ARTICLE IN PRESS

International Journal of Adhesion & Adhesives 25 (2005) 3946

The competitive inuence of specic interactions and extent

of reaction on the miscibility of ternary reactive polymer
blends: model for polyurethane adhesives
Daniel J. Duffya,b, Amy M. Heintza, Howard D. Stidhamb, Shaw L. Hsua,*,
Wu Suenc, Charles W. Paulc
a
Polymer Science and Engineering Department, University of Massachusetts (Amherst), Amherst, MA 01003, USA
b
Chemistry Department, University of Massachusetts (Amherst), Amherst, MA 01003, USA
c
National Starch, Bridgewater, NJ 08807, USA
Accepted 19 March 2004

Available online 18 May 2004

Abstract

A ternary blend of polyether, polyester and an acrylic was used to model a polyurethane-based reactive hot melt adhesive. The
miscibility behavior of this ternary blend was found to change signicantly during formation of the polyurethane prepolymer. The
competing effects of changing the functionality and increasing the molecular weight of polyether and polyesters have been analyzed.
It was found that incorporation of urethane groups tends to improve ternary blend miscibility. In contrast, an increase in the
molecular weight of the prepolymer destabilizes the ternary blends. These competing effects cause an oscillation in the free energy of
mixing. For prepolymers with low molecular weight, the ternary blend can exist as miscible or immiscible mixtures as a function of
molecular weight. The results of this study are useful in understanding how the phase behavior of reactive polyurethane blends
evolves as a function of the extent of reaction and the distribution of the reaction products formed.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Polymer blends; Specic interactions; Ternary phase diagrams; Polyurethane prepolymers; Reactive blends; Phase separation

1. Introduction polyester diols and diisocyanates are the basis for

Polyurethane-based materials are an integral part of
modern technology due to the wide range of perfor-
mance characteristics that can be achieved from the
same basic chemistry by variations in processing or
formulation. Many materials are prepared from reactive
blends; the morphology produced during the synthesis
and processing of these materials strongly inuences the
mechanical and performance properties of the blend.
The thermodynamic stability of the blend is the driving
force behind morphology development and is dependent
on both molecular weight and specic interactions
between repeat units of the polymer chains. Many
polyurethane prepolymers prepared from polyether or
*Corresponding author. Tel.: +1-413-577-1416; fax: +1-413-545-
0082.
E-mail address: slhsu@polysci.umass.edu (S.L. Hsu).
reactive coatings and adhesives [14]. However, other
polyurethane prepolymer systems are prepared from
blends of reactive polyester and polyether diols with a
compatibilizing third component [5]. Incorporation of a
high glass temperature acrylic component provides
greater control of green strength (viscosity) at elevated
temperatures. The relationship between prepolymer
chemistry and the miscibility behavior of these multi-
component reactive blends is not well understood,
however.
In previous studies [5], we concentrated on developing
both experimental and analytical tools for characteriz-
ing the miscibility behavior of a ternary blend. We also
followed the changing structure and side reactions as a
function of reaction [6]. In this paper we report on two
separate but related aspects of polyurethane prepolymer
chemistry, molecular weight and specic interac-
tions that inuence phase behavior. The system given

0143-7496/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2004.03.003
 ARTICLE IN PRESS
40 D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946
principal attention is composed of poly(propylene
glycol) (PPG), poly(hexamethylene adipate) (PHMA)
and a co-polymer of methylmethacrylate and n-butyl
methacrylate (P(MMAnBMA)) [5]. The chemical struc-
tures of the components are shown in Fig. 1. This model
system closely approximates commercial formulations
[5]. Its phase behavior provides considerable insight into
the morphological features responsible for the perfor-
mance of practical polyurethane adhesive and coating
systems.
Two levels of complexity exist and need separate
consideration before the inuence of prepolymer chem-
istry on the miscibility behavior of the overall formula-
tion can be properly understood. It is necessary to
characterize the contributions from specic interactions
and from the distribution of prepolymer reaction
products. In this study, we have two reactive polymers,
polyether (PPG) and polyester (PHMA) as the principal
components. To reduce the scope of the problem, we
focused rst on the inuence of PPG on ternary blend
miscibility behavior. The prepolymer reaction is a step
polymerization producing a distribution of oligomers
[6]. Several possible PPG prepolymer products are
shown in Fig. 2. Each acts to modify the miscibility of
the ternary blends differently depending on its function-
ality and molecular weight. Based on our experimental
data, incorporation of the urethane group and isocya-
nate functionality are important factors contributing to
specic interchain interactions. The urethane groups
Fig. 1. Chemical structures of starting materials used in the preparation of reactive blend model compounds.
participate in hydrogen bonding interactions which tend
to promote miscibility between components in a blend
[79]. Therefore, the ratio of OH to NCO of PPG
prepolymers is set as one parameter in our analysis. It is
also important to consider the degree of polymerization
of oligomers formed in the prepolymer formation. The
increase in molecular weight resulting from the reaction
reduces the entropic contribution to the free energy of
mixing (DGmix), de-stabilizing miscible blends.
By considering these two separate but interrelated
structural parameters, the miscibility behavior of the
ternary mixtures can be examined in a controlled
fashion. The molecular weight increase is accompanied
by an increase in the number of interacting functional
groups. The favorable enthalpic interactions can stabi-
lize the blend even at high degrees of polymerization if
the reduction in the entropic contribution is balanced by
the enthalpic contribution. Fig. 2(a) and (b) illustrate
dimer and trimer structures which are similar in
molecular weight to the starting PPG material but with
new urethane functionalities. Although their entropic
contributions to DGmix are expected be similar due to the
similar molecular weight, the enthalpic contributions
(DHmix) to DGmix are expected to be quite different due
to the presence of new chemical functionalities. Fig. 2(c)
and (d) show tetramer and pentamer structures which
are at least twice the molecular weight of the starting
material. The contribution to DSmix is expected to be
much smaller due to the increased molecular weight. It is
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D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946
Fig. 2. Distribution of reaction products (a-dimer, b-trimer, c-tetramer, d-pentamer.) formed during polyurethane prepolymer synthesis.
Fig. 3. PPG end capping reaction producing the model reaction product PPG-PI.
not obvious whether or not the urethane contribution to
DHmix compensates for the entropic contribution to
DGmix.
Ternary blends exhibit extremely fascinating phase
behavior. Small changes in the structure of any
particular component may cause signicant changes in
miscibility [5, 10]. A detailed analysis of the miscibility
behavior is also important from a practical perspective.
In partially miscible reactive mixtures, the reactive
components are not equally partitioned between the
co-existing liquid phases [11]. For a phase-separated,
reactive polyurethane system, the partitioning of various
monomers and reaction products in co-existing phases
associated with a phase-separated mixture may be quite
different from the overall stoichiometry. The situation is
even more complex if the miscibility behavior changes
dramatically when changes in the functionality and
molecular weight are taken into consideration. Because
not all reactive blends have an increase in specic
interactions as the molecular weight increases, phase
separation may occur as the reaction progresses [12, 13].
Knowledge of the point at which entropic and enthalpic
contribution balance is valuable for understanding how
to control morphology evolution through reaction
chemistry in polyurethane-based reactive blends. Our
results concerning the miscibility of ternary reactive
polymer blend and the balance of the competitive
enthalpic and entropic effects are reported here.
2. Experimental
PPG was obtained from ARCH Chemical; PHMA
were obtained from Dow Chemical and a random co-
polymer resin of P(MMAnBMA) was obtained from
41
INEOS Acrylics. Methylene bis(phenyl diisocyanate)
(MDI) and phenyl isocyanate (PI) were purchased from
Aldrich, stored under N2, but otherwise used as
received. The molecular structures of these ve compo-
nents are shown in Fig. 1. The characterization of the
molecular weight and composition of PPG, PHMA and
P(MMAnBMA) used here has been reported previously
[5, 6].
A model prepolymer of PPG was prepared by
reaction with PI to produce end-functionalized (capped)
PPG (PPG-PI) via the reaction shown in Fig. 3. This
reaction permits evaluation of the inuence of urethane
groups in the absence of higher molecular weight
products formed during reaction with a diisocyanate,
as shown in Fig. 2. Diols were dried under vacuum for
24 h at 100
C in three-neck, round bottom asks. The
reactor was heated to 120
C and back lled with N2. PI
was added via syringe and rubber septum, and the
reaction was allowed to run for 68 h. A 10%
stoichometric excess of PI was used to ensure complete
conversion of hydroxyl groups to urethane. Residual PI
was removed by low-pressure distillation conducted at
100
C for 6 h. Products were removed from the reactor
and stored under N2. Reaction of hydroxyl groups was
conrmed by FTIR and 1H-NMR analysis. The PPG
trimer molecule (PPG2-MDI) was prepared under
conditions similar to the PPG-PI by the reaction of 1/
2 equivalents of MDI with PPG at 120
C. All NCO
groups and MDI molecules were consumed in this
reaction so distillation was not necessary.
A fraction of the PPG2-MDI product was reacted
with PI to form a product with similar molecular weight
similar to the PPG2-MDI but with a higher urethane
content. The reaction scheme used to produce the high-
molecular weight samples is shown in Fig. 4. The
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42 D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946
Fig. 4. Synthesis of higher molecular weight prepolymer materials with different urethane contents.
Fig. 5. Chromatograms showing the distribution of molecular weights
for the PPG, PPG-PI, PPG2-MDI1 and PPG2-MDI1-PI model
prepolymers.
chromatograms of PPG, PPG-PI, PPG2-MDI and
PPG2-MDI-PI are shown in Fig. 5. The physical data
shown in Table 1 for the four polymers were calculated
from molar volume data [7, 14] and the repeat unit
volumes shown in Table 1. Molecular weights were
determined by size exclusion chromatography (SEC) in
conjunction with matrix-assisted laser desorption time-
of-ight (MALDI-TOF) mass spectrometry. A calibra-
tion curve of log(Mw) versus elution volume was
constructed for PPG prepolymers by combining the
peak molecular weight obtained from MALDI with
curve tting of SEC traces [6].
All MALDI-TOF spectra were obtained on a Bruker
Reex-III spectrometer. Matrix conditions were pre-
viously reported. [5, 6] SEC was conducted on a Waters
510 HPLC pump equipped with 3 columns from
Polymer Labs (5 mm bead size; two with MIXED-D
and one 50 A ( pore sizes). Tetrahydrofuran was used as
the mobile phase and a Waters R401 differential
refractometer was used for detection. 1H-NMR was
obtained on a Bruker DPX 300 spectrometer in CDCl3
or acetone-d6.
Melt miscibility of binary and ternary polymer blends
was evaluated by means of the following procedure.
Blends were prepared in glass vials by mass, placed in a
constant temperature oven at the melt temperature and
allowed to equilibrate under N2. The oven was opened
periodically and the blends mixed under N2. Since the
existence of multiple phases typically produces a cloudy
appearance, cloud point measurements were made using
either a microscope hot stage or a light scattering cell
coupled to a HeNe laser and photodiode detector.
Temperature and overall light transmission were both
controlled and recorded electronically.
3. Results and discussion
The miscibility behavior of prepolymers ternary
blends of different urethane functionality and molecular
weight (polyether, polyester and acrylate) shown in
Fig. 6 is quite interesting. Signicant differences were
achieved depending on the composition of the materials
and molecular structure. The blends of the unreacted
materials are shown in Fig. 6(a). All three binary
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D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946 43

Table 1
Physical parameters for raw materials and phenyl isocyanate end capped polymers

Mn Mw/Mn rliquid rsolid Mrepeat Nrepeat Vrepeat n

PPG 1906 1.01 1.003 58 33 57.4 33

PHMA 2505 1.59 1.051 1.158 228 11 216.2 44

PPG-PI 2144 1.07 1.034 58 33 57.4 37

PPG2-MDI1 9530 1.60 58 33 57.4 69
PPG2-MDI1-PI 8779 1.56 58 33 57.4 73

P(MMAnBMA) 30900 1.64 1.115 110.5 280 95.9 468

Fig. 6. Miscibility maps for ternary blends of (a) PPG, PHMA, P(MMAnBMA), (b) PPG-PI, PHMA, P(MMAnBMA), (c) PPG-MDI, PHMA,
P(MMAnBMA) and (d) PPG-MDI-PI, PHMA, P(MMAnBMA) in the melt at 140, 120, 120 and 120
C, respectively.

mixtures are partially miscible in the melt. A region of
miscible ternary composition is located near the center.
The boundary between the opaque and clear blends
changes signicantly with decreasing temperature [5].
The addition of more than 20% acrylic copolymer
appears to promote compatibility of polyether and
polyester components leading to optically clear blends.
The centrally located completely miscible region in Fig.
6(a) is interesting and islands of miscibility have been
observed in other polymer systems [5, 15]. We previously
demonstrated that the effect of polyester structural
change on miscibility of ternary blends is dramatic [5].
The miscibility of ternary blends of the PI-end-capped
PPG, PPG-PI, PHMA and P(MMAnBMA) is shown in
Fig. 6(b). This ternary blend system displays changes in
miscibility due to prepolymer products with low degrees
of polymerization. In this case, the urethane-to-PPG
chain ratio for the prepolymer is two. A dramatic
improvement is observed in compatibility of the three
components in comparison with unreacted materials
(Fig. 6(a)). Virtually all mixtures are miscible in the melt
except for compositions adjacent to the polyester
acrylic binary axis, i.e. those with very low polyether
content. It is apparent that the addition of the two
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44 D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946
terminal urethane groups to the polyether provides
sufcient specic interaction to achieve miscibility.
Fig. 6(c) illustrates the miscibility for ternary blends
containing PPG trimer molecules, i.e. two PPG chains
coupled by one MDI unit. This model polyether has a
urethane to PPG chain ratio of one. Fig. 6(c) shows that
the increase in molecular weight of the PPG chain has
offset the enthalpic gain achieved by addition of the
urethane groups shown in Fig. 6(b). The polyether,
acrylic and polyether, polyester binaries are partially
miscible again and the majority of the ternary blends are
unstable. This ternary system represents the situation
where the PPG trimer structures shown in Fig. 1(c) are
dominant. Fig. 6(d) shows the melt miscibility of ternary
blends containing the PI-end-capped PPG trimer
molecules. The urethane to chain ratio for these blends
is two. The polyether, acrylic and polyether, polyester
blends show an improvement in compatibility due to the
addition of urethane groups. The enthalpic contribution
due to specic interactions does not compensate
sufciently for the entropic effect due to increasing
chain length to produce complete miscibility. These
possibilities found during polyurethane reactions de-
pend on the relative concentrations of the polymers and
the isocyanate used.
The phase behavior of these blends can be analyzed
most conveniently by means of the thermodynamics
expressions based on a lattice model [1618]. We also
developed various simulation techniques to calculate
specic interaction constants in binary systems; these
constants were then applied to ternary blends [5]. The
relationship used in this investigation for free energy of
mixing relationship is shown in Eq. (1), where f is the
volume fraction of component 1, n1 and n2 are the
degrees of polymerization, and g12 is the binary
interaction parameter. Two competing factors, entropy
and enthalpy, determine the free energy change and
consequently the miscibility of polymeric mixtures. For
a binary mixture to be stable the spinodal condition
given by Eq. (2) must be satised. Eq. (3) shows the
critical interaction parameter, i.e. the maximum value
for a binary blend whereby the blend remains miscible in
all proportions. This represents the point where entropic
and enthalpic contributions are exactly balanced. These
expressions imply that a balance between the entropy
and enthalpy of mixing must be maintained to maintain
melt miscibility.
mix
DG1;2
NRT  
flnf 1  fln1  f
n1 n2
f1  fg12 ; 1 PPG-PI
 
1 1
 2g12 Z0; 2 PPG2-MDI1
fn1 1  fn2
1 1=2 1=2
2
gcritical
12 n1 n2 : 3
2
As mentioned in the introduction, during the poly-
urethane prepolymer reaction the molecular weight of
reactive polyether and polyesters increases. This de-
creases the value of gcritical and induces phase separation
if the value of g12 exceeds the critical value at some point
during the reaction. In this reaction, the value of gcritical
is decreased due to the increase in molecular size.
However, the favorable intermolecular interactions are
introduced simultaneously and increase with increasing
number of urethane groups being incorporated. If the
magnitude of specic interaction increase exceeds the
lowering of entropic contribution, the ternary blend will
phase mix. Conversely, if the interactions contribute
more to the free energy of mixing than the lowering of
entropic contribution, a miscible phase will be found.
The uctuation between miscible and immiscible binary
blends as a function of molecular weight and function-
ality of the prepolymer products is clearly observed in
Fig. 6. Changes in specic interactions and increase in
molecular weight are sufciently important to cause the
interaction parameter for binary blends to oscillate
about the critical value.
Table 2 presents the interaction parameters and
critical values for the PI-end-capped system and for
the PPG2-MDI1, PHMA and PPG2-MDI1-PI,
P(MMAnBMA) determined by the experimental and
computational techniques developed previously [5]. The
contributions of PPG and phenyl carbamate units are
considered to be additive and were used to predict
interaction parameters as a function of the degree of
polymerization. The interaction parameter for the
binary blends of PPG prepolymer and PHMA is given
by Eq. (4) where (x) is the volume fraction of phenyl
carbamate groups in the polymer chains. This volume
fraction will vary as the degree of polymerization
increases. The following notation is adopted in Eq. (4)
for the various binary systems. The subscript (a) refers
to PPG repeat units, (b) to PHMA repeat units, (d) to
P(MMAnBMA) repeat units and (f) to phenyl carba-
mate units. The critical interaction parameters can be
determined as a function of degree of polymerization
Table 2
Experimental and critical binary interaction parameters and segmental
interaction parameters used in prepolymer miscibility calculations
Polymer 1 Polymer 2 g(1,2) g(crit.)
PPG PHMA 0.0647 0.053
PPG-PI PHMA 0.0103 0.049
PPG P(MMAnBMA) 0.0272 0.024
P(MMAnBMA) 0.0177 0.022
PHMA P(MMAnBMA) 0.0233 0.019
PPG2-MDI1 PHMA 0.0401 0.037
P(MMAnBMA) 0.0157 0.013
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using Eq. (3) and the miscibility of the blends can be
evaluated as the reaction progresses.
gaf=b 1  xgab xgbf  x1  xgaf : 4 decreases as the degree of polymerization increases.
The molecular volume of the PPG chains, taken as the
number of MDI units (#MDI) plus the number of PPG
chains (#P), as a function of degree of polymerization is
shown in Fig. 7(a). The numbers in Fig. 7(a) correspond
to the number of PPG chains involved in each reaction
product. For products involving one PPG chain, there
are three possible cases: 1. one PPG chain and no MDI
units (starting material), 2. one PPG and one MDI unit
(Fig. 1(a)), and 3. one PPG and two MDI units (Fig.
1(b)). Fig. 7(b) shows the volume percentage of MDI as
Fig. 7. (a) Molecular volume and (b) volume percent of urethane
groups as a function of PPG degree of polymerization.
45
a function of degree of polymerization of PPG. For low
degrees of polymerization, large uctuations in the
volume percentage are observed. This uctuation
The volume percentage converges to 9% for an innite
degree of polymerization. The contribution from the
urethane groups to the binary interaction parameters is
largest at low degrees of polymerization and converges
to a nite value at high degrees of polymerization.
Fig. 8(a) shows the calculated and critical interaction
parameters for the binary blends of PPG and PHMA as
a function of degree of polymerization. Fig. 8(b) shows
the corresponding calculation for binary blends of PPG
and P(MMAnBMA). To illustrate the inuence of the
polyether prepolymer chemistry on blend miscibility,
only the molecular volume of the PPG component is
varied. In these calculations, the molecular volumes of
the PHMA and P(MMAnBMA) components are kept
Fig. 8. Interaction parameters for binary blends of (a) PPG, PHMA
and (b) PPG, P(MMAnBMA) as a function of the PPG degree of
polymerization.
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46 D.J. Duffy et al. / International Journal of Adhesion & Adhesives 25 (2005) 3946
constant. Two very different types of behavior are
observed for these binary systems at large degrees of
polymerization. In Fig. 8(a) the interaction parameter
corresponding to the unreacted materials is larger than
the critical value and the binary blends are partially
miscible as observed. The calculated behavior is in
agreement with the data shown in Fig. 6(a). Once the
urethane functionality is added during synthesis of
the prepolymer, the interaction parameter is lowered
below the critical parameter. The blends should be
miscible in the molten state in agreement with experi-
mental observations summarized in Fig. 6(b). Upon
coupling of two PPG chains, the interaction parameter
is raised above the critical value. Thus the blends will
phase-separate, forming immiscible mixtures depending
on the composition. This is in agreement with the
behavior observed in Fig. 6(c). As the reaction
continues, with urethane units being added and a
concurrent increase in molecular weight, the interaction
parameter converges to a value near zero (0.0006)
which lies below the critical interaction parameter
limit at an innite conversion. The PPG/PHMA
binary blend should be miscible at very high degrees
of polymerization.
Fig. 8(b) shows the corresponding calculation for
binary blends of PPG and P(MMAnBMA). A similar
oscillating behavior of the miscibility is observed at low
degrees of polymerization, but the interaction parameter
converges to a value (0.022) above its critical value at
innite degree of polymerization. This indicates that for
binary blends of PPG and P(MMAnBMA) to remain
miscible during reactive blending, the degree of poly-
merization of the PPG must remain low. As this gure
demonstrates, two very different types of behavior are
expected for binary blends at high degrees of polymer-
ization of PPG, and an oscillation between miscible
and immiscible blends is observed for low degrees of
polymerization.
4. Conclusions
This work demonstrates that the miscibility of ternary
polyether, polyester, and acrylic blends is sensitive to the
urethane volume fraction of polyether prepolymers.
Urethane groups improve compatibility of the poly-
ether/polyester and polyether/acrylic binary blends at
low degrees of polymerization due to strong specic
interactions. As the degree of polyether polymerization
increases, the polyether/polyester binary blends tend
toward a miscible state while polyether/acrylic binary
blends tend toward an unstable, partially miscible blend.
These results are useful for understanding how competi-
tion between molecular weight increase and specic
interactions associated with polyurethane prepolymer
chemistry compete and inuence the miscibility of
reactive ternary polymer blends.
Acknowledgements
This study has been supported by a Grant from NSF-
EPA TSE grant. In addition, the authors also wish to
acknowledge the support from National Starch.
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