2,2,0,0, 1,0,0,2,0, 0,3,0,0,4, 0,0,0,0
$---------------------------------------------------------------
$---------------------------------------------------------------
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$---------------------------------------------------------------
RPARM 16900., 0.0, 0.0, 0.0, 0., 518.15, 0.0, &
0.0, 0.0, 0.0, 150.0, 15.0, 0.0, 0.0, &
16900., 16900., 0.0, 0.008
$---------------------------------------------------------------
POLYMERS

$---------------------------------------------------------------
SUPPLE 1,1.8942D+10/ 9.7389D+04/ 1.2114D+10/ 8.6504D+04/ &
-2.4883D+04/ 3.9496D+00/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
5.9874D+05/ 8.3198D+04/ 4.3075D+07/ 7.8703D+04/ &
8.0268D+03/ -3.2997D+01/ 0.0/0.0/0.0/0.0/0.0/0.0/ &

0.0/0.0/0.0/0.0/0.0/0.0/ &
2.8558D+09/ 9.5606D+04/ 1.6377D+10/ 8.4148D+04/ &
-1.6923D+04/ -2.9068D+01/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
BATCH

FLASH UID=PRODUCT
FEED PROD_1
ISOT TEMP(K)=518.15, PRES(ATM)=5$
Example 11-3: Type II Step Growth Polymerization in a CSTR

used to model the bulk polymerization of ethylene glycol and adipic
acid. If solution polymerization is of interest, this problem can be
modified easily to add an input solvent component to the reactor
feed. It is important to note:
for the polymer polystyrene. The FILL=VANK keyword is used to
specify that van Krevelen prediction methods be used for poly-
mer properties.
1MW1000).
on this statement.
6. The product of the reactor unit is flashed isothermally in unit
POLYMERS
Table 11-4: Kinetic Rate Parameters for Ethylene Glycol/Adipic Acid

Polymerization
Step Rate Constant Prefactor Ac Prefactor Units Eac(J/gmol)
1 k1 2.2000e5 kg/kmol/hr 54392
Note: The heat of polymerization (-Haa) for ethylene glycol and adipic acid is 64500
joule/gmol.

Ethylene Glycol \ Adipic Acid CSTR Input File
TITLE PROJ=TYPE II, PROB=FPOLYMER, USER=SIM, DATE=12/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, EG1/B, ADIPIC1 , FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 4(4), 237(2)
COMPONENT DATA
LIBID 2,EG /3,ADIPIC /4,H20
POLYMER 1, FPOLYMER
MWAVG 1, 120
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION= 1,DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
1, 400, 200, 945/*
2, 400, 200, 945/*
3, 400, 200, 945/*
4, 400, 200, 945
ATTRIBUTE COMP=1, KINE = SG, MWD = *
10,20,30,40,50,60,70,80,90,100,*
110,120,130,150,200,300,500,700,*
1000,*
THERMO DATA
METHODS SYSTEM=FLORY
STREAM DATA
COMP(WT, KG/MIN)=0.0/4.850/11.450/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=FLORY-P CSTReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
POLYMERS

$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 1,1,4,0,0, 0,2,0,0,0, 1,2,3,0,0, 0,0,0,0,4, 0,0,0,0
$---------------------------------------------------------------
BATCH

$---------------------------------------------------------------
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$---------------------------------------------------------------
RPARM 64500., 100.0, 350., 2.5, 0., 439.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$---------------------------------------------------------------
$---------------------------------------------------------------
SUPPLE 1,0.0/0.0/2.2E+05/54392./0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
POLYMERS
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1

ISOT TEMP(K)=439.15, PRES(ATM)=10$
Example 11-4: Type II Step Growth Polymerization in a PFR

used to model the bulk polymerization of ethylene glycol and adipic
acid. If solution polymerization is of interest, this problem can be
modified easily to add an input solvent component to the reactor
feed. It is important to note:
1MW5000).
on this statement.
6. The product of the reactor unit is flashed isothermally in unit
POLYMERS

Ethylene Glycol/Adipic Acid PFR Input File
TITLE PROJ=TYPE II, PROB=FPOLYMER, USER=SIM, DATE=12/97
DIME SI
BATCH
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, EG1/B, ADIPIC1 , FILL=VANKREVELEN
STRUCTURE A, 4(2)/B, 4(4), 237(2)
COMPONENT DATA
LIBID 2,EG/3,ADIPIC/4,H20
POLYMER 1, FPOLYMER
MWAVG 1, 160
PHASE VLS=1
ENTHALPY (L,K,J/G,WT) CORRELATION= 1,DATA= *
1,400,200,-457.7994,1.676/*
2,400,200,-457.7994,1.676/*
3,400,200,-457.7994,1.676/*
4,400,200,-457.7994,1.676
1, 400, 200, 945/*
2, 400, 200, 945/*
3, 400, 200, 945/*
4, 400, 200, 945
ATTRIBUTE COMP=1, KINE = SG, MWD = *
10,20,30,40,50,60,80,100,120,150,*
170,200,500,700,800,900,1000,2000,*
3000,4000,5000,*
THERMO DATA
STREAM DATA
COMP(WT, KG/MIN)=0.0/4.850/11.450/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=FLORY-P PFReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ IPARM( 1) = REACTOR TYPE
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 3) = KINETICS TYPE
POLYMERS

$ IPARM( 4) = NUMBER OF REVERSIBLE POLYMERIZATION REACTION STEPS
$ IPARM( 5) = NUMBER OF IRREVERSIBLE POLYMERIZATION REACTION STEPS
$ IPARM( 6) = N/A
$ IPARM( 8) = INVOKE REVERSIBLE KINETICS REQ
$ IPARM( 9) = N/A
$ IPARM(10) = N/A

$---------------------------------------------------------------
IPARM 2,1,4,5,5, 0,2,2,0,0, 1,2,3,0,0, 0,0,0,0,4, 0,0,0,0
$---------------------------------------------------------------
$ IPARM(12) = MONOMER 1 ( A1-R1-B1 ) COMPONENT REQ
$ IPARM(14) = N/A
$ IPARM(15) = N/A
$ IPARM(16) = N/A
$ IPARM(17) = N/A
$ IPARM(18) = N/A
$ IPARM(19) = N/A
$ IPARM(23) = N/A
$---------------------------------------------------------------
$ RPARM( 1) = HEAT OF POLYMERIZATION (Hab) MONOMER 1, J/GMOL
$ RPARM( 6) = REACTOR TEMPERATURE, K, REQ
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(11) = PFR LENGTH, M REQ
$ RPARM(12) = PFR DIAMETER, CM REQ
$---------------------------------------------------------------
RPARM 64500., 1.0, 350., 2.5, 0., &
439.15, 0.0, 0.0, 0.0, 0.0, &
100.0,5.0,64500., 0.0, 0.0, 0.3535
-----------------------------------------------------------------
$---------------------------------------------------------------
SUPPLE 1,0.0/0.0/2.2E+05/54392./0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &

POLYMERS
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &

0.0/0.0/0.0/
FLASH UID=PRODUCT
FEED PROD_1

$$
Example 11-5: Type III Step Growth Polymerization in a CSTR

BATCH

used to model the bulk polymerization of BHET to form poly-
ethyleneterephthalate. If solution polymerization is of interest, this
problem can be modified easily to add an input solvent component
to the reactor feed. It is important to note:
mer properties.
1MW5000).
on this statement.
Table 11-5: Kinetic Rate Parameters for BHET Polymerization

Step Rate Constant Prefactor Ao Prefactor Units Ea (J/gmol)
3 k3 4.0800e7 kg/kmol/hr 7.7400e4
Note: The heat of polymerization (-Haa) for BHET is 62500 joule/gmol.
Table 11-6: Equilibrium Constant for Polyethyleneterephthalate

Step Equilibrium Constant Enthalpy H(J/kg) Entropy S(J/kg/K)
POLYMERS
1 K3 -2.4883e4 3.9496e0

BHET CSTR Input File
TITLE PROJ=POLYMER, PROB=PRE-PET, USER=SIM, DATE=12/97

DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, BHET1, FILL=VANKREVELEN
STRUCTURE A, 4(2),514(1)
COMPONENT DATA
LIBID 2,BHET/3,EG
PHASE VLS=1
POLYMER 1, PRE-PET
MWAVG 1, 250
ATTRIBUTE COMP=1, KINE = SG, MWD= *
10,20,30,40,50,70,100,150,200,250,*
300,500,700,1000,2000,3000,4000,*
5000,*
MMWD= PSI0, PSI1, PSI2
THERMO DATA
STREAM DATA
PROP STRM=FEED_0, TEMP(K)=433.15, PRES(ATM)=0.095, *
COMP(WT, KG/MIN)=0.0/7.150/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=PRE-PET CSTReactor
FEED FEED_0
PROD PROD_1
$---------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
POLYMERS
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 1,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, 0,3,0,0,0, 0,0,0,0
$---------------------------------------------------------------

BATCH

$---------------------------------------------------------------
$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A
$ RPARM(14) = N/A
$---------------------------------------------------------------
RPARM 62500., 1100.0, 350., 2.5, 0., 433.15, 0.0, &
0.0, 0.0, 0.0, 0.0, 0.0, 0.0, 0.0, &
0.0, 0.0, 0.0, 0.0
$---------------------------------------------------------------
$---------------------------------------------------------------
SUPPLE 1,0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
4.08E+07/7.740E+04/0.0/0.0/0.0/20.0D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
POLYMERS

FLASH UID=PRODUCT
FEED PROD_1
ISOT TEMP(K)=433.15, PRES(ATM)=0.095$

Example 11-6: Type III Step Growth Polymerization in a PFR
used to model the bulk polymerization of BHET to form polyethyl-
eneterephthalate. If solution polymerization is of interest, this prob-
lem can be modified easily to add an input solvent component to the
reactor feed. It is important to note:
mer properties.
1MW10000).
on this statement.
BHET PFR Input File
TITLE PROJ=POLYMER, PROB=PRE-PET, USER=SIM, DATE=12/97
DIME SI
PRINT RATE=WT
SEGMENT DATA
SEGMENT A, BHET1, FILL=VANKREVELEN
STRUCTURE A, 4(2),514(1)
COMPONENT DATA
LIBID 2,BHET/3,EG
PHASE VLS=1
POLYMER 1, PRE-PET
POLYMERS
MWAVG 1, 400
ATTRIBUTE COMP=1, KINE = SG, MWD= *
10,20,30,50,70,100,150,200,250,*
300,350,400,500,700,800,1000,2000,*
3000,5000,7000,10000,*
MMWD= PSI0, PSI1, PSI2
THERMO DATA
STREAM DATA

COMP(WT, KG/MIN)=0.0/7.150/0.00
UNIT OPERATION
US21 UID=REACTOR_1, NAME=PRE-PET PFReactor
FEED FEED_0
BATCH
PROD PROD_1
$---------------------------------------------------------------
$ = 1 FOR CSTR
$ = 2 FOR PFR
$ IPARM( 4) = N/A
$ IPARM( 5) = N/A
$ IPARM( 6) = N/A
$ IPARM( 8) = N/A
$ IPARM( 9) = N/A
$ IPARM(10) = N/A
$---------------------------------------------------------------
IPARM 2,1,5,0,0, 0,2,0,0,0, 1,2,0,0,0, 0,3,0,0,0, 0,0,0,0
$---------------------------------------------------------------
$---------------------------------------------------------------
POLYMERS

$ RPARM( 8) = N/A
$ RPARM( 9) = N/A
$ RPARM(10) = N/A
$ RPARM(13) = N/A

$ RPARM(14) = N/A
$---------------------------------------------------------------
RPARM 62500., 500.0, 350., 2.5, 0., 453.15, 0.0, &
0.0, 0.0, 0.0, 1000.0, 5.0, 1.0, 1.0, &
62500., 0.0, 0.0, 0.25
$---------------------------------------------------------------
$---------------------------------------------------------------
SUPPLE 1,0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
4.08E+07/7.740E+04/0.0/0.0/0.0/20.0D+01/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/ 0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/0.0/ &
0.0/0.0/0.0/0.0/0.0/0.0
FLASH UID=PRODUCT
FEED PROD_1
POLYMERS

POLYMERS
Chapter 12
Interpreting the Output
The definitions given below will provide a better understanding of

the output reports generated for polymer systems.
Live Chains The live or growing chains contain an active center and
as such can be considered macroradicals. The activity
of the live chains has not been curtailed by a transfer or
termination reaction, and the live chains continue to
incorporate monomer. In the case of the free radical
copolymer, the live chain may be terminated with an
active radical formed from either the A monomer or B
monomer. These radicals are labeled as Live A and
Live B Chains, respectively. In step growth kinetics all
chains are considered live.
Dead Chains The dead or polymer chains are chains that have
undergone a transfer or termination reaction and are no
longer growing. These chains are labeled as Dead
Chains.
Bulk Chains The bulk chain is defined as the average chain in the
product. The properties of the bulk chain are derived
from the arithmetic average of the equivalent proper-
ties of all types of chains found in the product. For free
radical kinetics, the dead chain properties dominate the
POLYMERS
bulk material properties. For step growth kinetics, the

bulk chain properties are equivalent to the live chain
properties.

Kinetic Chain In free radical kinetics, the kinetic chain length is
Length defined as the ratio of the rate of monomer incorpora-
tion into the polymer to the rate of the generation of
BATCH
free radicals. The kinetic chain length indicates the

number of monomer molecules reacted per free radical
generated.
Number Average The number average molecular weight is the molecular

Molecular Weight weight based on the number of monomer units incor-
porated into an average polymer molecule.
Weight Average The weight average molecular weight is the molecular

Molecular Weight weight based on the weight of monomer units incorpo-
rated into an average polymer molecule.
Polydispersity The polydispersity index is the ratio of the weight

Index average molecular weight to the number average
molecular weight. Weight average and number average
molecular weights are defined in a subsequent section.
Polydispersity is an indicator of the molecular unifor-
mity of the polymer product and is reflected in the
breadth of the molecular weight distribution function.
Molecular Weight Kinetic rate data describing initiation, propagation,

Distribution transfer, and termination mechanisms have been used
to obtain number and weight average molecular
weights and polydispersities. An assumed molecular
weight distribution has been described with the
ATTRIB statement of the input file. In the POLYMER
MOLECULAR WEIGHT DISTRIBUTION section of the
Polymethylmethacrylate-Polyvinylacetate CSTR Out-
put File, the simulated or predicted molecular weight
distribution function has been distributed into the
given molecular weight distribution function.
POLYMERS
12-2 Interpreting the Output

Polymer Characterization via Moments
The reaction scheme followed in the production of synthetic poly-
mers can be a complicated set of series and parallel kinetic reaction
steps that lead to a distribution from chain to chain in molecular size
and shape. In this model, the distribution in molecular size or
weight is addressed by the method of moments. The distribution is
characterized by an infinite series, with the coefficients of the series
being the moments. The lower order moments are retained, and
properties of interest are extracted from the moments. The zeroth-
order moment is related to the concentration of the polymer chain
molecules, while the first-order moment is related to the number of
monomer units in the average length polymer chain model. From
these moments, the number average and weight average molecular
weights can be obtained.
The definitions of the moment of the live chains terminated by an
active monomer A and an active B monomer are

*
k = nk [ Pn ]
n=1
and

*
k = nk [ Qn ]
n=1
respectively. The definition of the dead chain moment is

*
k = nk [ Dn ]
n=1
The number and weight average molecular weights for the dead
chains can be obtained as

M n = -----1
0
and

M w = -----2
1
POLYMERS
Molecular weights and polydispersities from these calculations are

given in the output file on the next page for live chains terminating
in monomer A, live chains terminating in monomer B, and for dead
or inactive chains. The corresponding variables for the bulk chains
are obtained from the arithmetic average of the live and dead chains.
The moments on which these calculations are based are present in
the Stream output also presented in the output file.

Polymethylmethacrylate - Polyvinylacetate CSTR Output File
SIMULATION SCIENCES INC. R PAGE P-5
PROJECT COPOLYMER PRO/II 386/EM
BATCH
PROBLEM PMMAC-VAC OUTPUT SIM

POLYMER CSTR SUMMARY 06/01/99
========================================================
UNIT 1, REACTOR, 1st PMMAC-VAC CSTReactor
FEED STREAM S1
PRODUCT STREAM S2
OPERATING CONDITIONS
POLYMER REACTOR TYPE ISOTHERMAL CSTR
TEMPERATURE, K 333.15
VOLUME, M3 1.0000
DUTY, M*KJ/HR -8.678E-03
TOTAL HEAT OF REACTION, M*KJ/HR 8.678E-03
SPACE-TIME, HR, AT OUTLET CONDITIONS 6.9357
SPACE-VELOCITY, /HR, AT OUTLET CONDITIONS .1442
FREE RADICAL COPOLYMERIZATION DATA

POLYMER REACTOR MASS BALANCE
RATES, KG/HR
PERCENT
COMPONENT FEED CHANGE PRODUCT CONVERTED

1 PMMAC-VA POLYMER .000 13.525 13.525
2 MMAC MONOMER A 18.000 -10.341 7.659 57.452
3 VACT MONOMER B 90.000 -3.143 86.857 3.492
4 BNZN SOLVENT 36.000 -1.042E-03 35.999 2.738E-03
5 BOBZ INITIATOR A .180 -3.966E-02 .140 22.032
TOTAL 144.180 .000 144.180
POLYMER REACTOR HEAT BALANCE
FEED PRODUCT
AT OPERATING CONDITIONS
TEMPERATURE, K 333.1300 333.1500
PRESSURE, KPA 506.6265 101.3253
ENTHALPY, M*KJ/HR .0145 .0145
POLYMER CHARACTERIZATION DATA

POLYMERS
COPOLYMER COMPOSITION
NUMBER FRACTION MONOMER A .739

NUMBER FRACTION MONOMER B .261
FREE RADICAL KINETICS
KINETIC CHAIN LENGTH .1535E+03
POLYDISPERSITY DATA

LIVE A CHAINS:
WEIGHT FRACTION IN POLYMER .2127E-04
NUMBER AVERAGE MOLECULAR WT .2865E+05
WEIGHT AVERAGE MOLECULAR WT .5709E+05
POLYDISPERSITY INDEX 1.9924
LIVE B CHAINS:
WEIGHT FRACTION IN POLYMER .1758E-07
DEAD CHAINS:
WEIGHT FRACTION IN POLYMER .1000E+01
BULK CHAINS:
POLYMER MOLECULAR WEIGHT DISTRIBUTION
MOL. WT. WT FRAC

- -
5.0000E+02 .0002
7.0000E+02 .0004
1.0000E+03 .0007
3.0000E+03 .0051
5.0000E+03 .0121
7.0000E+03 .0209
1.0000E+04 .0362
3.0000E+04 .1364
4.0000E+04 .1647
5.0000E+04 .1768
6.0000E+04 .1762
8.0000E+04 .1522
1.0000E+05 .1169
3.0000E+05 .0011
5.0000E+05 .0000
7.0000E+05 .0000
1.0000E+06 .0000
POLYMERS

STREAM WEIGHT COMPONENT RATES 06/01/99
BATCH
==================================================================
STREAM ID POLYMER_MELT S1 S2
NAME
PHASE LIQUID LIQUID LIQUID
FLUID RATES, KG/HR

1 PMMAC-VAC .0000 .0000 .0000
2 MMAC 7.6587 18.0000 7.6587
3 VACT 86.8568 90.0000 86.8568
4 BNZN 35.9990 36.0000 35.9990
5 BOBZ .1403 .1800 .1403
6 1MW500 2.8984E-03 .0000 2.8984E-03
7 1MW700 5.3079E-03 .0000 5.3079E-03
8 1MW1000 .0101 .0000 .0101
9 1MW3000 .0693 .0000 .0693
10 1MW5000 .1640 .0000 .1640
11 1MW7000 .2828 .0000 .2828
12 1MW10000 .4892 .0000 .4892
13 1MW30000 1.8455 .0000 1.8455
14 1MW40000 2.2277 .0000 2.2277
15 1MW50000 2.3913 .0000 2.3913
16 1MW60000 2.3834 .0000 2.3834
17 1MW80000 2.0584 .0000 2.0584
18 1MW100000 1.5809 .0000 1.5809
19 1MW300000 .0144 .0000 .0144
20 1MW500000 4.5020E-05 .0000 4.5020E-05
21 1MW700000 1.0255E-07 .0000 1.0255E-07
22 1MW1000000 .0000 .0000 .0000
TOTAL RATE, KG/HR 144.1800 144.1800 144.1800
TEMPERATURE, K 333.1500 333.1300 333.1500

PRESSURE, KPA 506.6250 506.6250 101.3250
ENTHALPY, M*KJ/HR .0145 .0145 .0145
MOLECULAR WEIGHT 93.1723 85.4614 93.1723
WEIGHT FRAC VAPOR .0000 .0000 .0000
WEIGHT FRAC LIQUID 1.0000 1.0000 1.0000
POLYMERS

POLYMER ATTRIBUTES 06/01/99
==================================================================
STREAM ID POLYMER_MELT S2
NAME
PHASE LIQUID LIQUID
1 PMMAC-VAC FREE RADICAL POLYMER

MMWD - LIVE CHAINS IN SINGLE A BOND IN LIQUID KG-MOL/M3
psi0 6.939E-08 6.939E-08
psi1 1.988E-03 1.988E-03
psi2 113.500 113.500
MMWD - LIVE CHAINS IN SINGLE B BOND IN LIQUID KG-MOL/M3
psi0 5.790E-11 5.790E-11
psi1 1.644E-06 1.644E-06
psi2 9.383E-02 9.383E-02
MMWD - DEAD CHAINS IN SINGLE A BOND IN LIQUID KG-MOL/M3
psi0 1.722E-03 1.722E-03
psi1 93.484 93.484
psi2 7868632.111 7868632.111
POLYMER CHAIN WEIGHT FRACTIONS IN LIQUID
LIVE A 2.127E-05 2.127E-05
LIVE B 1.758E-08 1.758E-08
DEAD A 1.000 1.000
POLYMERS

POLYMERS
Chapter 13
Wiped Film Evaporator
A wiped film evaporator (WFE) separates volatiles (e.g. monomers,

solvents, initiators, inhibitors, etc.) from a viscous liquid. WFEs are
employed when the mass transfer of volatiles out of a liquid is a
rate-limited process governed by the diffusion of the volatiles
through the liquid. A standard application for a WFE is the devola-
tilization of a polymer melt.
A WFE consists of a shaft that passes through the center of a verti-
cal cylindrical drum. A motor turns the shaft powers about its verti-
cal axis. A structure of wiper blades extends from the shaft towards
the interior wall of the WFE. There is a liquid inlet at the top of the
shell and a liquid outlet at the bottom. Vapor is collected in the inte-
rior space of the shell and is drawn out of the top of the WFE under
vacuum. Figure 13-1 illustrates basic WFE design.
Figure 13-1: A Wiped Film Evaporator - Outside and Inside Views
POLYMERS

The polymer melt fed into the top of a WFE is spread over the inte-
rior wall by the rotating wiper blades. The melt is transported axi-
ally by the flow of the bow wave. The bow wave is the accumulated
BATCH
polymer melt that is pushed along on the leading edge of the wiper
blades. For polymer melts of high viscosity, it is usually beneficial
to tilt the wiper blades so that they propel the melt downward rather
than allowing pure gravity-induced flow. The melt in the bow wave
is under shear. This assists in the vertical transport of Bingham and
pseudoplastic fluids by decreasing their viscosity in this region.
The melt devolatilizes as it advances through the WFE. The thin
film of melt on the wall provides a large surface-area-to-volume
ratio that is critical in rate-limited mass transfer. The wiper blades
serve both to transport the melt axially, as well as to remix it, thus
maintaining the maximum concentration of volatiles near the liq-
uid-vapor interface. Mass transfer is increased by the periodic
remixing of the melt as it enters a bow wave and is subsequently
smeared back onto the wall.
PRO/II Wiped Film Evaporator Model
Operating Modes
There are two WFE operating modes: rating and design. In the rat-
ing mode, you specify an existing piece of equipment. The model
can then be used to evaluate the performance of that equipment
under various process conditions. In the design mode, you must
specify the desired outlet weight fraction of consecutive volatile
components. A relative tolerance around this specification may also
be given (default 10-5). The design mode calculations will predict
the required WFE diameter and height to meet the specification.
The design mode can be used with any of the combinations of feed-
back ratio, temperature profile, and blade configuration described in
this section.
One important parameter in the design mode calculations is the bow
wave to film area ratio. The bow wave area is determined by the
POLYMERS
WFE feed volumetric flow rate. The bow wave to film area ratio is
used to determine the design diameter of the WFE directly. You can
specify this parameter or accept the default of 0.05. As this ratio
gets larger, the design diameter decreases. The implications are that
too large a diameter will result in extreme power consumption,
while too small a diameter will require a very long WFE to meet the
specification. Adjustment of this parameter is important in obtain-
13-2 Wiped Film Evaporator

ing an acceptable design. It should be matched to real operating
data if possible.
Another important operating parameter in design mode is shaft rota-
tion speed. A faster rotation translates to greater mass transfer rates.
However, increasing the shaft speed also increases power costs. In
rating mode, a Controller unit might be employed to limit the WFE
shaft speed to the minimum value that meets the product specifica-
tion. A design mode WFE does not attempt to adjust the shaft speed
because choosing an optimum value requires knowledge of process
constraints and utility and power costs. Because of its effect on
operating costs, the shaft speed is a good target for optimization
using the PRO/II Optimizer unit. Figure 13-2 illustrates the rela-
tionship between the volatile concentration using the PRO/II Opti-
mizer consumption and the shaft rotation rate for a specific,
undisclosed case. Your data will vary with each problem; however,
these trends will be similar.
Figure 13-2: Final Concentration and Power as a Function of Rotation Rate
4500 100
90
4000 Final Concentration
80
3500 Power (%)
Concentration (ppm)
70
3000
60
2500
50
2000
40
1500
30
1000 20
500 10
0 0
0 0.5 1 1.5 2 2.5 3
Rotation Rate
Feedback Ratio
PRO/II models a Wiped Film Evaporator unit operation as a series
of levels. A level consists of a number of identical stages equal to
the number of blades in its cross section. Each stage consists of a
POLYMERS
mixing step and a devolatilization step. The mixing step occurs in

the bow wave. The devolatilization step occurs in the film. As a
wiper blade moves through a stage, it picks up the devolatilized
melt in front of it and receives the axial flow from the bow wave of
the stage above. It simultaneously lays down a film of polymer melt
behind it and loses some melt to the stage below it. A parameter
called the feedback ratio determines the degree of mixing that

occurs between the melt entering from the stage above and the melt
that is picked up from the current stage. If the feedback ratio is 1.0,
the entering and picked-up melts are thoroughly mixed. Some of
BATCH
this mixed melt is then wiped behind the blade, and the rest is
passed to the next lower stage. If the feedback ratio is 0.0, the model
is called Surface Renewal. The picked up melt is passed to the next
stage and the bow wave from above is wiped behind the blade. The
PRO/II model allows continuous intermediate values of the feed-
back ratio to simulate imperfect mixing.
Figure 13-3: Surface Renewal Model
From stage n-2 Devolatilization step To stage n+1
Stage n-1 Mixing step Stage n
Figure 13-4: Feedback Model

q
Evaporation element
Q Q
Mixing element
From level n-1
To level n
Stage n in level n
Figure 13-5: Comparison of Feedback and Surface Renewal Models

18
16
Surface Renewal
Concentration (1000 ppm)
14
Feedback
12
POLYMERS
10
0
0 5 10 15 20 25 30 35 40 45 50
Number of Stages

Figure 13-5a: Enlargement of Fig. 13-5 Stages 30-42
320
300
Surface Renewal
280
Feedback
Concentration (ppm)
260
Equilibrium Concentration
240
220
200
180
160
140
120
30 32 34 36 38 40 42
Number of Stages
Blade Configurations
A WFE unit operation can have either vertical, pitched, or alternat-
ing blade configuration. The selection of blade configuration
depends on the properties of the polymer melt. Pitched or alternat-
ing blades are preferred for high-viscosity solutions. Note that
pitched blades with an angle of zero degrees are not the same as
vertical blades, because with vertical blades axial velocity is deter-
mined by gravity flow, while with pitched blades axial velocity is
determined by the pitch angle and rotation rate of the wiper blades.
With pitched or alternating blades, you must specify their pitch
angle or a default of 22.5 degrees will be assumed. Additionally,
you must specify the number of blades in a horizontal cross section
of the WFE or accept the default of eight. If alternating blades are
specified, there must be an even number.
You should also specify blade length, blade width, and wall clear-
ance.
Figure 13-6: Feasible Blade Configurations

Film
POLYMERS
Straight
Wall Pitched
Alternating
Blades

Temperature Profiles
A WFE unit operation can have one of four temperature profiles:
isothermal, adiabatic, jacketed, or user-defined. If isothermal opera-
BATCH
tion is selected, you should specify the operating temperature. If an

operating temperature is not specified, the combined feed tempera-
ture will be used. An adiabatic temperature profile will not allow
heat transfer into the system other than viscous heating of the poly-
mer melt due to the action of the wiper blades. A jacketed tempera-
ture profile includes the viscous heating term as well as a heat
transfer term from a heating/cooling jacket. If the jacketed profile is
used, you should specify the jacket fluid temperature (default:
100C) and the overall heat transfer coefficient between the jacket
fluid and polymer melt (default: 50 W/m2/C). If a user-defined pro-
file is used, you must specify 11 evenly spaced temperatures, the
first being the inlet temperature and the last the outlet temperature.
Component and Melt Physical Properties

The WFE model requires that transport property calculations be
enabled for the thermodynamic set that it will use. Only liquid vis-
cosity and liquid diffusivity need to have methods selected. The
other transport property methods may be set to none, unless they are
required by another unit operation that uses the same thermody-
namic set.
Liquid Viscosity
You can specify liquid viscosity for the polymer as shown in Chap-
ter 5. Take note, however, that this release of PRO/II applies a molar
mixing rule to polymer mixtures. This will cause the system to gen-
erate inaccurate viscosity estimates for a polymer melt containing
volatiles. For this reason, the WFE model allows you to input a zero
shear melt viscosity to be used in the model. This viscosity is inter-
nal to the WFE model and will not be shown in any section of the
output other than the WFE report. If you do not input the zero shear
melt viscosity, the WFE will use the viscosity predicted by PRO/II
as its default.
POLYMERS
Because polymers are non-Newtonian fluids and the WFEs wiper

blades can exert considerable shear on the polymer film, it is impor-
tant to model viscosity as a function of shear rate. The WFE incor-
porates the Carreau model to evaluate viscosity as a function of
shear rate. You should specify relaxation time (default: 0.3) and
power law index (default: 0.3) for the polymer melt. The WFE will
apply the Carreau model to the zero shear melt viscosity discussed

above. The following equation shows the Carreau model for viscos-
ity as a function of shear rate:
n 1
------------
2
2
- = ( 1 + ( ) )
------------------
o
where m is the shear viscosity, o is the zero shear viscosity, is

the infinite shear viscosity, which is equal to zero; g is the shear
rate, l is the relaxation time, and n is the power law index.
The actual viscosity used by the WFE is taken as a weighted aver-
age between the zero shear viscosity and the shear viscosity. The
weighting is determined by the user-supplied Omega parameter. A
value of 1.0 (default) indicates that the shear viscosity will be used.
A value of 0.0 indicates that the zero shear viscosity will be used.
Intermediate values weight the average. You can enter the shear rate
to be used in these calculations or allow them to be calculated by
PRO/II. The shear rate will be calculated by assuming a linear shear
profile between the blade and the wall.
Note: If you specify the melt viscosity for the WFE, the WFE will
not consider the variance of viscosity with temperature. This is
especially important when specifying temperature profiles and
may wish to enter the zero shear melt viscosity as the average
between the inlet and outlet temperatures.
Liquid Diffusivity
The WFE model is very sensitive to the diffusivities of the volatiles
in the polymer melt. The predictive diffusivity method within
PRO/II may give inaccurate results; therefore, you will probably
want to input diffusivity data for the specific system. Refer to the
PRO/II Keyword Manual or the PRO/II Users Guide for informa-
tion on entering diffusivity data. Enter data for the binary pairs of
volatiles (i) diffusing through every other component (j). If the
polymer component is number 1 and the solutes are numbers 2 and
3, you must enter data for D21, D23, D31, and D32. In most cases, you
will enter the same coefficients for all ij pairs of the same ith index.
Example 13-1 shows the proper syntax for the DIFDATA statement.
POLYMERS
These diffusivity values are not expected to be the exact values for
mass diffusivity. Since the film is never entirely stagnant, it is safer
to think of these values for diffusivity as effective diffusivities.
The diffusivity data are probably the best choices for attempting to
tune a WFE model. For design estimates, true diffusivity data will
provide a conservative estimate. Values of Dij on the order of 10-6 to

10-12 are normal. Values much less than 10-12 m2 will predict negli-
gible transfer rates while values much greater than 10-6 m2 are
inconsistent with a diffusion-limited model.
BATCH
Output
Both modes will output the height, diameter, operating pressure,
mass flow of evaporate, heat duty, and shaft power requirements of
the WFE. In addition, the WFE output report will contain a zone
report that will show conditions at periodic levels within the WFE.
The diffusivities for volatile components at the entering and exiting
conditions will also be shown.
Data Required by the Wiped Film Evaporator Unit

Component Data For information about entering polymer
component data, see Chapters 3 and 4.
Thermodynamics Data Select a thermodynamic method that
is suitable for VLE calculations with polymer systems: ALM,
Flory-Huggins, UNIFAC Free Volume, SAFT, or PHSC. For
information about entering thermodynamic data, see Chapter 7.
Enable transport property calculations; the WFE needs only
liquid viscosity and liquid diffusivity. For information about
entering liquid viscosity and liquid diffusivity data, see the
PRO/II Keyword Manual.
WFE Unit Data
Physical Dimensions Height1, Diameter2, Length of
Wiper Blade2, Blade-Wall Clearance2, Blade Width2, Blade
Configuration2, Number of Blades2.
Operating Parameters Shaft Rotation Rate2, Inlet
Pressure2, Inlet Pressure Drop, Shear Rate at Blade Tip2,
Heating/Cooling Jacket Fluid Temperature2, Heat Transfer
Coefficient2, Temperature Profile Type2, Isothermal
Temperature2, Temperature Profile Data (required if user-
POLYMERS
defined profile is selected).

Model Parameters Calculation Mode2, Number of Zones
to Report2, Model Selection2, Power Parameter2.
1. Required entry for rating mode.

2. Default used if these data are omitted.

Viscosity Parameters Viscosity Parameter (Omega)2, Vis-
cosity at Zero Shear2, Viscosity Relaxation Time2, Power
Law Index2.
Design Mode Parameters Starting Component of Design
Specification3, Ending Component of Design
Specification2, Design Target Mass Fraction3, Design Rela-
tive Tolerance2.
Using the Wiped Film Evaporator to Model Systems

The PRO/II WFE can be used to model any polymer devolatiliza-
tion process. It performs best when the volatile concentration in the
feed is at or below 10% by weight. If the volatile concentration gets
too high, the diffusion limited model is not valid, and the WFE may
get inaccurate results. In order to model a WFE with a higher
weight percent volatile streams, model the top portion of the WFE
as a concentration-specified flash, then pass the equilibrium liquid
on to a shorter WFE for the rate-limited modeling.
Wiped Film Evaporator Keyword Input

Keyword Summary
Unit Identification (required)

WFEVAPORATOR UID=uid, {NAME=text}
Feeds and Products (required)

FEED sid, {sid,}
PROD sid1, sid2
Operating Parameters (required)

IPARM i, j, k,
RPARM i, j, k,
Thermodynamic Set Selection (optional)

METHOD SET=setid
POLYMERS
General Information
The wiped film evaporator unit operation provides the capability to
separate solvents and/or monomers from a polymer melt. A wiped
film evaporator should be used when the removal of volatiles from a
viscous polymer melt is diffusion limited. The blades inside the
3. Required entry for design mode.

wiped film evaporator continually mix and spread a thin film of the
melt on the wall of the evaporator. As the melt moves down the
evaporator, the volatiles diffuse out of it and into the vapor space of
BATCH
the evaporator. The volatiles are pulled out of the evaporator under
vacuum.
A mixture of up to ten feed streams is allowed and the unit requires
both an overhead and a bottoms product.
The wiped film evaporator can be modeled under several heating
conditions. It can be modeled isothermally (using the combined
feed temperature or user-specified temperature), adiabatically
(allowing heat input only through friction with the wiper blades), at
steady state (allowing heat input from a heating/cooling jacket), or
with a user-specified temperature profile.
The wiped film evaporator will operate at the lowest of the feed
stream pressures unless an inlet pressure and/or inlet pressure drop
are specified.
Note: The wiped film evaporator models a rate-limited process. It

should receive liquid feeds only. If there is vapor in the feed
stream, it will assume that it was the product of an equilibrium
flash. It will attempt to condense the vapor and set the feed to the
non-equilibrium state specified by the unit operating parameters
(temperature and pressure). Then the wiped film evaporator will
commence modeling the rate-limited devolatilization of the poly-
mer melt as it tries to reach thermophysical equilibrium.
Keyword Description
Unit Identification (required)

WFEVAPORATOR UID=uid, {NAME=text}
This must be the first statement of a Wiped Film Evaporator unit.
Section 42, Unit Operation Input, of the PRO/II Keyword Manual
describes all optional entries.
Feeds and Products (required)

POLYMERS
FEED sid, {sid,}

PROD sid1, sid2
One FEED and one PROD statement are required. At least one feed
stream must be supplied, and a maximum of 10 may be provided. A
bottoms product stream (sid1) and an overhead product stream (sid2)
must be provided on the PROD statement.

Operating Parameters (required)
IPARM i, j, k,
RPARM i, j, k,
Input variables are specified on one IPARM statement for integers
and one RPARM statement for real variables. Table 13-1 describes
the values that can be entered on each statement and the associated
outcome. Entries are separated by commas, unspecified values may
be left blank or filled with a 0 except the first entry on each state-
ment, which must be specified or filled with a zero. The numbers
listed in Table 13-1 in parentheses following the words IPARM or
RPARM indicate the position on the appropriate statement that corre-
sponds to the attribute described. For example, IPARM(1) indicates
that the first position on the IPARM statement is associated with the
rating or design mode choice, IPARM(2) is associated with the choice
of blade pitch, and IPARM(3) is associated with the number of blades
used. The statement IPARM 1,2,8, indicates that rating mode,
pitched blades, and eight blades are to be used.
Variables are further divided into input and output. Real output vari-
ables begin at RPARM(144). These values may be the target of a
SPEC command in a CONTROLLER. IPARM variables are not accessi-
ble to the SPEC system.
The default units of measure defined in the DIMENSION section of
the input file are used for all input unless otherwise specified. Indi-
vidual qualifiers for units of measure are not supported.
POLYMERS

Table 13-1: Wiped Film Evaporator Variables
Variable Rating Design Description
IPARM Input Variables

BATCH
IPARM(1) In In Calculation mode 1. Rating

2. Design
IPARM(2) In In Blade configuration 1. Vertical
2. Pitched
3. Alternating number of
blades.In [IPARM(3)]
must be an even
number if alternating
configuration is used.
IPARM(3) In In Number of blades. Default is 8; see IPARM(2).
IPARM(4) In In Temperature 1. Isothermal
profile type 2. User Defined
3. Adiabatic
4. Steady State
IPARM(5) In In Number of zones in zone report. Default is 20
IPARM(6) In Starting component of design specification.
IPARM(7) In Ending component of design specification.
Default is value of IPARM(6)
RPARM Input Variables

RPARM(1) In* Out Evaporator height
RPARM(2) In Out Inside evaporator diameter. Default is 0.85 m.
RPARM(3) In In Length of pitched blade. Default is evaporator
height in rating mode. In design mode, default
is evaporator height (if given) or 0.5 m if not
given.
RPARM(4) In In Blade-wall clearance
RPARM(5) In In Blade width
RPARM(6) In In Blade pitch (radians). Default is p/8.
RPARM(7) In In Rotation rate (1.5/s)
RPARM(8) In In Inlet pressure. Default is lowest of the feed
stream pressures.
POLYMERS
RPARM(9) In In Inlet pressure drop - pressure drop from inlet

(or lowest feed stream) and the evaporator.
RPARM(10) In In Ratio of bow wave to film area. Default is 0.05.
Default values are underlined.
In columns 2 and 3, In indicates the variable may be input, Out indicates it may be output.
* Required input.
Required input in design mode only.
In user input units.

RPARM(11) In In Viscosity at zero shear. If no input is given for
viscosity, PRO/II data are used.
RPARM(12) In In Shear rate at blade tip (1/s). Default is
calculated from the assumption of a straight
line velocity profile. If no value is entered or if
the value entered is zero the default value will
be used.
RPARM(13) In In Viscosity relaxation time. Default is 0.3.
RPARM(14) In In Power law index. Default is 0.3.
RPARM(15) In In Model selection 1. Complete feedback
model; intermediate
values are acceptable
0. Complete surface
renewal model
RPARM(16) In In Power parameter - Fraction of the calculated
power required to push the bow wave. Does
not effect the power required to overcome the
drag force of the polymer on the blade. Default
is 1.
RPARM(17) In In Viscosity parameter, , where: effective
viscosity = * viscosity under shear + (1 - )
* viscosity at zero shear. Default = 1.
RPARM(18) In In Heating/cooling jacket fluid temperature (e.g.
steam temperature).
RPARM(19) In In Overall heat transfer coefficient between jacket
fluid and polymer melt.
RPARM(20) In In Design target concentration (mass fraction) for
component numbers IPARM(6) through
IPARM(7) in the outlet melt.
RPARM(21) In In Design mode relative tolerance for
convergence on outlet concentration supplied
in RPARM(20).
RPARM(22) In In For isothermal operation, temperature 1 is the
inlet temperature of the evaporator. If no value
is specified for temperature 1, the feed stream
POLYMERS
temperature is used.
* Required input.

RPARM In In Temperatures 2-11. For a user specified
BATCH
(23-32) temperature profile, all these must have values.

Values begin at RPARM(22) and are given at
evenly spaced intervals through RPARM(32).
RPARM Output Variables

RPARM(144) Out Out Evaporator operating pressure.
RPAMR(145) Out Out Shaft power required by evaporator blades.
RPARM(146) Out Out Mass flow of vapor from evaporator.
RPARM(147) Out Out Heat duty required by evaporator. Negative
values reflect a cooling requirement.
RPARM(151) Out Out Mass rate of polymer melt entering evaporator.
RPARM(152) Out Out Mass rate of polymer melt leaving evaporator.
RPARM(153) Out Out Density of polymer melt entering evaporator
RPARM(154) Out Out Density of polymer melt leaving evaporator.
RPARM(155) Out Out Viscosity of polymer melt entering evaporator
RPARM(156) Out Out Viscosity of polymer melt leaving evaporator.
RPARM(157) Out Out Volumetric flow rate of vapor from evaporator.
* Required input.
Example 13-1
This example problem describes a polystyrene polymerization and
separation process, comprised of a polymer CSTR, a flash, a con-
troller, and a WFE. The CSTR produces a continuous polymer
molecular weight distribution that it uses to calculate the polymer
pseudocomponent concentrations in its product stream. The flash
and controller work to reduce the volatile concentration in the prod-
uct stream to the point where the process becomes rate-limited. The
WFE then takes the equilibrium liquid from the flash as its feed.
POLYMERS
Notice that the operating temperature of the WFE is higher than that
of the flash. This puts the feed stream in a non-equilibrium condi-
tion in the WFE. If an equilibrated liquid stream is fed to a WFE,
and the WFE temperature and pressure are not different (higher
and/or lower, respectively) from the feed conditions, the feed will
not devolatilize.

Example 13-1 Input File
TITLE DATE=06/01/99
PRINT STREAM=ALL, RATE=WT, FRACTION=M,WT
DIMENSION SI, STDTEMP=273.15, STDPRES=101.325
SEQUENCE SIMSCI
CALCULATION RVPBASIS=APIN, TVP=310.93
SEGMENT DATA
SEGMENT A,A, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)
COMPONENT DATA
LIBID 2,STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLY 1,PSTYR
PCOMPOSITION 1,1(A)
PHASE VLS=4
MWAVG 1,31000
ATTRIBUTE COMP=1,KINETICS=FR,&
MWD=2000,4000,6000,8000,10000,20000, &
30000,40000,60000,80000,100000,120000,150000,&
200000,300000,400000, MMWD=M0,M1,M2
VISCOSITY(V,K,PAS) TABULAR=300,500/1,0.001,0.001
VISCOSITY(L,C,PAS) TABULAR=30,100,500/1,500,450,300
CONDUCTIVITY(V,K,W/MK) TABULAR=300,500/1,1,1
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE, DIFFUSIVITY=DATA,&
SET=ALM01, DEFAULT
KVAL(VLE)
ALME 3,A,0.06555,0,0
ALMC A,1.56677
DIFFUSIVITY(L)
DIFDATA(K) 2,1,-18.420680744,0,0 / 3,1,-
16.8112428315,0,0 / &
2,3,-18.420680744,0,0 / 3,2,-16.8112428315,0,0 / &
2,4,-18.420680744,0,0 / 3,4,-16.8112428315,0,0 / &
4,1,-20.7232658369,0,0/ 4,2,-20.7232658369,0,0 / &
4,3,-20.7232658369,0,0
STREAM DATA
PROPERTY STREAM=FEED_0, TEMPERATURE=343, PRESSURE=1013.3,&
PHASE=M, COMPOSITION(M,KGM/H)=2,10.4188/4,0.15
UNIT OPERATIONS
POLYMERS
PCSTR UID=PC1
FEED FEED_0
PRODUCT PROD_1
IPARM =1,1,1,,79,,,,1,3,1,2,,3,4,0,0,0,0,0,0
RPARM =69900,200,0,0,0,355,0,0.5,0,0,,,1,
SUPPLEMENTAL=1,1.58E15/128870/0/0/1.05E7/29540/0/0/13,0/ &
0/0/0/0/0/0/0/25,0/0/0/0/0/0/0/0/37,0/0/0/0/45,0/0/0/0/ &
53,0/0/0/0/61,0/0/0/0/69,0/0/0/0/77,0/0/0/0/85,1.05E7/ &
29540/0/0/101,0/0/0/0/109,0/0/0/0/117,0/0/0/0/125,0/0/0/&

133,0/0/0/0/141,0/0/0/0/149,0/0/0/0/157,0/0/0/0/165,0/ &
0/0/0/173,0/0/0/0/181,0/0/0/0/189,0/0/0/0/213,0/0/0/0/ &
229,1.26E9/7030/0/0/245,0/0/0/0/261,0/0/0/0/269,0/0/0/ &
BATCH
0/277,0/0/0/0/285,0/0/0/0/293,0/0/0/0/301,0/0/0/0
FLASH UID=F1
FEED PROD_1
PRODUCT V=VAP1, W=PROD_2
ISO TEMPERATURE=400, PRESSURE=0.666
CONTROLLER UID=CN1
SPEC STREAM=PROD_2,FRACTION(WT), COMP=2,4, VALUE=0.02
VARY FLASH=F1, TEMP, PCT2=10
CPARAMETER IPRINT, NOSTOP
WFEV UID=WFE1
FEED PROD_2
PRODUCT PROD_3,VAP4
IPARM =1,,,1
RPARM =3,0.50,0.2,,,,,,,,500,,,,,,,,,0.0001,1E-5,460
END
POLYMERS

Example 13-1 Output File
PROJECT PRO/II 386/EM
PROBLEM OUTPUT
WIPED FILM EVAPORATOR UNIT SUMMARY 06/01/99
=====================================================================
UNIT 4, 'WFE1'
WIPED FILM EVAPORATOR - RATING MODE
TEMPERATURE PROFILE: ISOTHERMAL
FEEDS PROD_2
PRODUCTS VAPOR VAP4
LIQUID PROD_3
OPERATING CONDITIONS
INLET TEMPERATURE, DEG K 460.0000
OUTLET TEMPERATURE, DEG K 460.0000
EVPORATOR PRESSURE, KPA .6660
REQUIRED SHAFT POWER, KW 2.0861
REQUIRED HEAT DUTY, KW 4.4966
VOLUMETRIC VAPOR FLOW RATE, M3/HR 107.7954
PHYSICAL CONFIGURATION
DIAMETER, M .5000
HEIGHT, M 3.0000
NUMBER OF VERTICAL BLADES 8
BLADE LENGTH, M .2000
BLADE WIDTH, M 5.000E-03
BLADE TO WALL CLEARANCE, M 5.000E-03
FEEDBACK RATIO 1.0000
POWER PARAMETER (GAMMA) 1.0000
VISCOSITY PARAMETER (OMEGA) 1.0000
VISCOSITY RELAXATION TIME, SEC .3000
POWER LAW INDEX .3000
BOW WAVE TO FILM AREA RATIO .0500
SHAFT ROTATION RATE, REV/SEC 1.5000
VELOCITY PROFILE, 1/SEC 471.2389
STREAM PROPERTIES
LIQUID LIQUID VAPOR
POLYMERS
INLET OUTLET OUTLET
STREAM ID PROD_2 PROD_3 VAP4
MASS FLOW RATE, KG/HR 143.2308 140.9980 2.2328
DENSITY, KG/M3 972.6086 976.6445
VISCOSITY, PAS 500.0000 500.0000

DIFFUSIVITY REPORT (DIFFUSIVITIES Ids M2/S)
LIQUID LIQUID
COMPONENT INLET OUTLET
BATCH
STYRENE .1000000E-07 .1000000E-07

EBZN .5000000E-07 .5000000E-07
BOBZ .1000000E-08 .1000000E-08
ZONE REPORT
DISTANCE LIQUID LIQUID LIQUID MASS VAPOR MASS

FROM TOP TEMPERATURE VISCOSITY DENSITY FLOWRATE FLOWRATE
M DEG K PAS KG/M3 KG/HR KG/HR
1 .1529 460.0000 15.6210 975.3908 141.8115 .0419
2 .3061 460.0000 15.6210 976.2098 141.3456 .0138
3 .4508 460.0000 15.6210 976.4450 141.1833 6.0254E-03
4 .6041 460.0000 15.6210 976.5397 141.1040 3.6379E-03
5 .7573 460.0000 15.6210 976.5844 141.0610 1.7342E-03
6 .9021 460.0000 15.6210 976.6076 141.0372 1.0589E-03
7 1.0554 460.0000 15.6210 976.6221 141.0219 6.4036E-04
8 1.2001 460.0000 15.6210 976.6304 141.0131 4.7831E-04
9 1.3534 460.0000 15.6210 976.6359 141.0072 2.4609E-04
10 1.5067 460.0000 15.6210 976.6393 141.0036 1.5046E-04
11 1.6514 460.0000 15.6210 976.6412 141.0015 9.4541E-05
12 1.8047 460.0000 15.6210 976.6425 141.0001 6.9007E-05
13 1.9580 460.0000 15.6210 976.6433 140.9993 3.5557E-05
14 2.1028 460.0000 15.6210 976.6437 140.9988 2.2346E-05
15 2.2560 460.0000 15.6210 976.6440 140.9985 1.3662E-05
16 2.4008 460.0000 15.6210 976.6442 140.9983 1.0246E-05
17 2.5541 460.0000 15.6210 976.6443 140.9982 5.2832E-06
18 2.7074 460.0000 15.6210 976.6444 140.9981 3.2331E-06
19 2.8521 460.0000 15.6210 976.6444 140.9980 2.0327E-06
20 3.0000 460.0000 15.6210 976.6445 140.9980 5.5237E-07
POLYMERS

Appendix A
van Krevelen Structural Groups
Table A-1: van Krevelen Structural Groups

ID Group Structural Formula Name Additional Description Chain
Aliphatic hydrocarbon chain groups
000 -H H Hydrogen Also atomic contribution -
001 >C < | Carbon, 4 -valent, Also atomic contribution -
C aliphatic
|
002 >CH- | Methylidene -
CH
|
003 -CH2- CH2 Methylene General contribution -
004 -CH2-main CH2 Methylene In an aliphatic main chain +
005 -CH2-alpha CH2 Methylene Alpha position in a main +
chain with heterogroups
006 -CH2-beta CH2 Methylene Beta position in a main chain +
with heterogroups
007 -CH2-gamma CH2 Methylene Gamma position in a main +
chain with heterogroups
008 -CH2- Methylene correction Correction for hydrogen +
H-bonding bonded aliphatic main chain;
correction for each methylene group in
POLYMERS
main chain
009 -CH2- Methylene correction Correction for main chain +
one heterogroup with 1 heterogroup per unit;
correction for each methylene group in
main chain
+ Indicates main chain group - Indicates side group
PRO/II 7.1 Add-On Modules Users Guide A-1

Table A-1: van Krevelen Structural Groups (cont.)
010 -CH2- Methylene correction Correction for main chain +
BATCH
two with 2 heterogroups per

heterogroups unit; for each methylene
correction group in main chain
011 -CH2- side CH2 Methylene In side chain -
012 -CH3 CH2 Methyl General contribution -
013 -CH3 replaces -H CH3 Methyl substitution Methyl group as +
replacement for hydrogen
014 >CHCH< | | Ethane, 1,1,2,2- General contribution -
CC tetrasubstituted
| |
H H
015 -CH(CH3)- CH(CH3) Methylmethylene Substituted main chain or +
general contribution
016 -C(CH3)2- C(CH3)2 Dimethylmethylene Substituted main chain +
(free rotation) without steric hindrance for
rotation or general
contribution
017 -C(CH3)2- C(CH3)2 Dimethylmethylene Substituted main chain with +
(hindered) (hindered rotation) steric hindrance for rotation
from one side
018 -C(CH3)2- C(CH3)2 Dimethylmethylene Substituted main chain with +
(two-side (two-side hindered steric hindrance for rotation
hindered) rotation) from two sides, especially
when enclosed between
rings
019 -CH(CH3)2 CH(CH3)2 Isopropyl General contribution -
020 -CH[CH(CH3)2]- CH[CH(CH3)2] Isopropylmethylene Substituted main chain or +
021 -CH(CH3)2 Isopropyl substitution Replacement of hydrogen by +
(subst) isopropyl
022 -C(CH3)3 C(CH3)3 Tert-butyl General contribution -
023 -C(CH3)3 Tert-butyl substitution Replacement of hydrogen +
(subst) by tertbutyl
POLYMERS
024 -CH[C(CH3)3]- CH[C(CH3)3] Tert-butylmethylene Substituted main chain or +

025 -CH[CH2CH Isobutylmethylene Substituted main chain or +
(CH3)2]- CH[CH2CH(CH3)2] general contribution
026 -CH2C(CH3)3 Neopentyl substitution Replacement of hydrogen +
(subst) by neopentyl
A-2 van Krevelen Structural Groups

030 -CH2- (5r) CH2 Methylene Contribution for a -
5-membered ring
031 -CH2- (6r) CH2 Methylene Contribution for a -
6-membered ring
Aliphatic hydrocarbon ring groups
032 Ring 3 3-membered ring Correction for a 3-member -
nonaromatic ring
nonaromatic ring
nonaromatic ring
nonaromatic ring
036 Ring7 7-membered ring Correction for a 7-member -
nonaromatic ring
037 Ring(other) other ring Correction for another -
nonaromatic ring
040 -C5H9, ring Cyclopentyl General contribution -
041 -C6H11, ring Cyclohexyl General contribution -
042 -C6H10(cis)- 1,4-cis- Cyclic main chain unit or +

Cyclohexylene general contribution
043 -C6H10(trans)- 1,4-trans- Cyclic main chain unit or
Cyclohexylene general contribution
044 -CH(C5H9)- Cyclopentylmethylene Substituted main chain or +

POLYMERS
045 -CH(C6H11)- Cyclohexylmethylene Substituted main chain or +

046 -C6H11, ring Cyclohexyl substitution Replacement of hydrogen +

(subst) by cyclohexyl

Unsaturated hydrocarbon groups
BATCH
050 >C= >C= Carbon, aliphatic with Also atomic contribution -

double bond
051 -CH= CH = Methylidene, aliphatic General contribution -
with double bond
052 CH2= = CH2 2 Methylene, aliphatic General contribution -
with double bond
053 =C= =C= Carbon, aliphatic with Also atomic contribution -
two double bonds
054 DoubleBond Double bond correction Correction for double bond -
055 Cis-DoubleBond Cis configuration of Correction for Cis -
double bond configuration of double bond
056 Trans- Trans configuration of Correction for Trans -
DoubleBond double bond configuration of double bond
057 Conjug- Conjugation of double Correction for conjugation -
DoubleBonds bonds of double bonds
058 Conjug- Conjugation of double Correction for conjugation of -
DoubleBonds bonds in ring double bonds in ring for
(Ring) each double bond
060 >C=CH- Vinylidene General contribution -
061 -CH=CH-(cis) Cis-Vinylene Vinylene group in Cis +

configuration; main chain
unit or general contribution
062 -CH=CH-(trans) Trans-Vinylene Vinylene group in Trans +
configuration; main chain
063 -CH=C(CH3)- Cis-Methylvinylene Methylvinylene group in Cis +
(cis) configuration; main chain
064 -CH=C(CH3)- Trans-Methylvinylene Methylvinylene group in +
(trans) Trans configuration; main
chain unit or general
contribution
POLYMERS
065 -C(CH3)=C(CH3) Cis-1,2- 1,2-Dimethylvinylene group +

-(cis) Dimethylvinylene in Cis configuration; main
contribution

066 -C(CH3)=C(CH3) Trans-1,2- 1,2-Dimethylvinylene group +
-(trans) Dimethylvinylene in Trans configuration; main
contribution
070 -C C= Carbon, aliphatic with Also atomic contribution -
triple bond
071 HC HC= Methylidene, aliphatic General contribution -
with triple bond
072 TripleBond Triple bond correction Correction for triple bond -
073 -CC- C=C Ethynylidene Triple bond group; main +
contribution
074 -CCH HC=C Ethynyl Triple bond group -
Aromatic hydrocarbon groups
100 C,ar(exo) Carbon, aromatic, Also atomic contribution -
on the edge of aromatic
system
101 C,ar(endo) Carbon, aromatic, Also atomic contribution -
inside of the aromatic
system
102 CHar Nonsubstituted carbon, Also atomic contribution -
aromatic, on the edge
of aromatic system
105 OrthoSubst Correction for ortho Correction for ortho -
substitution substitution in aromatic ring
106 MetaSubst Correction for meta Correction for meta -
107 ParaSubst Correction for para Correction for para -
110 Ph- Phenyl General contribution -
111 Ph- (subst) Phenyl substitution Replacement of hydrogen by +

phenyl
POLYMERS
112 -Ph-(o) 1,2-Phenylene -
113 -Ph-(m) 1,3-Phenylene Main chain fragment for +

non-conjugated ring or

114 -Ph-(m)c 1,3-Phenylene; one Main chain fragment +
BATCH
side conjugated conjugated from one side
115 -Ph-(m)cc 1,3-Phenylene; two Main chain fragment +

sides conjugated conjugated from both sides
116 -Ph-(p) 1,4-Phenylene Main chain fragment for +

non-conjugated ring or
117 -Ph-(p)c 1,4-Phenylene, one Main chain fragment +
side conjugated conjugated from one side
118 -Ph-(p)cc 1,4-Phenylene two Main chain fragment +

sides conjugated conjugated from both sides
120 -Ph< Phenylidene General contribution -

121 >Ph<(1,2,3,5) Phenyl tetra- General contribution -
substituted in positions
1,2,3,5
122 >Ph<(1,2,4,5) Phenyl tetrasubstituted General contribution -
in positions 1,2,4,5
123 >Ph<(1,2,3,4,5) Phenyl General contribution -

pentasubstituted
124 >Ph<(1,2,3,4,5, Phenyl hexasubstituted General contribution -

6)
130 Naph- Naphthyl -
131 Naph< Naphthylene General contribution, can +

also be used as main chain
fragment
132 Naph<(1,4) 1,4-Naphthylene General contribution, can +
also be used as main chain
fragment
140 2-MePh(1,4)< 2-Methyl-1,4- Main chain fragment or

POLYMERS
Phenylene general contribution
141 1-MePh(2,4)< 1-Methyl-2,4- Main chain fragment or


142 1,3- 1,3-Dimethyl-2,5- Main chain fragment or +
Me2Ph(2,5)< Phenylene general contribution
143 1,3-Ph2Ph(2,5)< 1,3-Diphenyl-2,5- Main chain fragment or +

144 -CH(C6H5)- Phenylmethylene Substituted main chain unit +

or general contribution
145 -CH(p- (4- Methylphenyl) Substituted main chain unit +

C6H4CH3)- methylene or general contribution
146 -C(CH3)(C6H5)- 1-Phenyl-1- Substituted main chain unit +

methylmethylene or general contribution
147 -C(C6H5)2- Diphenylmethylene Substituted main chain unit +

150 MePh- (subst) 4-Methylphenyl Replacement of hydrogen by +

substitution 4- methylphenyl
Groups containing oxygen
200 -O-(al) O Oxygen atom in General contribution; also, +
aliphatic chain atomic contribution and
non-conjugated main chain
fragment, mainly in ethers
201 -O-(ar) O Oxygen atom General contribution; also, +
connected with atomic contribution and
aromatic ring main chain fragment, mainly
in aromatic ethers
POLYMERS
202 -O-(acetal) O Oxygen atom in acetals Special contribution for +

acetals; also, a main chain
unit
203 -O-(epoxide) O Oxygen atom in Special contribution for
epoxides epoxides; also, a main chain
unit

204 O2(ester) Oxygen atoms in esters Special atomic contribution -
BATCH
for esters
210 -OH(pri) OH Primary hydroxyl group -
211 -OH(sec) OH Secondary hydroxyl -
group
212 -OH(tert) OH Tertiary hydroxyl group -
213 -OH(phen) OH Phenolic hydroxyl -
group
214 -OH(hydr.bond) OH Hydrogen bonded Special contribution for -
hydroxyl group hydrogen bonded hydroxyl
group
215 -OH(twin or Correction for twinned Correction for each hydroxyl -
alpha) or alpha positioned group on adjacent or
hydroxyl group hydroxyl- bisubstituted
carbon atoms
220 -CH(OH)- CH(OH) Hydroxymethylene Substituted main chain unit +
221 -CH(OH)(wet)- CH(OH) Hydroxymethylene - Substituted main chain unit +
wet or general contribution
222 -CH(OCH3)- CH(OCH3) Methoxymethylene Substituted main chain unit +
230 -CO- O Carbonyl group General contribution -
||
C
231 -CO-(nc) O Non-conjugated Main chain unit or general +
|| carbonyl group as main contribution
C chain fragment
232 -CO-(c) O One-side conjugated Main chain unit or general +
C chain fragment
233 -CO-(cc) O Two-side conjugated Main chain unit or general +
C chain fragment
234 -CHO O Aldehyde group General contribution -
POLYMERS
||
CH
235 -COO- O Ester group General contribution (not -
|| O conjugated)
C

236 -COO-(acryl) O Acrylic ester group General contribution for -
|| O acrylic ester group
C
237 -COO-(nc) O Non-conjugated ester Main chain unit (not +
|| group as main chain conjugated) or general
CO fragment contribution
238 -COO-(c) O One-side conjugated Main chain unit (one-side +
|| ester group as main conjugated)
CO chain fragment
239 -COO-(cc) O Ester group as main Main chain contribution +
|| chain fragment (between aromatic rings -
CO between two aromatic rigid system)
rings
240 -COOH O Carboxylic group General contribution -
||
C OH
241 HCOO- O Formic group General contribution -
||
HCO
242 -OCOO- O Carbonate group Main chain unit or general +
|| contribution
OCO
243 -COOCO-(nc) O O Anhydride group (not General contribution or main +
|| || conjugated) chain unit
CO C
244 -COOCO-(c) O O Anhydride group General contribution or main +
|| || (conjugated on one chain unit
CO C side)
245 -COOCO-(cc) O O Anhydride group General contribution or main +
|| || (conjugated on two chain unit
COC sides)
246 -OCOCOO- O O Oxylate group Main chain unit or general +
|| || contribution
- O C C O-
250 -CH(OOCCH3)- Methylene acetate Substituted main chain unit +
POLYMERS
251 -CH(COOCH3)- Methyl Substituted main chain unit +

methylenecarboxylate or general contribution

252 -C(CH3)(COO Methyl Substituted main chain unit
BATCH
CH3)- methylmethylene or general contribution

carboxylate
Groups containing fluorine

300 -F F Fluoride General contribution -
301 -F(disubst) F Fluoride (disubstituted) Each of two fluoride atoms -
substituted to a carbon atom
302 -F(trisubst) F Fluoride (trisubstituted) Each of three fluoride atoms -
substituted to a carbon atom
303 -F(double) Fluoride (double bond) Correction for fluoride -
connected to a carbon atom
with a double bond
304 -F(subst) Fluorine (aliphatic Tentative contribution for +
substitution) hydrogen replacement by
fluorine
310 -CHF- CHF Fluoromethylene General contribution or main +
chain fragment
311 -CF2- CF2 Difluoromethylene General contribution or main +
chain fragment
312 -CF2-(per) CF2 Difluoromethylene General contribution or main +
(perfluoro) chain fragment for perfluoro
compounds
313 -CF3 CF3 Trifluoromethyl General contribution -
314 -CF3(per) CF3 Trifluoromethyl General contribution for -
(perfluoro) perfluoro compounds
315 -CF(CF3)- CH(CF3 ) Difluoromethylene General contribution or main +
(perfluoro) chain fragment
316 -CH=CF- CH = CF Fluorovinylene General contribution or main +
chain fragment
317 -CF=CF- CH = CF 1,2-Difluorovinylene General contribution or main +
chain fragment
POLYMERS

Groups containing chlorine (or fluorine and chlorine)
320 -Cl(al) Cl Chlorine (aliphatic) General contribution for -
chlorine in aliphatic
compound
321 -Cl(pri) Cl Chlorine (primary) Contribution for chlorine -
connected to a primary
aliphatic carbon atom
322 -Cl(sec) Cl Chlorine (secondary) Contribution for chlorine -
connected to a secondary
323 -Cl(disubst) Cl Chlorine (disubstituted) Contribution for each of two -
chlorines connected to an
324 -Cl(trisubst) Cl Chlorine Contribution for each of -
(trisubstituted) three chlorines connected to
an aliphatic carbon atom
325 -Cl(double) Chlorine (double bond) Correction for chlorine -
connected to a double
bonded carbon atom
326 -Cl(ar) Cl Chlorine (aromatic) Contribution for chlorine -
connected to an aromatic
carbon atom
327 -Cl(subst, aliph) Chlorine (aliphatic Tentative contribution for +
substitution) hydrogen replaced by
chlorine in an aliphatic
compound
328 -Cl(subst, arom) Chlorine (aromatic Tentative contribution for +
substitution) hydrogen replaced by
chlorine in an aromatic
compound
330 -CH2Cl CH2Cl Chloromethyl General contribution -
331 -CHCl2 CHCl2 Dichloromethyl General contribution -
332 -CCl3 CCl3 Trichloromethyl General contribution -
333 -CHCl- CHCl Chloromethylene General contribution and +
POLYMERS
main chain fragment

334 -CCl2- CCl2 Dichloromethylene General contribution and +
main chain fragment
335 -CFCl- CFCl Chlorofluoromethylene General contribution and +
main chain fragment

336 -CH(CH2Cl)- CH(CH2Cl) 2-Chloroethylene-1,1 General contribution and +
BATCH
main chain fragment

337 -C(CH2Cl)2- C(CH2Cl)2 Di(chloromethyl)- General contribution and
methylene main chain fragment
338 -CH=CCl- CH=CCl Chlorovinylene General contribution and +
main chain fragment
340 2-ClPh(1,4)< 2-Chloro-1,4- General contribution and
Phenylene main chain fragment
341 1-ClPh(2,4)< 1-Chloro-2,4- General contribution and +

Phenylene main chain fragment
Groups containing bromine

350 -Br(al) Br Bromine General contribution for -
(aliphatic) bromine in an aliphatic
compound
351 -Br(disubst) Br Bromine Contribution for each of two -
(disubstituted) bromines connected to an
352 -Br(trisubst) Br Bromine Contribution for each of -
(trisubstituted) three bromines connected to
353 -Br(double) Br Bromine Correction for bromine -
(double bond) connected to a double-
bonded carbon atom
354 -Br(ar) Br Bromine Contribution for bromine -
(aromatic) connected to an aromatic
carbon atom
355 -Br(subst) Bromine Tentative contribution for +
(substitution) hydrogen replaced by
bromine
POLYMERS

Groups containing iodine
360 -I I Iodine General contribution for -
iodine
361 -I(disubst) I Iodine Contribution for each of two -
(disubstituted) iodines connected to an
362 -I(trisubst) I Iodine Contribution for each of -
(trisubstituted) three iodines connected to
363 -I(double) Iodine Correction for iodine -
(double bond) connected to a double-
bonded carbon atom
Groups containing nitrogen (or nitrogen and oxygen)
400 -N< N< Nitrogen atom General and atomic -
contribution
401 -N= N= Nitrogen atom with General and atomic -
double bond contribution
402 N(ar) Nitrogen atom in General and atomic -
aromatic ring contribution
403 -NH- NH Imine group General contribution and +
main chain fragment
404 -NH2 NH2 Amine group General contribution -
405 -CN C=N Nitrile group General contribution -
406 -CN(subst) Nitrile group Hydrogen substituted by a +
(substitution) nitrile group
407 -CH(CN)- CH(CN) Nitrilmethylene General and main chain +
fragment contribution
408 -C(CN)2- C(CN)2 Dinitrilmethylene General and main chain +
fragment contribution
410 -CONH-(nc) O N-substituted non- Main chain contribution (not +
|| conjugated amide conjugated) or general
C NH group as a main chain contribution
fragment
POLYMERS
411 -CONH-(c) O N-substituted one-side Main chain contribution +

|| conjugated amide (one-side conjugated)
C NH group as a main chain
fragment

412 -CONH-(cc) O N-substituted two-side Main chain contribution +
BATCH
|| conjugated amide (two-side conjugated -

C NH group as a main chain between rings in rigid
fragment aramides)
413 -CONH-(wet) O N-substituted wet Main chain unit or general +
|| amide group contribution
C NH
414 -OCONH- O Carbonimide as main Main chain or general +
|| chain fragment contribution
O C NH
415 -NHCONH- O Urenide as main chain Main chain or general +
|| fragment contribution
NH C NH
416 -CONH2 O Amide group General contribution -
||
C NH2
417 -CON< O N,N-disubstituted General contribution -
|| amide group
CN<
418 HCON< O N,N-disubstituted General contribution -
|| formamide group
HCN<
419 HCONH- O N-substituted General contribution -
|| formamide group
H C NH
420 >NCON< O N,N,N,N- General contribution -
|| tetradisubstituted
>NCN< urenide group
421 -N=C=O N =C = O Isocyanide group General contribution -
422 -NHNH- NH NH Hydrazine group Main chain unit or general +
(N,N'-disubstituted) contribution
423 >NNH2 > N NH2 Hydrazine group General contribution -
(N,N-disubstituted)
424 -NHNH2 NH NH2 Hydrazine group General contribution -
(N-substituted)
POLYMERS
425 -N=N- N=N Azo group General contribution -

426 N N N=N Diazo group General contribution -
427 -N=C=N- N=C=N General contribution -

428 >C=N-N=C< >C=NN=C< Azine group General contribution -

430 -NO2 (al) NO2 Nitro group in aliphatic General contribution -
compounds
431 -NO2 (ar) NO2 Nitro group in aromatic General contribution -
compounds
432 -ONO2 ONO2 Nitrate group General contribution -
433 -ONO ON=O Nitrite group General contribution -
440 -Pyr Pyridine group General contribution -
(substituted in
position 4)
441 -Pyrrol Pyrrolidone group General contribution -
(substituted)
442 -Carbazole Carbazole group (N- General contribution -

substituted)
443 -Quinoxaline< Quinoxaline (2,3,6 - General contribution -

trisubstituted)
Groups containing sulfur (or sulfur and oxygen)

450 -S- S Sulphide Main chain fragment or +
451 Sar Sulphur (aromatic) General contribution -
452 -SS- SS Disulphide Main chain fragment and +

453 -SH SH Mercaptyl group General contribution -
460 -SO- O Sulphinyl group General contribution -
||
S
461 -SO2- O Sulphonyl group (not Main chain fragment and +
|| conjugated) general contribution
S
||
O
POLYMERS
462 -SO2-(c) O Sulphonyl group (one- Main chain fragment and +

|| side conjugated) general contribution
S
||
O

463 -SO2-(cc) O Sulphonyl group (two- Main chain fragment and +
BATCH
|| side conjugated) general contribution

S
||
O
464 -SO3H O Sulphonic group General contribution -
||
S OH
||
O
Groups containing silicon
480 Si | Silicone group General contribution -
Si
|
481 -Si(CH3)2- Si(CH3)2 Dimethylsilicone group Main chain fragment and +
(not sterically hindered) general contribution
482 -Si(CH3)2-(sh) Si(CH3)2 Dimethylsilicone group Main chain fragment and +
(sterically hindered) general contribution
Complex groups (combinations of elementary groups)
500 -1,4-C6H4-CH2- Main chain fragment and +
1,4-C6H4- general contribution
501 -1,4-C6H4- Main chain fragment and +
C(CH3)2- general contribution
1,4-C6H4-
C(CH3)(C6H5)- general contribution
1,4-C6H4-
C(C6H5)2- general contribution
1,4- C6H4-

1,4-C6H4-
POLYMERS
505 -1,4-C6H4 Main chain fragment and +

[-C(CH3)2- general contribution
1,4- C6H4]2-
506 -1,4-C6H4- 4,4-diphenylene group Main chain fragment and +
507 -1,4-C6H4-CO- Main chain fragment and +


508 -1,4-C6H4-O- Main chain fragment and +
509 -1,4-C6H4[-O- Main chain fragment and +
1,4- C6H4]2- general contribution
510 -1,4-C6H4-S- Main chain fragment and +

511 -1,4-C6H4-SO2- Main chain fragment and +
1,4- C6H4- general contribution
512 -CH2-1,4-C6H4- Flexible main chain fragment +
CH2- or general contribution
513 -O-1,4-C6H4-O- Flexible main chain fragment +
514 -OCO-1,4- Flexible main chain fragment +
C6H4-COO- or general contribution

517 -NHCO-1,4- Flexible main chain fragment +

C6H4-CONH- or general contribution
518 -NHCO-1,3- Flexible main chain fragment +

C6H4-CONH- or general contribution
519 -O-1,4- Main chain fragment in rigid +

C6H4-CO- arylates or general
contribution
520 -O-1,3-C6H4- Main chain fragment in rigid +
CO- arylates or general
contribution
521 -NH-1,4-C6H4- Main chain fragment in rigid +
CO- aramides or general
contribution
POLYMERS
NHCO-1,4- aramides or general

C6H4-CO- contribution
NHCO-1,3- aramides or general
C6H4-CO- contribution

600 -C3H4N2O- 2-Imidazolidone group Main chain fragment or +
BATCH
(1,3-disubstituted) general contribution
601 -C4H2N2O2- Uracil group (1,3- Main chain fragment or +

disubstituted) general contribution
602 -C5H4N2O2- Thymine group (1,3- Main chain fragment or +

disubstituted) general contribution
603 -C2N2O- 1,2,4-oxadiazol group Main chain fragment or +

(one-side conjugated)
604 -C2N2S- 1,2,4-thiodiazol group Main chain fragment or +

(two-sides conjugated)
605 -C3HNS- Thiazol group (2,5- Main chain fragment or +

disubstituted) (two- general contribution
sides conjugated)
606 -C8H3NO2- Phthalimide group (N Main chain fragment or +

and ring disubstituted) general contribution
(not conjugated)
607 -C8H3NO2-(c) Phthalimide group (N Main chain fragment or +

and ring disubstituted) general contribution
(one-side conjugated)
608 -C9H12N2O2- 5-cyclohexylhydantoin Main chain fragment or +

group (1,3- general contribution
disubstituted)
609 -C7H4N2O- 2(3H)-benzimidazolone Main chain fragment or +

group (1,3- general contribution
disubstituted)
POLYMERS
610 -C11H6N2O- Main chain fragment or +


611 -C10H2N2O4- Pyromellitic diimide Main chain fragment or +
(N,N-disubstituted) general contribution
612 -C7H4N2- Benzimidazole group Main chain fragment or +

(2- and ring general contribution
disubstituted) (two-
sides conjugated)
613 -C8H4N4- Benzimidazole group Main chain fragment or +
614 -C8H2N2S2- Benzothiazole group Main chain fragment or +

Special contributions of additional effects
700 Even(-O-) Special contribution of Main chain contribution +
a sequence of an even
number of CH2 units in
a main chain with ether
groups
701 Even(-S-) Special contribution of Main chain contribution +
a main chain with
thioether groups
702 Even(-OCOO-) Special contribution of Main chain contribution +
a main chain with
carbonate or equivalent
groups
703 Even(-OCONH-) Special contribution of Main chain contribution +
a main chain with
carbonamide or
equivalent groups
POLYMERS
704 Odd(-O-) Special contribution of Main chain contribution +

a sequence of an odd
a main chain with ether
groups

705 Odd(-S-) Special contribution of Main chain contribution +
BATCH
a main chain with
thioether groups
706 Odd(-OCOO-) Special contribution of Main chain contribution +
a main chain with
carbonate or equivalent
group
707 Odd(-OCONH-) Special contribution of Main chain contribution +
number of CH2 unit in a
main chain with
carbonamide or
equivalent groups
708 Backbone atom Special contribution of -
each backbone atom (in
a main chain)
709 Cross link Special contribution of -
a side-chain bivalent
group
710 Side group Special contribution of -
side-chain group
711 Small molecule Special contribution for -
a small molecule - (not
polymeric)
712 Symmetry(1p) One plane of symmetry -
- special contribution
713 Symmetry(2p) Two planes of -
symmetry - special
contribution
714 Symmetry(mp) More than two planes -
of symmetry - special
contribution
POLYMERS

Index
A Binary parameters for homopolymer segment-solvent

pairs , 7-22
Binary temperature-dependent parameters , 7-12
Addition polymerization , 1-1
Blades
Additivity principle , 3-1 configurations , 13-5
Advanced lattice model length , 13-5
attributes , 7-2 number of , 13-5
example , 7-6 width , 13-5
K-value data , 7-3 Bow wave , 13-2
METHOD statement , 7-2
Bulk chains , 12-1
overview , 7-2
Bulk polymerization , 1-4
pure component properties , 7-2
two liquid phase behavior , 7-2
typical usage , 7-2
Application ranges
C
UNIFAC free volume model , 7-7
Attributes Carreau model , 13-6
advanced lattice model , 7-2 Chain length , 7-17
equations of state , 7-16 kinetic , 12-2
example of MWD or MMWD , 5-6 Chain polymerization
example of PCFRAC , 5-7 See Addition polymerization
Flory-Huggins model , 7-10 Chain propagation , 9-8
MWD or MMWD , 5-3, 5-4
Chain termination , 9-10
PCFRAC , 5-5, 5-6
Chain transfer , 9-8
Chains
Average molecular weight , 2-3, 12-2, 12-3
bulk , 12-1
POLYMERS
Axial velocity , 13-5

dead , 12-1
live , 12-1
types of , 5-11, 11-3
B Component data
entering , 2-2, 3-8
Binary energetic parameters , 7-3 estimating polymer properties , 3-1
Binary interaction parameters, types , 7-26 supplying polymer pure properties , 4-1
Component properties
PRO/II 7.1 Add-On Modules Users Guide I-1

liquid diffusivity , 13-7 K-values , 7-17
liquid viscosity , 13-6 METHOD statement , 7-17
options , 13-6 options , 7-15
Components parameters for homopolymer segments , 7-20
adding , 5-10 parameters for solvents , 7-17
solid , 5-2 pure component properties , 7-16
Concentration as a function of rotation rate , 13-3 typical usage , 7-16
Condensation polymerization , 1-2 Equilibrium constants

nylon 6 , 11-13
Coordination Complex Kinetic
mechanisms , 10-4 Example
advanced lattice model , 7-6
Coordination Complex Kinetics
coordination copolymerization in a CSTR , 10-19
catalyst initiation , 10-7
coordination homopolymerization in a
chain propagation at catalyst site , 10-7 CSTR , 10-15
chain termination , 10-7
coordination polymerization in a CSTR , 10-24
chain transfer at catalyst site , 10-7
coordination polymerization in a PFR , 10-31
Coordination complex kinetics equations of state , 7-22
polymerization via , 10-2 Flory-Huggins model , 7-15
Copolymer , 1-3 free radical copolymerization in CSTR , 9-33
Correlation, gel and glass effects , 9-11 free radical copolymerization in PFR , 9-38
Cross-linking , 1-3 free radical homopolymerization in CSTR , 9-23
free radical homopolymerization in PFR , 9-29
CSTR , 2-7, 8-1, 9-1, 10-1, 11-1, 13-14
MWD or MMWD attributes , 5-6
coordination copolymerization , 10-19
PCFRAC attributes , 5-7
coordination homopolymerization , 10-15
type 1 step growth polymerization in CSTR , 11-12
coordination polymerization , 10-24
type 1 step growth polymerization in PFR , 11-15
free radical copolymerization , 9-33
free radical homopolymerization , 9-23
mass and energy balances , 8-2
type 1 step growth polymerization , 11-12
UNIFAC free-volume model , 7-9
van Krevelen structural groups , 3-4
wiped film evaporator , 13-14
D
F
Dead chains , 12-1
Devolatilization , 13-1
Feedback model , 13-4
Diffusivity , 13-6
Feedback ratio , 13-3
Flory-Huggins model
attibutes , 7-10
E example , 7-15
POLYMERS
K-values , 7-11
Emulsion polymerization , 1-4, 5-3 METHOD statement , 7-10
Energy operating equations overview , 7-9
CSTR , 8-2 typical usage , 7-10
PFR , 8-4 Flowsheet, building the , 2-6
Energy parameter , 7-17 Free radical initiation , 9-7
Equations of state Free radical kinetics
attributes , 7-16 mechanisms , 9-2
example , 7-22 polymerization via , 9-2

user-added subroutines , 9-13 K
Free radical polymerization , 1-1, 9-2
MWD or MMWD attributes , 5-3
Keyword summary
PCFRAC attributes , 5-5
example , 3-4
schemes , 9-3
invariant properties , 4-2
Free radical recombination , 9-9 METHOD statement , 7-2, 7-8, 7-10, 7-17
Fugacity , 7-3, 7-11 polymer attributes , 4-1
Fugacity coefficient , 7-3, 7-8, 7-11 POLYMER components , 3-2
polymer definition , 4-1
PRINT statement , 6-1
G stream polymers , 5-2
STRUCTURE statement , 3-2
temperature-dependent properties , 4-2
Gel and glass effects , 9-10
user-added subroutines , 9-13, 10-9, 11-8
Group transfer polymerization , 1-1 van Krevelen group contribution method , 3-1
van Krevelen structural groups , 3-3
VANKRE qualifier , 3-2
H wiped film evaporator , 13-9
Kinetic chain length , 12-2
Hardness , 1-3 Kinetic data, entering , 2-7
Heat Kinetic rate constants , 8-2, 11-7
conditions of wiped film evaporator , 13-10
Kinetic rate parameters
controls , 1-2 caprolactum polymerization , 11-12
removal/addition of , 1-1 ethylene polymerization , 9-30
Heat transfer coefficient , 8-5 methylmethacrylate , 9-34
Henrys law data , 7-3, 7-8, 7-11 vinyl acetate polymerization , 9-34
High-viscosity solutions , 13-5 Kinetic type , 2-4
Homopolymer , 1-3 Kinetics
Homopolymer segments Coordination complex , 10-2
binary parameter for , 7-22 free radical , 9-2
equations of state parameters for , 7-20 stepwise , 11-2
Homopolymer segment-solvent pairs , 7-4, 7-13 K-values
advanced lattice method , 7-3
equations of state , 7-17
I Flory-Huggins model , 7-11
UNIFAC free volume method , 7-8
Input description
invariant properties , 4-5 L
polymer attributes , 4-3
polymer definition , 4-2
temperature-dependent properties , 4-5 Live chains , 12-1, 12-3
POLYMERS
Invariant properties
input description , 4-5
keyword summary , 4-2 M
types , 4-1
Ionic polymerization , 1-1 Macromolecules , 1-2
IPARM variables , 9-13, 10-9, 11-8 Mass operating equations
definitions , 13-11 CSTR , 8-2
entering , 2-7 PFR , 8-4
I-3 Index
Melt physical properties
liquid diffusity , 13-7
P
liquid viscosity , 13-6
options , 13-6 Pairs
homopolymer segment-colvent , 7-4, 7-13
METHOD statement
advanced lattice model , 7-2 Parameters
equations of state , 7-17 binary interaction , 7-3
Flory-Huggins model , 7-10 equations of state for solvents , 7-17
UNIFAC free volume model , 7-8 Omega , 13-7
operating, wiped film evaporator , 13-9, 13-11
Mole balances , 8-3, 8-4
pure chain length , 7-17
Molecular weight distribution , 12-2
pure energy , 7-17
calculating , 2-3, 4-8
pure size , 7-17
entering data , 2-4, 4-9, 5-10
pure species , 7-26
moments , 4-1, 5-1
PCFRAC attributes
providing , 4-1
free radical , 5-5
Molecular weight fractions , 5-11 step-growth polymerization , 5-6
Molecular weight, average , 2-3, 12-3 Ziegler-Natta , 5-5
Moment expansions , 8-7 Perturbed hard-sphere-chain (PHSC) theory
Moments , 8-3, 8-4, 12-3 See Equations of state
Monomers , 1-1, 1-2, 1-3, 9-2 PFR , 8-1, 9-1, 10-1, 11-1
coordination polymerization , 10-31
MWD or MMWD attibutes
Ziegler-Natta polymerization , 5-4 free radical copolymerization , 9-38
free radical homopolymerization , 9-29
MWD or MMWD attributes
mass and energy balances , 8-4
example , 5-6
free radical polymerization , 5-3
step growth polymerization , 5-4
PFRAC attributes, example , 5-7
N Phase equilibrium calculations , 7-1
Poly(vinylchloride) , 1-2
Non-Newtonian fluids , 13-6 Polyamides , 1-2
Nylon 6 , 11-13 Polydispersity index , 12-2
Polyesters , 1-2
Polyethylene , 1-2
O Polymer blend , 1-3
Polymer chain , 1-3
Omega parameter , 13-7 Polymer characterization conversion , 6-2
Operating data , 2-7 Polymer characterization conversion utility , 5-1
Operating modes, wiped film evaporator , 13-2 Polymer characterization via moments , 12-3
Operating parameters, wiped film evaporator , 13-9, Polymer components
POLYMERS
13-11 adding , 2-2

Optimizer unit , 13-3 deleting , 2-3
Output reports entering distribution data , 2-4, 4-9
interpreting , 12-1 enterring data , 3-8
options , 6-1 kinetic type , 2-4
PRINT statement , 6-1 Polymer melt , 13-2
PWRATE and PCONV statements , 6-2
Polymer module
Output, wiped film evaporator , 13-8 building the flowsheet , 2-6

calculating molecular weight distributions , 2-3, Polystyrene , 1-2
4-8 Polyurethane , 1-2
choosing thermodynamic methods , 2-5
Population balance , 8-6
entering component data , 2-2
entering polymer segment data , 2-2 Power as afunction of rotation rate , 13-3
entering PWRATE and PCONV values , 6-2 Poynting correction , 7-3, 7-11
entering stream polymer data , 5-9 Predicted properties
general approach for using , 2-1 equations of state , 7-16
selecting a thermodynamic method , 7-24 Pressure effects , 8-5
selecting polymer reactors , 2-6 PRINT statement , 6-1
selecting the units of measure , 2-1
PRO/II
using in PRO/II , 2-1
polymer characterization conversion utility , 5-1
Polymer properties user-added subroutines , 9-13, 10-10, 11-8
estimating component data , 3-1 using the polymer module in , 2-1
supplying pure component data , 4-1
wiped film evaporator , 13-2
Polymer reactors
Properties predicted by van Krevelen method , 3-5
selecting , 2-6
Pseudocomponents , 2-3
Polymer segments
definition , 1-3 Pure chain length parameter , 7-17
entering data , 2-2, 3-8 Pure component properties , 7-10
STRUCTURE statement , 7-7 advanced lattice model , 7-2
Polymer stream data , 5-1 equations of state , 7-16
Polymerization
addition or chain , 1-1 Pure energy parameter , 7-17
bulk , 1-4 Pure size parameter , 7-17
chain types , 11-3 Pure species parameters , 7-26
condensation or step growth , 1-2
emulsion , 1-4
exothermic reactions , 1-2
free radical , 9-2
MWD or MMWD attributes for free radical , 5-3
R
MWD or MMWD attributes for step growth , 5-4
MWD or MMWD attributes for Ziegler-Natta , 5-4 Rate constants, kinetic , 8-2, 11-7
PCFRAC attributes for free radical , 5-5 Rate-limited process , 13-10, 13-14
PCFRAC attributes for step growth , 5-6 Reactions
PCFRAC attributes for Ziegler-Natta , 5-5 chain propagation , 9-8
schemes , 9-3 chain termination , 9-10
solution , 1-4 chain transfer , 9-8
suspension , 1-4 chain transfer and reinitiation , 9-4
via Coordination complex kinetics , 10-2 decomposition and initiation , 9-3
via free radical kinetics , 9-2 free radical initiation , 9-7
via stepwise kinetics , 11-2 free radical recombination , 9-9
Polymers gel and glass effects , 9-10
POLYMERS
derivatives , 1-2 propagation , 9-4

hardness , 1-3 side , 9-6
introduction , 1-1 termination , 9-6
keyword summary , 4-1 Reactive center , 9-2
properties , 1-3 Reactor models or Reactors
synthesis methods , 1-1, 1-2 See User-added polymer reactor models
terminology , 1-3
Reactor unit US21 , 9-23, 10-15, 11-12
thermoplastic , 1-1
Reactors, selecting polymer type , 2-6
thermosetting , 1-2
I-5 Index
Report options SUPPLE variables , 9-13, 10-9, 11-8
output , 6-1 entering , 2-7
PRINT statement , 6-1 Surface renewal model , 13-4
Suspension , 5-3
Rotation rate, wiped film evaporator , 13-3
Suspension polymerization , 1-4
RPARM variables , 8-5, 9-13, 10-9, 11-8
definitions , 13-11
entering , 2-7 T
S Temperature profiles , 13-6

Temperature-dependent properties , 3-5
input description , 4-5
SCHULZ-FLORY distribution , 5-1
keyword summary , 4-2
Segment data , 2-3 types , 4-1
Segment-solvent pairs , 7-4, 7-13, 7-22 Terminology , 1-3
Shear rate , 13-7 Thermodynamic method
Simulation binary energetic parameters , 7-3
creating for a polymer system , 2-1 choosing , 2-5
Size correction factor , 7-3 equations of state , 7-15
Solid components , 5-2 fugacity coefficient , 7-3, 7-8, 7-11
Henrys law , 7-3, 7-8, 7-11
Solution polymerization , 1-4
homopolymer segment-solvent pairs , 7-4, 7-13
Solvents
K-values , 7-3, 7-8, 7-11
equations of state for , 7-17
METHOD statement , 7-2, 7-8, 7-10, 7-17
Statistical associating fluid theory (SAFT) Poynting correction , 7-3, 7-11
See Equations of state
selecting , 7-24
Step growth polymerization wiped film evaporator keywords , 13-9
chain types , 11-3
Thermophysical properties , 7-1
kinetic mechanisms , 11-5
MWD or MMWD attributes , 5-4 Thermoplastic polymer
PCFRAC attributes , 5-6 creating , 1-1
See Also Condensation polymerization definition , 1-3
Stepwise kinetics Thermosetting polymer
polymerization via , 11-2 creating , 1-2
user-added subroutines , 10-10, 11-8 definition , 1-3
Stream data Two liquid phase behavior , 7-10
supplying , 5-9 advanced lattice model , 7-2
Stream output report equations of state , 7-16
options , 6-1 UNIFAC free volume method , 7-7
PRINT statement , 6-1
Streams
U
POLYMERS
emulsion/suspension , 5-3
entering PWRATE and PCONV , 6-2 UNIFAC free volume model
limits for wiped film evaporator , 13-10 application ranges , 7-7
MWD or MMWD attributes , 5-3, 5-4 attributes , 7-7
PCFRAC attributes , 5-5, 5-6 example , 7-9
polymer keyword summary , 5-2 K-values , 7-8
polymer solids in , 5-1 METHOD statement , 7-8
supplying data , 5-1 overview , 7-7
wiped film evaporator keywords , 13-9, 13-10 pure component properties , 7-7

two phase behavior , 7-7 Viscosity , 13-6
typical usage , 7-7 Volatiles, mass transfer of , 13-1
UNIFAC structures , 2-3, 3-10
Unit
wiped film evaporator keyword , 13-9, 13-10 W
Units of measure
selecting , 2-1 Wall clearance , 13-5
User-added polymer reactor models WFE
conditions , 8-1, 9-1, 10-1, 11-1 See Wiped film evaporator
energy operating equations , 8-2, 8-4 Wiped film evaporator
heat transfer coefficient , 8-5 axial velocity , 13-5
kinetic rate constants , 8-2, 11-7 blade configurations , 13-5
mass operting equations , 8-2, 8-4 bow wave , 13-2
mechanisms , 9-2 Carreau model , 13-6
moment expansions , 8-7 component properties , 13-6
overview , 8-1, 9-1, 10-1, 11-1 design mode calculations , 13-2
polymerization via free radical kinetics , 9-2 example , 4-7, 13-14
polymerization via stepwise kinetics , 11-2 feedback model , 13-4
population balance , 8-6 feedback ratio , 13-3
pressure effects , 8-5 functions of rotation rate , 13-3
required data , 9-12, 10-8, 11-7 general summary , 13-9
user-added subroutines , 9-13, 10-9, 11-8 heating conditions , 13-10
user-added polymer reactor models inside view , 13-1
polymerization via Coordination complex keyword input , 13-9
kinetics , 10-2
liquid diffusivity , 13-7
User-added routines liquid viscosity , 13-6
stepwise kinetics , 10-10, 11-8 melt physical properties , 13-6
User-added subroutines number of blades , 13-5
communicating with PRO/II , 9-13, 10-10, 11-8 operating modes , 13-2
free radical kinetics , 9-13 optimization , 13-3
keyword input , 9-13, 10-9, 11-8 output , 13-8
reactor unit US21 , 9-23, 10-15, 11-12 outside view , 13-1
Utility polymer melt , 13-2
polymer characterization conversion , 5-1 PRO/II , 13-2
rate-limited process , 13-10
rating mode , 13-3
V required entries , 13-8
shear rate , 13-7
van Krevelen method surface renewal model , 13-4
group contribution , 3-1 temperature profiles , 13-6
group contribution, example , 7-6 unit identification , 13-9, 13-10
predicted properties , 3-5 variables , 13-12
POLYMERS
van Krevelen structural groups

description , 3-3
example , 3-4 Z
table , A-1
van Krevelen structures , 2-3 Ziegler-Natta polymerization , 1-1
I-7 Index
POLYMERS

Polymers Module

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Polymers Module

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POLYMERS MODULE

Chapter 1 Introduction to Polymers

Chapter 2 Using the Polymer Module with PRO/II

Chapter 3 Estimating Polymer Component Property Data

Chapter 4 Supplying Polymer Pure Component Property Data

Input Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4-2

Chapter 5 Supplying Polymer Stream Data

PRO/II 7.1 Add-On Modules Users Guide 3

Chapter 6 Stream Output Report Options

Chapter 7 Specifying the Thermodynamic Method

Chapter 8 User-Added Polymer Reactor

Population Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-6

Chapter 9 User-Added Free Radical Polymerization Model

Chapter 10 User-Added Coordination Complex Polymerization

Chapter 11 User-Added Step Growth Polymerization Reactor

Required Data for the Polymer Reactor Unit . . . . . . . . . . . . . . . . . . . .11-7

PRO/II 7.1 Add-On Modules Users Guide 5

Chapter 12 Interpreting the Output

Chapter 13 Wiped Film Evaporator

Appendix A van Krevelen Structural Groups

Polymers form the basis of many useful, synthetic materials com-

Addition or Chain Polymerization

polymerization are special types of addition polymerization.

PRO/II 7.1 Add-On Modules Users Guide 1-1

Poly(vinylchloride) or PVCused in pipes, adhesives, and

Condensation or Step Growth Polymerization

Polymerization reactions are exothermic in nature and require

1-2 Introduction to Polymers

Polymer chain A high molecular weight structure made up of a large

Polymer A representative section of the polymer chain that con-

Cross-linking A process in which polymer chains react with each

Monomer A building block unit of a polymer. Monomer units can

Homopolymer A polymer formed by a single type of monomer unit.

Copolymer A polymer formed by two types of monomer units.

Thermosetting A polymer that remains rigid and insoluble when

Thermoplastic A polymer that softens or hardens by the addition or

Polymer blend A non-homogeneous mixture of polymers that results

in desired polymer properties. Special compatibilizers

Condensation or A process in which monomer units are combined by

PRO/II 7.1 Add-On Modules Users Guide 1-3

Bulk A process in which monomer units are combined in

Solution A process in which monomer units are combined in the

Suspension A process in which monomer units are combined in the

Emulsion A process in which monomer units are combined in the

1-4 Introduction to Polymers

To create a simulation for a polymer system using PRO/II, follow

Selecting the Units of Measure POLYMERS

The current version of the polymers module in PRO/II requires the

PRO/II 7.1 Add-On Modules Users Guide 2-1

Click Initialize from UOM Library... to display the Initialize Units of

Entering Polymer Segment and Component Data

Click the Component Selection button on the toolbar (or select

2-2 Using the Polymer Module with PRO/II

Complete all the segment data by entering the segment names

Calculating Molecular Weight Distributions

To calculate or input the molecular weight distributions, first enter

PRO/II 7.1 Add-On Modules Users Guide 2-3

Component Properties dialog box.

To enter the distribution data for a polymer component:

2-4 Using the Polymer Module with PRO/II

Choosing Thermodynamic Methods

PRO/II 7.1 Add-On Modules Users Guide 2-5

To enter the following, click Enter Data.... Detailed information

Building the Flowsheet and Selecting Polymer Reactors