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SUMMARY:
Polyvinyl acetate precipitates from aqueous solution as it is formed. When potassium
persulphate is used as initiator the polymer suspension is stable and constitutes the prin-
cipal locus of reaction. The effect of reaction conditions on the rate of polymerization and
on the number of particles formed ha5 been studied. The surface charge density appears to
be the factor which determines the number of particles formed and which limits the rate
of reaction.
ZUSAMMENFASSUNG:
Polyvinylacetat f a t bei seiner Bildung aus wainriger Losung aus. Bei Verwendung von
Kaliumpersulfat a l s Initiator ist die Polymersuspension bestandig und stellt den haupt-
sachlichen Ort der Reaktion dar. Der Eidul3 der Reaktionsbedingungen auf die Poly-
merisationsgeschwindigkeit und auf die Zahl der sich bildenden Polymerteilchen wird
untersucht. Es scheint, dal3 die Oberflachedadungsdichte die Zahl der Polymerteilchen be-
stimmt und auch die Reaktionsgeschwindigkeit begenzt.
Introduction
207
A. S. DUNNand P. A. TAYLOR
Experimental
Materials. Vinyl acetate monomer provided by Vinyl Products Ltd. was redistilled
before use. Potassium persulphate was recrystallized from water: a 1yo solution was pre-
pared just before use. Sodium dodecyl sulphate was purified by HARROLD'S method15):
the critical micelle concentration, determined with a DE NOUYtensiometer was sharp a t
4. M: Polyvinyl alcohol was DuPont "Elvanol" 52-22 containing about 12 mole-%
residual acetate.
Polymerizations were followed dilatometrically using dilatometers with a capacity of
about 21 ml. having a stem approximately 1.7 mm. in diameter. All experiments were a t
60 "C. In some experiments solutions were degassed by repeated freezing and evacuation;
usually, the amount of oxygen in solutions was limited by boiling out the water just before
use.
The soZuGiZity was determined at 20 and 50 "C.to be 2.5 g. vinyl acetate per 100 g. water:
variation with temperature in this range was negligible.
Bromometric titrations. A bromate-bromide solution was acidified to give a solution
0.1222 N in bromine. A reaction time of about one hr. a t 0 "C. was allowed. The method was
tested by determining the purity of redistilled vinyl acetate which was found to be 99.6%.
Determinations I J ~Numbers of Particles. Particle sizes were determined by the light
scattering technique of BURNETT,LEHRLE,OVENALL,and P E A K E R ~ ~ ) a BRICE-
using
PHOENIX Light Scattering Photometer.
208
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
Some results were confirmed by electron microscopy of gold shadowed carbon replicas
u3ing a Philips EM 75 electron microscope.
Results
Contraction on polymerization
I n order to convert observed dilatometer contractions to rates of
polymerization, the contraction corresponding t o complete polymeriza-
tion must be known. The polymer formed corresponding t o an observed
contraction was weighed after water and residual monomer had been
removed. Three distinct techniques of removing the liquid residue were
tried : evaporation at 100 "C. after addition of hydroquinone, evaporation
a t 60°C. in a stream of oxygen, and sublimation of the frozen solution.
These gave concordant results, the mean of fifteen determinations being
15.7 f 0.4 yo contraction for complete polymerization. This agrees with
NAPPERand PARTS13) who also find 15.7% for polymerization of mono-
mer in aqueous solution at 60°C. but differs from STARKWEATHER and
TAYLOR'S value of 26.8 yo for bulk monomer a t 70 "C. This might result
from solvation of the vinyl acetate in aqueous solution.
Effect of oxygen
The rate of polymerization increases with time initially (Fig. 1).Since
oxygen inhibits the polymerization such an acceleration could occur
whilst the last traces of oxygen are being consumed. However degassing
the solution rigorously eliminated the inhibition period without affecting
the subsequent course of the reaction. Rigorous degassing made it difficult
to observe the start of the reaction which was masked by expansion as the
Time(min.)
209
A. S. DUNNand P. A. TAYLOR
Fig. 2. Polymerization of 2 yo v. /v. vinyl acetate with 0.02 yow. /v. persulphate. A Ionic
strength increased by addition of 4% w./v. potassium sulphate. o Ferric-hydrogen per-
oxide initiation. (H,O,) 0.047 M , (Fe+++) 3.5.10-5 M, giving a similar rate of initiation
to 0.02 yo persulphate
210
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
211
A. S. DUNNand P. A. TAYLOR
2 12
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
Table 1. Variation of rate and number of particles with initiator concentration. Initial
monomer concentration 1yo v. /v.
Particle diameter
% K2S20, Maximum rate No. particles/mL
w./v. D w (4 (. 10-12)
(at lo0 yo conversion)
I I I
I I I
0.005 1.9 2950 0.74
0.010 3.2 2740 0.93
0.015 4.0 2600 1.09
0.020 4.8 2480 1.25
0.030 - 2440 1.30
0.040 7.5 2310 1.54
5 1400 1.38
16 1700 1.48
37 2180 1.17
62 2900 0.85
1.0 1 0.01
100
6
17
3280
740
1250
0.91
91.0
28.2
32 1590 19.8
49 1780 16.0
66 1980 14.8
100 2280 12.7
213
A. S. DUNNand P. A.TAYLOR
(100 yo conversion)
330
2 14
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
Time (min
Fig. 3. Effect of sodium dodecyl sulphate on the rate of polymerization of 2 yo v./v. vinyl
acetate with 0.02% persulphate. yo w./v. sodium dodecyl sulphate: - 0, --- 0.00046,
_ _ _ 0.004-0.049
Discussion
215
A. S. DUNNand P. A. TAYLOR
% Polymerization
Fig. 4. Correlation of the rate of polymerization - - - with the total amount of monomer
dissolved in the polymer phase -
The size of the suspended particles is some ten times larger than those
formed in the experiments of SMITHand later workers4-6). It has been
shown 21) that several polymer radicals can co-exist in such large particles.
Calculations have been made of the number of radicals per particle which
would be required t o explain the observed maximum rates of reaction,
assuming the propagation rate constant, k,, to be constant and to have
a value19)of 3,000 1. mole-1 sec-l. From the data of Table 3, ii the average
number of radicals per particle was calculated (Table 7) from the observed
number of particles per litre, using M,, the monomer concentration in the
particles derived from the concentration of monomer remaining in the
aqueous phase determined by bromometric titration and the distribution
expression. Then
- dM/dt = fi kp (Mp) N/N* (2 )
216
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
Table 7. Variation of the number of radicals (ii) per particle with conversion
217
A. S. DUNNand P. A. TAYLOR
Transfer reactions can retard the rate of polymerization 23) because of the
introduction of a n alternative termination reaction.
Termination between a polyvinyl acetate and a polyvinyl alcohol
radical may be favoured because t h e approach of a charged radical t o a
charged particle is not involved. But polyvinyl alcohol increases the
stability of smaller particles (Table 5): these must have a lower surface
charge density which should increase the rate of termination b y sulphate
radicals.
Thus t h e factors which determine the rate of polymerization and the
size of the particles formed in this reaction are quite different from those
operative in the emulsion polymerization of styrenel-Q : i t is hoped t h a t
application of the theory of t h e stability of lyophobic t o this
system will provide a more quantitative explanation of its behaviour.
218
The Polymerization of Vinyl Acetate Initiated by Potassium Persulphate
219