J. POLYMER SCI.: Symposium No. 5 2 .

5 5 - 6 6 (1975)

ACRY LONITRILE COPOLYMERIZATION. VII SOLVENTS EFFECTS IN STYRENE COPOLYMERIZATION

C . PlCHOT, E. ZAGANIARIS,* and A. GUYOT

CNRS- Ciiigtique Chimique Macroiiiol;c.ulaire, 69626 Villeurbanne, France

SYNOPSIS
The styrene-acrylonitrile radical copolymerization kinetics have been studied for polymerizations carried out in two different solvents, toluene and dimethylformamide (DMF), in the whole range of monomer mixture compositions and at various dilutions. The copolymer prepared in toluene solutions are poorer in acrylonitrile than those prepared in bulk. The reverse situation is observed in DMF solution, where the polymerization rate is the highest. In the latter case, also for acrylonitrile rich mixtures, the relative polymerization rate of styrene tends to increase with conversion; this effect is attributed to preferential solvation of styrene. Possible explanation of these facts are briefly discussed.

INTRODUCTION
In the previous paper of this series [ l ] , it has been shown that kinetic deviations from the accepted theory of radical copolymerization was the rule in the case of acrylonitrile copolymerization with many comonomers. A possible cause of such a behavior, namely the cyclization reaction involving the attack of a CN group on the penultimate unit by the chain-end radical, previously suggested for the copolymerization with vinyl chloride [2], is not a satisfactory explanation in the other cases, especially with a nonpolar, pure hydrocarbon monomer such as butadiene or styrene. The apparent correlation between the difference in polarity and the extent of the kinetic deviation led us now to turn toward a physical explanation. On the other hand, and contrary to the generally accepted view, it has been shown recently that the reactivity ratios in radical copolymerization involving polar monomers are dependent on the nature of the solvents. This is important chiefly in thc case o f acrylamide copolymerization [3-61. Some results have been published also for acrylonitrile-methyl-methacrylate 171 and styrene-methacrylonitrile [8] . The present paper deals with the system styrene@)-acrylonitrile(AN). A previous study has been carried out using two different solvents, toluene and dimethylformaniide for the two different parts of the composition range in order t o be sure
*Present address: Physical Chernistry Laboratory, University of Patras, Greece.

55
0 1975 by John Wiley & Sons, Inc.

56 PICHOT, ZAGANIARIS, AND GUYOT

that the copolymers formed were fully soluble in the reaction medium. The results were interpreted in terms of penultimate effect [9]. This study was extended in both solvents in the whole range of composition and also used the dilution as a parameter. The results point out a strong dependence of the reactivity ratios upon the nature, as well as the amount, of the solvents. Other effects are shown.

RESULTS AND DISCUSSION Reactivity Ratios

The copolymerization reactions have been carried out at 60C using azobisisobutyronitrile (AIBN) as initiator in three series: two in DMF with dilution around 2 mole/liter and 0.6 mole/liter, respectively, and the third one in toluene at about 2 mole/liter. The charge of the reaction, the composition ratio A/S in the monomer mixture (XA) (or the reverse xs = S/A) and in the copolymer initially formed (nA), (ns), the initial individual consumption rate of each monomer (dpA and dps) corrected from the influence of the initiator concentration I by r', and finally some results of intrinsic viscosity data in DMF at 25'C, are reported in Tables I, 11, and 111 for each series of copolymerization runs. The kinetic data have been used to draw the Fineman-Ross [lo] plot for the extreme ends of the composition range, illustrated in Figures 1 and 2, respectively.
TABLE I
(AN-Styrene) Copolymerization in DMF Solutiona; Charges and Kinetic Results

AN

ONF
RUN

STYR

AIBN I[

d A

d S
S. min.

moles

moles

molws

moles

5 min,

4.45 4.81

0.013 0.104 0.145 0.36

1.02 0.95 0.66 0.67 0.487 0.370 0.236 0.117 0.059 0.037

4.89 4.86 4.89 4.87 4.47 4.91 4.57 4.98 4.88 4.92

.0.396
0.320

0.118

0.012 0.110

0.04

0.143 0.130 1.65

0.25
0.45
0.66

5.33
5.55

0.267 0.205 0.126

0.101 0.140

0.22
0.535 1.08

5.50
5.10

0.530
0.648 0.880 1.07 1.171

0.133
0.184

0.87
0.96
1.40 2.65

1.76

5.50
4.80 5.00
6.00

0.345
3.373

3.73
9.17 20.25 33.34

0.106
0.095 0.093

0.520
0.56

3.70
5.60

1.23

aDilution: 2 mole/liter.

SOLVENT EFFECTS IN STYRENE-AN

57

TABLE I1 (AN-Styrene) Copolymerization in DMF Solutiona; Charges and Kinetic Results

OMF
AN

RUN

STYR

AIEN 10

viscosity
11

moles

moles

moles

moles

1' 6
210 2 11 212
1' 3

4.85 5.45
6.06

0.0094 0.047 0.113

0.200
0.226

0.185 0.201 0.212 0.095

0.050

4.02 3.96 4.22 4.76 4.57 4.88 4.88

9.16

5.74 5.26
6.5

19.62 17.72 13.75 14.45

p28 ' 2 9

0.2984
0.408

0.0134 0.0080

6.8

aDilution: 0.6 mole/liter.

TABLE 111 (AN-Styrene) Copolymerization in Toluene Solutiona; Charges and Kinetic Results

TOLUENE

AN

STYR

I B N 10

RUN

dpA

dPS

moles

moles

moles

moles

% min

% min.

5
5 1.02 0.98 0.197 0.0268 0.0675
0.026

4.86 4.89 4.9 4.9 4.89 4.88 4.89 2.12 4.55 1.78 2.18

0.051

-0.364
0.338
38.10

5.34 1.64
4.6

0.038

14.60
7.6

86.7

0.804 5
4.42 4.35
3.0

0.092 0.100 0.327

8.74 0,027
0.050

0.645
0.665

0.186 0.127
0.126

6.40

0.96
0.80

2.03 1.07
0.65

36.0
32.7

0 ' .525
0.372 0.262
0.03E

0.500
0.575

0.066
0.063

0.56
0.605

0.091
0.029

4.60
2.50

1 ,260
0.830 0.980

0.09 0.089 0.160

0.208 0.0435 0.0185

0.356 0.126E 0.0685

0.031 0.043

2.60

0.018

aDilution: 2 mole/liter.

- --

58 PICHOT, ZAGANIARIS, AND GUYOT

FIG. 1. Fineman Ross plot for copolymerization with high acrylonitrile contents: (X) polymerization in bulk (ref. 11); (0) in toluene solution (2 mole/liter); (0)in DMF solution (0.6 rnole/liter); (A) in DMF solution (2 mole/liter).

FIG. 2. Fineman Ross plot for copolymerization with high styrene contents: (X) polymerization in bulk (ref. 11); (0)in toluene solution (2 mofe/liter); ( 0 ) in DMF solution (0.6 molefliter); (A) i n DMF solution (2 mole/liter).

SOLVENT EFFECTS IN STYRENE-AN 59

4 ,
"A -

xA 0.3

/ /

0.2

0. I

I/"
I
I

0 . 1
(0)

0.2
(0)

FIG. 3. Derivation of IA: (X) bulk; mole/liter).

toluene;

DMF (0.6 mole/liter); ( a ) DMF (2

The data from bulk copolymerization by Thomson and Raines [ l 11 have been included for comparison. Obviously, it is not possible to draw straight lines for each series of data, so that the deviations from the Lewis and Mayo theory are confirmed. Further, the results are strongly dependent upon the nature of the solvent and even the dilution. In order to derive the reactivity ratios, the plots of n/x versus x or l/x (Figures 3 and 4) were used and extrapolation to XA = 0 and I/XA = 0, respectively, for rs and rA. The results are reported in Table IV, together with the previous results and

I
0
0 . 2
(0)

XA

OX

0 . 6
(0)

FIG. 4. Derivation of IS: (X) bulk; mole/liter).

toluene;

DMF (0.6 molelliter); (a) DMF (2

60 PICHOT, ZAGANIARIS, AND GUYOT

TABLE IV Reactivity Ratios

Temp. Solvent

Plethad

Oilutlor
mole/l
Ref.

FR extr b ' Toluene FR

I1

from 11
9
t h i s work

extr.
extr. 60 DMF

this work
t h i s work

0.6

extr.

aFR = (Fineman Ross plot): best fit with straight line for a large composition range. bextr. = extrapolation using plots n/x v e m s x or UX.

those derived from bulk polymerization. In the latter case, there is practically no difference between the values obtained using the best straight line of a Fineman-Ross plot for the whole range of monomer mixture composition, or from extrapolation of the data to xA = 0 or l / X A = 0. In solution, the differences are large, especially for the acrylonitrile radical; its relative reactivity versus acrylonitrile is larger than in bulk and is enhanced by the use of DMF and upon dilution in this solvent. It is well known that the nitriles are strongly associated through dipolar bonding [I21 ; thus, possibly, the acrylonitrile monomer may react in two ways: as a free monomer and in associated form; upon dilution the first one is favored. Further, it has been shown [I31 that acrylonitrile may be associated with DMF, which is a solvent with about the same polarity and dielectric constant (see Table V). So, a third kind of acrylonitrile monomer species may be expected in this study. The large change in acrylonitrile radical reactivity in DMF upon dilution may
TABLE V Selected Physical Properties of Monomers and Solvents
DIPOLAR MOMENT DIELECTRIC CONST.
~~~~~~~~~

CoMPoUNo

p [Oebye 20'

C1

(25' C1

125' C l

DMF ACRYLONITRILE STYRENE TOLUENE

3.82 3.88

35

12.1

38
2.43 2.88

10.4
8.6

0.37

0.39

8.9

SOLVENT EFFECTS IN STYRENE-AN 61

reflect the competition between the three different species. Possibly also one has to consider solvation and association effects concerning the radicals, as suggested by Cameron [8] for the similar system styrene-methacrylonitrile. Initial Composition When a copolymer system does not follow the classical theory of Lewis and Mayo, a set of two reactivity ratios is not sufficient to describe the copolymer compositions in the whole range. The deviation from ideality may be estimated from Ang/ngc where Ans is the difference between the experimental value o f nS and the nsc calculated from reactivity ratios. From Table IV it may be seen that for bulk copolymerization, the two sets of possible reactivity ratios are very close together. Using the extrapolated rA = 0.06 and rS = 0.34, the calculation of An/n gives the results illustrated in Figure 5. In toluene solution, the copolymers are richer in styrene than expected, chiefly for acrylonitrile rich monomer mixtures; admitting the explanation given above, and because styrene and toluene have about the same electrical properties, the change in composition might be caused by an enhanced participation of free acrylonitrile monomer. On the other hand, upon dilution in DMF the reverse composition change is observed: the copolymer becomes richer in acrylonitrile. We may expect that this effect is caused by the participation of DMF-associated acrylonitrile monomer. Initial Rate In Figures 6 and 7 the initial rates are plotted, expressed as individual yield per minute for each monomer, and corrected from the minor changes in initiator concentrations upon multiplying by I-. The corresponding data in bulk are not
I

100

- 0.2
-0.4 0 . 6

FIG. 5. Copolymer composition deviations in: 1, DMF (2 mole/liter); 2, DMF (0.6 molelliter); 3, toluene; 4, bulk. From the calculated values assuming rs = 0.34 and A = 0.06.

62 PICHOT,ZAGANIARIS, AND GUYOT

50

100

FIG.6. Corrected initial rate (yield in %/min.mole.liter-' ) for styrene conversion versus percent styrene i n monomer mixture for copolymerization in ( 0 ) toluene (2 mole/liter); (0) DMF (2 mole/liter); (A) DMF (0.6 mole/liter).

IACRYLONITRIL~
0
50

v.
100

FIG.7. Corrected initial rate (yield i n %/min.mole/liter) for acrylonitrile conversion versus
percent acrylonitrile in monomer mixture for copolymerization in DMF (2 mole/liter); (A) DMF (0.6 molelliter).
(0)

toluene (2 mole/liter);

(0)

SOLVENT EFFECTS IN STYRENE-AN

63

given in reference 11 and others papers in the literature so that we may only compare the effect of solvents and dilution. In the case of styrene (Fig. 6 ) and in styrene-rich mixtures the polymerization is not dependent on the dilution in DMF and this fact shows that the order of the reaction versus monomer concentration is first-order as expected. The rate is lower in toluene. The reason for that might be a change in initiator efficiency which may be larger in DMF because the transfer reaction in DMF may allow the primary radicals t o escape from their initial cage. The transfer reaction in DMF of polymer radicals is shown here by the lower values of molecular weight although the polymerization rates are higher in DMF. Upon increasing the acrylonitrile contents, the styrene polymerization rate increases; that may be assumed to be a copolymerization effect because the acrylonitrile radicals are more reactive versus styrene than styrene radicals. For acrylonitrile (Fig. 7) a t high acrylonitrile contents, the rate is again higher in DMF and increases a little upon dilution; that might mean that the DMF-associated acrylonitrile monomer is more reactive. The rate tends to increase with styrene content, after a plateau value or even a slight minimum, if copolymerization is carried out in toluene solution. The situation is very different here from that of vinyl chloride-acrylonitrile copolymerization described in a previous paper [2]. We have suggested to explain the depression in the rate by the formation of imine radicals upon a cyclization reaction involving the attack of a C 5 N bond by the growing radicals. This reaction causes a marked coloration of the vinyl chloride-acrylonitrile copolymers. However, in the case of styrene-acrylonitrile copolymers, the optical density at 290 nm remains very low and does not increase notably upon dilution.

Conversion Effect
In a previous work [9] it has been shown that the composition of the copolymer of styrene and methyl methacrylate with acrylonitrile, at high acrylonitrile contents do not follow, upon increasing conversion, the law expected from the initial composition for various monomer mixture composition; the acrylonitrile content is lower than expected and the discrepancy increases with increasing conversion. This effect has been interpreted at first in terms of acrylonitrile monomer trapped by association with nitrile groups of the copolymer and, thus, not yet available for polymerization. However it appeared that this effect was not general: for instance it has not been observed in the case of vinyl chloride or vinyl acetate copolymerization with acrylonitrile [14]. So another kind of explanation is necessary. In this work, the effect has been confirmed for copolymerization in DMF solution with acrylonitrile-rich monomer mixtures. But it is not observed in the same solvent with styrene-rich monomer mixtures, and it is not observed for copolymerization in toluene in the whole range of composition. The results are illustrated in Figures 8 and 9. The deviation observed in DMF solution increases obviously with the value of XA, i.e., with the amount of copolymer formed. It is

64 PICHOT, ZAGANIARIS, AND GUYOT

"S

25 -

20 -

/' /'

FIG. 8. Copolymer composition ns versus xs for styrene-rich monomer mixture (2 mole/liter) composition for acrylonitrile-styrene copolymerization in: ( 0 ) toluene; ( 0 ) DMF.

"A

lo

' b

5 -

XA

50

'

100

FIG. 9. Copolymer composition nA versus acrylonitrile-rich monomer mixture composition (---) initial composition curve, ( ) composition at increasing conversion. Copolymerization in: ( 0 ) toluene (2 mole/liter); ( 0 ) DMF (2 mole/liter); (A) DMF (0.6 mole/liter). The data for bulk copolymerization (x) (ref. 11) are given for comparison.

SOLVENT EFFECTS IN STYRENE-AN

65

"A,O-

"A,t

STYRENE

,CONVERSION Y,
50
100

FIG. 10. Relative enrichment of the copolymer in styrene as a function of the styrene conversion for copolymerization in DMF solution. The initial conditions are: 0, XA,O = 22.2 (dilution 0.6 mole/liter); 0 , XA,O = 20.2 (dilution 2 mole/liter); A , XA,O = 9.15 (dilution 2 mole/liter).

also larger upon dilution. It is interesting to consider the deviation expressed by (no - n)/no, as shown in Figure 9. It appears that the deviation increases a great deal with styrene conversion (Fig. 10) and is slightly dependent on factors such as initial composition and dilution. The cause of this behavior might be a preferential solvation of styrene by the polymer formed. Obviously, as shown in Table V, styrene is very different from DMF and acrylonitrile and has physical properties close to that of toluene. One may consider that the reaction medium is not totally homogeneous as soon as the polymer is formed. There are polymer-rich regions where the polymerization rate is the highest, owing to the effect of diffusion on the termination rate, and if styrene is preferentially adsorbed in these regions, the relative polymerization of styrene becomes more and more rapid. Such a situation is obviously not valid if the solvent is toluene. Preferential solvation has been shown recently to occur in the styrene-acrylonitrile polymerization in the presence of polybutadiene [ 151

CONCLUSIONS
It is clear that in the present system, the nature of the solvent has a large influence on the behavior of the solution copolymerization, although the effect is not so large as in the case of acrylonitrile-acrylamide copolymerization [ 6 ] . Secondary reactions such as the cyclization reaction involving the internal copolymerization of the nitrile groups, are probably negligible in the present case. A reasonable explanation of the deviations from the Lewis and Mayo theory seems to

66 PICHOT, ZAGANIARIS, AND GUYOT

be the various reactivity of acrylonitrile in the various possible forms: free monomer (upon dilution in nonpolar solvent) dimer associated by dipolar nitrile-nitrile bonds, or polar-solvent-associated monomer. Possibly also the association may involve not the monomer but the radicals. However, another explanation is not excluded, based on physical factors: owing to their large difference in solubility parameter or dipolar moment, styrene and acrylonitrile might be segregated in solution. The presence of polymer may increase this tendency through a phenomenon of preferential solvation. If such a situation actually occurs, it might cause some tendency to blockiness in the copolymer and might be detectable through a study of sequence distribution. Our future work will be directed in this way.

REFERENCES
[ 11 A. Guyot, M. Dumont, Ch. GraiUat, J. Guillot, and C. Pichot, J. Macromol. Sci. C h e m , i n press. 121 Ch. Graillat, J. Guillot and A. Guyot, J. Macromol. Sci Chem A 8, 1099 (1974). [3] G . Saini, A. Leoni, and S. Franco, Macromol. Chem., 144, 235 (1971); 146, 165 (1971). [4] L. M. Minsk, C. Kotlarchik, and R. S . Darlack, J. Polym. Sci. Polym Chem. Ed., 11, 353

(1973). [5] L. M. Minsk, C. Kotlarchik, and G. N. Meyer, J. Polym. Sci. Polym. Chem. Ed., 11, 3037 (1973). [6] L. Perec, Polym Lett. 11, 267 (1973); A. Chapiro and L. Perec-Spritzer, Eur. Polym. J., 11. 59 (1975). [7] M. M. Zafar, R. Mahmud and A. M. Syed, Makromol. Chem, 175, 1531 (1974). [8] G. C. Cameron and G. F. Esslemont, Polymer /G. B.), 13, 435 (1972). [9] A. Guyot and J. Guillot, J. Macromol. Sci (Chem), A I , 793 (1967); A 2, 889 (1968). [ l o ] M. Fineman and S. D. Ross, J. Polym Sci, 5 , 259 (1950). [ l l ] B. R. Thomson and R. M. Raines, J. Polym Sci., 41, 265 (1959). [12] A.M. Saum, J. Polym S c i , 42, 57 (1960). [13] C. Spritzer, J. Chim Phys, 68, 340 (1971). [ 141 J. Guillot, unpublished results. [ 151 J. L. Locatelli and G. R i m , Makromol. Chem., 27, 201 (1974).