PJ 197229
PJ 197229
PJ 197229
2, pp 226-233 (1972)
The theory of the mechanism of emulsion wish to report, in this paper, on the effects of
polymerization was quantitatively formulated by types of various initiators on the kinetics of the
Smith and Ewart. 1 This theory was adapted to emulsion polymerization of V Ac in the pre-
the emulsion polymerization of styrene, 2 ' 3 but sence of PV A as emulsifier.
is unapplicable to the emulsion polymerization
of VAc. 4 According to Okamura, et al., who
EXPERIMENTAL
have studied the effect of emulsifiers on the
emulsion polymerization of VAc, the deviation Materials
from the Smith-Ewart theory is due both to A VAc monomer was purified by distillation
the relatively high solubility of VAc into water under reduced pressure in a stream of nitrogen.
and to the reactivity of radicals toward emulsi- The initiators employed were both the KPS-
fiers. 4 A number of studies have been carried AsA system and the RPO - AsA system.
out on the emulsion polymerization of V Ac These reagents were the purest chemicals com-
using persulfate as initiator. s-s The use of per- mercially available, and were used without
sulfate would result in the sulfate end groups further purification. The PV A (NL-05) was
in polymer molecules. 9 • 10 However, if RPO is obtained from the Nippon Synthetic Chemical
used as the initiator of polymerization, the Industry Co., Ltd. Sodium acetate contained
hydroxyl groups must be linked to the ends of in PV A and the low molecules of PV A were
the polymer molecules. Although many reports removed by dialysis over one week. The degree
on the emulsion polymerization of VAc have of polymerization of PV A dialyzed was calculated
been published, there have been few studies by measuring the intrinsic viscosity in water at
concerning the effect of the end groups of the 30°C, using the equation proposed by Nakajima,
polymer molecules on the polymerization. 11 We et al., 12 and was determined to be 720.
226
Emulsion Polymerization of Vinyl Acetate
60
50
C
0
-~ 30
<ll
>
C
8 20
10
20 30
Polymerization time (min)
molecules coming from the initiators, most of KPS-AsA system is illustrated in Figure 4.
which would be present on the particle surface. Even if the PV A concentrations in the reaction
The dalatometer was calibrated gravimetrically system were varied, the results obtained fell on
by weighing the polymer, and the volume con- the same curve. As can be seen from the shape
tractions of VAc at the conversion of 100% of the curve, the reaction of the emulsion poly-
were found to be 12.2% at 20°c and 13.8% at merization of V Ac is also divided into three
40°C, respectively. The time-conversion curves stages. It is obvious from the second stage that
were obtained by use of these contractions. the instantaneous rate of polymerization is kept
The results of the emulsion polymerization of constant at conversions above about 10%. The
V Ac in the presence of PVA at 20°c are illustrat- values of the maximum rate of polymerization
ed in Figures 2 and 3. Figure 2 shows the re- obtained from Figure 2 are summarized in
sults obtained by using the KPS-AsA system, Table I, together with the results determined
while Figure 3 indicates the results which the
HPO-AsA system was used as the initiator. Table I. The maximum rate of polymerization
The PVA concentrations ranged from 0. 74 to (Rp) of the emulsion polymerization of VAc
4.44 g/l in water. When PVA was used as the initiated by the KPS-AsA system at 20°C
emulsifier, all the latices obtained were stable,
[PVA], [VAc]x 10,
[KPS]x [AsA]x
103, 103, Rv,
regardless of the type of initiator. g/l %/min
mo!// mol// mo!//
The KPS-AsA System
As is well known, the reaction of emulsion 0.00 2.29 2.51 2.50 7.0
polymerization is divided into the following three 0.74 2.29 2.51 2.50 7.3
stages. 13 The rate of polymerization increases 1.48 2.29 2.51 2.50 7.3
2.22 2.29 2.51 2.50 7 .1
during the formation of the polymer particles
4.44 2.29 2.51 2.50 7.2
(first stage), and then remains constant because
the number of the polymer particles is kept 0.74 2.29 3.76 2.50 9.2
constant (second stage), and finally becomes first 1.48 2.29 3.76 2.50 9.1
2.22 2.29 3.76 2.50 9.2
order with respect to the monomer concentrations
2.96 2.29 3.76 2.50 9.2
(third stage). 4.44 2.29 3.76 2.50 9.3
From the results in Figure 2, the instantaneous
rate of polymerization-conversion curve which 2.22 2.29 1.26 2.50 5.9
2.22 2.29 2.51 2.50 7 .1
refers to the polymerization initiated by the
2.22 2.29 3.76 2.50 9.2
2.22 2.29 5.02 2.50 10.3
~IO~----------------,
E
' 8 1.2
C:
<= ·e
.,-
- o
-~ 6 '1.0
::-11
0
2
ON
"-"i:
Q) 4 a.0.8
"'E
:::, >.
c::
o-
-Eo....
O>
Q) 0
6 0. 2 _3 0,6
II)
<= 10 20 30 40 50 0.4 0.8 1.0 1,2 1.4 1.6
Conversion (%) l+Log(PVA] (9/J)
Figure 4. Instantaneous rate of polymerization Figure 5. Maximum rate of polymerization (Rp)
vs. conversion in the emulsion polymerization of vs. PVA concentration in the emulsion polymeri-
VAc by the KPS-AsA system at 20°C: [PVA]= zation of VAc by the KPS-AsA system at 20°C:
0, 0.74 g/l;C), 1.48 g//; . , 2.22 g/l; 0, 4.44 g//; (1) [KPS]=2.51xl0-3 mol//; (2) [KPS]=3.76xlQ-3
[VAc]=2.29 x 10-1 mol//; [KPS]=2.51 x 10-3 mol//; mol//; [VAc]=2.29 x 10-1 mol//; [AsA]=2.50 x 10-3
[AsA]=2.50 x 10-3mo!//. mo!//; [PVA] was varied.
under various conditions. The relationships be- centration on the rate of polymerization has
tween the maximum rate of polymerization and been studied at 20°C. The other conditions of
the PV A concentration are plotted at the KPS polymerization were at the AsA concentration
concentrations of 3.76x 10- 3 and 2.51 x 10- 3 mol/ of 2.50x 10- 3 mol//, the PVA concentration of
/ in Figure 5. The reaction order with respect 2.22 g// and the monomer concentration of 2.29
to the VP A concentration was found to be zero, X 10- 1 mol//. Figure 6 shows the time-con-
independent of the KPS concentration. This version curves, while in Figure 7 the relation
result was the same as that found for the between the maximum rate of polymerization
emulsion polymerization of VAc by Okamura, and the KPS concentration obtained from Figure
et al., 4 where sodium dodecyl sulfate was used 6 is indicated. It may be seen from the slope of
as emulsifier. the straight line in Figure 7 that the rate of
The influence of the variation in KPS con- polymerization varies with the KPS concentration
at the power 0.42. The result is in good agree-
ment with the exponent of 0.5 found in the
60 polymerization without emulsifiers by Oka-
mura, 14 where the V Ac concentration was below
50 2% and KPS was used as initiator. Unfort-
unately, since the micelles of PVA are not ob-
l 40 served in water 15 and the rate of polymerization
initiated by the KPS-AsA system is independent
of the PV A concentration, we would not be
able to explain the results obtained in the pre-
sent work by the Smith-Ewart theory,1 which
10
is based on the mechanism that the polymeri-
zation takes place in the soap micelles.
Therefore, considering the rate equation result-
10 20 30
Polymerization time (min) ing, the following elementary reactions may be
written according to Litt, et al. 16
Figure 6. Conversion vs. polymerization time in Decomposition of initiator
the emulsion polymerization of VAc by the KPS
-AsA system at 20°C: (1) [KPS]=l.26x 10-3 mol/ I ~ R-
/; (2) [KPS]=2.51 x 10-3 mo!//; (3) [KPS]=3.76 x
10-3 mol//; (4) [KPS]=5.02xl0- 3 mol//; [PVA]= Initiation
2.22 g//; [VAc]=2.29 x 10-1 mo!//; [AsA]=2.50 x 10-3 ki
mo!//. R- + Maq - Paq"
Propagation
1.2
C: kp
.
E Paq· + Maq----+ Pap· or Pp·
'- i.O>-- kp
Pp·+ MP ----+ Pp·
o.. O.8>--
0:: Entrance of radical into particle
OI
_3 0.6
Termination
--
0.4~~'-~'-~'~-~-~
1.0 1.2 1.4 1.6 1.8
4+ Log [KPS) (mol/1) k2
Paq" + Paq" Paq
Figure 7. Maximum rate of polymerization (Rp) ks
Paq· + Pp· PP
vs. KPS concentration in the emulsion polymeri-
zation of V Ac by the KPS-AsA system at 20°C:
[PVA]=2.22 g//; [VAc]=2.29 x 10-1 mo!//; [AsA]=
2.50 x 10-3 mo!//; [KPS] was varied.
Pp· + pp.
- k,
solution; Mp, the monomer in particle; Pap· , the _ d[M] = k k 1;2[I]1;2 { ( ~ )112 /[Maq]
growing radical in water which is soluble in dt P ct 1-2/ k
water; Pp·, the particle in which radical exists;
Pp, the particle in which radical does not exist.
When a steady state is reached, assuming that
+ (1 ~42/ f 2 [Mp] } (7)
in the presence of many particles, the formation According to Litt, et al., since / is about
of new particles and the termination between 1/1300, (1-2/) can be considered as unity. Equa-
the growing radicals in water are ignored be- tion 7 predicts the square root dependence on the
cause the growing radicals in water are easily initiator concentration. This theoretical ex-
swept up by particles, eq 1 and 2 result: ponent is very close to the experimented result.
The HPO-AsA System
d[~;· J kd[l]-k1[Paq• ][Pp]-ks[Paq• ][Pp• ]=0 Figure 8 shows the relationships between the
conversion and the instantaneous rate of poly-
(l)
merization obtained from the data of Figure 3.
d[Pp·] =k 1(Paq· ](Pp]-ks[Paq· ][Pp· ]-k4(Pp· J2 The polymerization reactions are also divided
dt
=0 (2)
C
The rate of polymerization is the sum of the
consumption rates of monomer in the polymeri-
zations which take place in aqueous solution 4
and in the polymer particles, and is defined as C
follows: .,--~
C
1.,.•;;::,
3
d(M) .,
- ~-=kp[Paq• ][Maq]+kp[Pp· ][Mp] ( 3) ., E
dt g~2
8.
0
where M represents the monomer. C't- I
If the polymer particles are so small that _g O .
.,
termination takes place very rapidly every time C:
OO IO 20 30 40 50
two free radicals are in the same particle, it is Conversion (%)
considered k 1=k 3 • Thus, from eq 1, the fol- Figure 8. Instantaneous rate of polymerization vs.
lowing equation is obtained conversion in the emulsion polymerization of VAc
by the HPO-AsA system at 20°C: [PVA]=O,
[M J- kd[I] 1.4s g;1; •· 2.22 g/1; o, 2.96 g11; e, 3.10 g/1; o,
aq• - k([Pp]+[Pp•]) (4)
4.44 g//; [VAc]=2.04 x I0-1mol/1; [HPO]=2.47 x
where k=.k 1 =ks. I0-3 mol/1; [AsA]=2.50 x 10-3 mol//.
If the fraction of polymer particles having
radicals against the total number of particles in three stages. The dependence of the PV A
(N) is taken as /, since [Pp· ]=fN and [Pp]= concentration for the rate of polymization was
(1-/)N, the eq 4 is rewritten by eq 5: not observed in Figure 4 where the KPS-AsA
system was used, but was obviously found in
[P aq. ] = kct[I] ( 5) Figure 8 where the HPO-AsA system was used.
kN
Data of the maximum rate of polymization
Substituting eq 5 in the eq 2, (Pp·] is ex- initiated by the HPO-AsA system are listed in
r
pressed as follows Table II.
Figure 9 shows the relationship between the
[Pp·]= { z: (l-2/)[I]
2
( 6) maximum rate of polymerization and the PVA
concentration. From this result, it can be seen
Thus the rate of polymerization can be ob- that in the polymerization initiated by the HPO
tained from the eq 3 by substituting eq 5 and -AsA system at 20°C, the maximum rate of
6: polymerization is proportional to 0.22 power of
system
·e
C
1.0
Polymeri- [PVA], [VAc] [HPO] [AsA]
zation //
R
x 10, x 103 , x 103 , %/~in '
-o.8
temp, °C g mol// mol// mol// I
&-
1.48 2.04 2.47 2.50 3.9 o,0,6
0
2.22 2.04 2.47 2.50 4.5 ...J
20 2.96 2.04 2.47 2.50 4.6 0,4
3.70 2.04 2.47 2.50 4.6
0,8 1,0 1.2 1,4 1,6 1.8
4.44 2.04 2.47 2.50 5.0 I+ Log (PvA) ( 9/ I)
0.74 2.21 0.88 1.14 8.9 Figure 9. Maximum rate of polymerization (Rp)
1.48 2.21 0.88 1.14 10.3 vs. PVA concentration in the emulsion polymeri-
40
2.22 2.21 0.88 1.14 11.4 zation of VAc by the HPO-AsA system: (1) at
2.96 2.21 0.88 1.14 13.4 20°C, [VAc]=2.04 x 10-1 mol//, [HPO]=2.47 x lQ-3
2.22 2.04 1.24 2.50 3.3 mol//, [AsA]=2.50x10-3 mol//, [PVA] was varied;
2.22 2.04 2.47 2.50 4.5 (2) at 40°C, [VAc]=2.21 x 10-1 mol//, [HPO]=2.47
20 2.22 2.04 3.71 2.50 5.0 x 10-3 mol//, [AsA]=2.50 x 10-s mol//, [PVA] was
2.22 2.04 4.94 2.50 6.0 varied.
2.22 2.04 6.18 2.50 6.3
Recently, Matsumoto, et al.,9 investigated the
polymer latices of styrene prepared by KPS, and
the PV A concentration. proved by electrophoresis that most of the sulfate
It is believed to form different radicals from end groups of the polymer molecules are present
both initiator systems used, that is, the -sulfate on the surface of the polymer particles. On
ion radical and the hydroxyl radical, as shown the other hand, van den Hul et al., 10 have
below. pointed out that the latex particles of poly-
The KPS-AsA system styrene are stabilized by the sulfate end groups
O=C-
H0-6 I
0=?-1
O=C
I o I o
1;2
HO-C
I
I O=C
I I + HS04- +
H-C- H-C-
1 I
HO-C-H HO-C-H
I I
CHzOH CH 2OH
(AsA) (Dehydro-AsA)
recent knowledge, 4 • 8 - 10 the emulsion polymeri- end groups of the polymer molecules, so that
zation of YAc in the presence of PYA can be since the resulting particles come to be protected
explained as follows. by the PVA molecules which are present in the
Since YAc is a hydrophilic monomer, the reaction system, the number of polymer particles
polymerization of YAc in aqueous solution can is also affected by the PVA concentration.
be started by initiators which are soluble in Furthermore, the maximum rate of polymeri-
water, even in the absence of any emulsifiers. zation at 40°C varied with the PV A concent-
Then, when the polymer particles are formed in ration at power 0.32, unlike the result at 20°C
water, most of the end groups of the polymer as shown in Figure 9. The difference may be
molecules exist on the surface of the resulting explained by the fact that the effect of the hy-
particles, and these must contribute to the stabili- droxyl end groups on particle stabilization de-
zation of the latex particles both through electri- creases the as temperature rises.
cal repulsion and hydration effects, which the Figure 10 shows the variation of the time-
end group itself carries naturally. The sulfate
end group has both effects, whereas the hy-
droxyl end group has only one i.e., the hydra-
tion effect. Therefore, the degree of stabilization 50
for particles with the sulfate end groups must be
more powerful than the hydroxyl end groups.
As was previously mentioned, when the KPS- C:
30
AsA system was used as the initiator of poly- E
Q)
on stabilization for particles of the sulfate end Figure 10. Conversion vs. polymerization time in
groups is superior to that of the hydroxyl end the emulsion polymerization of VAc by PHO-
groups. AsA system at 20°C: (1) [HPO]=1.24x 10-a mol/
In the polymerization initiated by the KPS- l; (2) [HPO]=2.47x 10-3 mol/l; (3) [HPO]=3.71 x
AsA system in the presence of PYA, the maxi- 10-3 mol/l; (4) [HPO]=4.94x 10-3 mol/l; (5) [HPO]
mum rate of polymerization was independent =6.18 x 10-3 mol/l; [PVA]=2.04 x 10-1 mol//; [AsA]
of the PV A concentration, as shown in Figure =2.50x 10-3 mol//.
5. It therefore seems possible to conclude that
the stabilization of the resulting particles is 1.0
satisfactorily explained by the sulfate end groups
in the polymer molecules, and that the formation ..!;:o.Bf-
:,e
of the latex particles would be related, not to 0