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Determination of Reactivity Ratios for the Copolymerization of Styrene and StyreneAcrylonitrile with Polybutadienes

ROBERT A. HAYES, Central Research Laboratory, Firestone Tire and Rubber Co., Akron, Ohio 4431 7 Synopsis
The copolymerization of styrene and styrene-acrylonitrile with polybutadienes of various microstructures was studied and the reactivity ratios determined. It was shown that for the styrene/ acrylonitrile/polybutadiene systems the 1,2 structure is twice as reactive as the trans and four times as reactive as the cis. Studies in the temperature range of 5O-8O0C reveal that the reactivity of the polybutadiene increases as the temperature rises. When styrene is the monomer the reactivity of polybutadiene and the temperature effect is less intense than when styrene-acrylonitrile is used.

INTRODUCTION
In the preceding article' it was shown that the polymerization of styreneacrylonitrile in the presence of a relatively low vinyl content polybutadiene follows a relationship derived from the copolymerization equation. A technique was established for the determination of reactivity ratios for these systems. In this article the previous work is confirmed and expanded to the determination of reactivity ratios for styrene and styrene-acrylonitrile with polybutadiene. The effect of microstructure of polybutadiene and temperature is also studied.

EXPERIMENTAL DETAILS
A variety of polybutadienes was used in this study. Table I lists the polymers and their microstructures as analyzed by infrared (IR). The monomers were styrene and a 75/25 by weight mixture of stryene and acrylonitrile. Commercial grade materials were used as received. Polymerization procedures were the same as described in the preceding article,' except for the runs that contained styrene and a low-vinyl-content polybutadiene, which were run with cyclohexane as solvent instead of tetrahydrofuran (THF). The catalyst used was azoisobutyronitrile (AIBN) in all cases. Conversions were always less than 15%.

% cis

%trans
55.1 54.8 31.0 7.6
1.8

% 1,2

I
I1 I11 IV

33.8 36.8 21.8 7.9 96.1

11.1 8.4 41.2 84.5


2.1

Journal of Polymer Science: Polymer Chemistry Edition, Vol. 19,993-997 (1981) 0 1981 John Wiley & Sons, Inc. CCC 0360-6376/81/040993-05$01.00

994

HAYES
TABLE I1 Styrene-Acrylonitrile with Low-Vinyl-Content Polybutadienea Wt ratio MD in charge
3 3 4 4 5 5

Run No.
62-1 62-2 62-3 62-4 62-5 62-6

Sulfole 120 (pt/100 M)


0 1.0 0 1.0

WH

M n x~10-3
24.1 15.9 30.5 20.6 38.2 21.9

rlb

0 1.0

0.776 0.883 0.812 0.862 0.768 0.871

1270 1580 1410 1306 1150 1210

a Polybutadiene: 36.8% cis, 55.1% trans, 8.4% 1,2. Catalyst: AIBN, temperature: 70C, solvent: THF. r1 = 1320 f 150.

Analyses of the weight fraction of homopolymer and its molecular weight were done by high-speed gel permeation chromatography (GPC) with the techniques already described.' All runs except those involving the high cis-polybutadiene were easily analyzed by this technique. This rubber has some ultraviolet (UV) absorption when examined as received. Therefore it was necessary to correct for this condition in determining the weight fraction of homopolymer. The broad molecular weight distribution of this polymer also presented some difficulties
TABLE 111 Styrene-Acrylonitrile with Medium-Vinyl-Content Polybutadienea Wt ratio

MID
Run No.
55-1 55-2 55-3 55-4 55-5 55-6

in charge
3 3 4 4 5 5

Sulfole 120 (pt/100 M)


0 1.0

WH

M,,~ x 10-3
22.1 16.0 24.6 19.0 35.9 20.1

rlb

0 1.0 0 1.0

0.69 0.79 0.78 0.84 0.76 0.81

807 889 973 1050 1040 744

a Polybutadiene: 21.8%cis, 31.0% trans, 47.2% 1,2. Catalyst: AIBN, temperature: 7OoC, solvent: THF. rl = 917 f 125.

TABLE IV Styrene-Acrylonitrile with High-Vinyl-Content Polybutadienea Wt ratio

MID
Run No.
56-1 56-2 56-3 56-4 56-5 56-6

in charge
3 3 4 4 5 5

Sulfole 120 (pt1100 M)


0 1.0

WH

M,H x 10-3
20.2 13.9 21.7 16.2 26.8 18.7

nb
585 749 616 676 653 577

0 1.0 0 1.0

0.62 0.75 0.70 0.79 0.72 0.78

a Polybutadiene: 7.9% cis, 7.6% trans, 84.5%1,2. Catalyst: AIBN, temperature: 7OoC, solvent: THF. rl = 643 i 65.

DETERMINATION O F REACTIVITY RATIOS


TABLE V Styrene-Acrylonitrile with High-Cis-Polybutadienea Wt ratio

995

M/D
Run No.
54-1 54-2 54-3 54-5 54-6

in charge
3 3 4 5 5

Sulfole 120 (pt/100 M)


0 1.0

WH

M ~ H x

10-3

rlb

0 0 1.0

0.88 0.89 0.84 0.84 0.94

26.6 17.2 32.5 43.0 24.9

2650 1860 1790 1920 2970

Polybutadiene: 96.1% cis, 1.8%trans, 2.1% 1,2. Catalyst: AIBN, temperature: 7OoC,solvent: THF. brl = 2240 f 540.

because of a slight overlapping of the UV trace for homopolymer and grafted polymer. These difficulties were not considered serious enough to eliminate it from our studies.

RESULTS AND DISCUSSION


Reactivity ratios were calculated from the following equation in which M n ~ is the number-average molecular weight of the homopolymer, m is the weight ratio of monomer to polydiene in the charge, and W H is the weight fraction of homopolymer obtained.
rl

= M , ~ / 5 4m ( 1 - w1-1~1~)

This equation was obtained by rearranging eq. (9) from the preceding article' and assuming that y is equal to 1.00 (no polymer initiated by polydiene radicals). This assumption was justified by subjecting the data in Tables 11-VIII to linear regression analysis and determining ~ ' from 1 the ~ intercept. All values fell within 1.00 f 0.02. Tables 11,111,IV, and V show the results obtained when polybutadienes of different microstructure are copolymerized with styrene-acrylonitrile. A steady increase in reactivity of the polybutadiene (decrease in r l ) is shown as the vinyl content is increased. Tables VI, VII, and VIII reveal the same trend when styrene is the monomer. I t is also noted that styrene is less reactive than styrene-acrylonitrile in all cases.
TABLE VI Styrene with Low-Vinyl-Content Polybutadienea Wt ratio M/D in charge
3 3 4 4 5 5

Run No.
86-1 86-2 86-3 86-4 86-5 86-6

Sulfole 120 (pt/100 M) 0 0.33 0 0.33 0 0.33

WH

M,H x 10-3
37.3 17.2 45.7 17.2 50.7 22.4

r lb

0.86 0.92 0.90 '0.93 0.91 0.95

3150 2590 4070 2210 4080 3320

a Polybutadiene: 33.8% cis, 55.1% trans, 11.1% 1,2. Catalyst AIBN, temperature: 70C, solvent cyclohexane. rl = 3240 f 760.

996

HAYES
TABLE VII Styrene with Medium-Vinyl-Content Polybutadienea Wt ratio

M/D
Run No.
64-1 64-2 64-3 64-4 64-5 64-6
a

in charge
3 3 4 4 5 5

Sulfole 120 (pt/100 M)


0 1.0 0 1.0 0 1.0

WH

M,,H x 10-3
10.3 6.2 14.4 6.8 20.0 7.2

rlb

0.90 0.92 0.90 0.94 0.90 0.96

1221 935 1310 1050 1460 1330

Polybutadiene: 21.8% cis, 31.0% trans, 47.2% 1,2. Catalyst: AIBN, temperature: 7OoC,solvent:
rl = 1220 f 190.

THF.

To determine the effect of temperature on the reactivity ratios runs a t 50 and 8OoCwith styrene and styrene-acrylonitrile with polybutadienes of relatively low vinyl content were made. A comparison of the results in Tables IX and X indicates that the styrene-acrylonitrile system is more temperature sensitive than styrene alone. An energy of activation for the former was calculated to be about 7000 cal. The differences in values of r-1 for the styrene system were too small to calculate any meaningful energy of activation. Many workers have suggested that if copolymerization did take place in these systems it would occur only with the vinyl groups. If this were the case, the
TABLE VIII Styrene with High-Vinyl-Content Polybutadienea Wt ratio M/D in charge
3 4 4 6 5

Run No.
65-1 65-3 65-4 65-5 65-5
a

Sulfole 120 (pt/100 M)


0 0 1.0 0 1.0

WH

M,,H x

lo+

rlb

0.89 0.90 0.92 0.91 0.94

10.9 14.3 7.5 12.4 8.4

1180 1300 850 1000 1040

Polybutadiene: 7.9% cis, 7.6% trans, 84.5% 1,2. Catalyst: AIBN, temperature: 70C, solvent:
rl = 1070 f 170.

THF.
TABLE IX Styrene-Acrylonitrile with Low-Vinyl-Content Polybutadienes Wt ratio

M/D
Run No.
84-1 84-3 84-5 82-1 82-3 82-6

in charge
3 4 5 3 4 5

Temperature ("C)
50 50 50 80 80 80

WH

M,,H x 10-3
60.4 87.2 98.9 13.0 16.0 19.0

r1b

0.73 0.68 0.70 0.81 0.83 0.85

2480 2310 2250 800 830 900

Polybutadiene: 36.8% cis, 66.1% trans, 8.4% 1,2. Catalyst: AIBN, solvent: THF. rl(50OC) = 2350 f 120; rl (8OOC) = 840 f 50.

DETERMINATION OF REACTIVITY RATIOS


TABLE X Styrene with Low-Vinyl-ContentPolybutadiene" Wt ratio

997

MID
Run No.
89-1 89-3 89-5 88-1 88-3 88-5
a

Temperature

in charge
3 4 5 3 4 5

("0
50 50 50 80 80 80

WH

M ~ H

10-3

rlb
3420 3610 4560 2890 2610 3140

0.86 0.88 0.90 0.91 0.91 0.93

40.5 48.6 62.8 21.5 25.9 30.5

Polybutadiene: 33.8% cis, 55.1% trans, 11.1% 1,2. Catalyst: AIBN, solvent: cyclohexane. rl(50OC) = 3860 f 610; rl(8O"C) = 2880 f 260.

values of llrl should give a constant value if they are multiplied by the percentage of vinyl in the polybutadiene. Examination of the results shows that the low vinyl compounds are too reactive for this to be true and that the cis and trans double bonds are participating in the reaction. The variation of microstructure in the polybutadienes used for the styrene-acrylonitrile studies is sufficient to set up four simultaneous equations and to solve them for the best values of l l r l of cis, trans, and 1,2. The values of rl so obtained are 2400,1200, and 580, respectively. Use of these values in back calculations yields results that agree extremely well with those measured. Although examination of the styrene-polybutadiene systems shows that the cis and trans structures are active in the copolymerization reaction, the ratios of cis to trans in the polymers studied are too similar to permit a determination of the reactivities of each. It appears that the 1,2 structure is about four times as reactive as the 60:40 ratio of trans to cis. These data reinforce the conclusion drawn in the preceding article1that the grafting that occurs when vinyl monomers are polymerized in the presence of polybutadiene proceeds by copolymerization. As already noted,l the values of r l for the styrene-acrylonitrile systems should be labeled "apparent" because the mixture of monomers was treated as a single monomer. These apparent values will change as the ratio of styrene to acrylonitrile is changed.

Reference
1 . R. A. Hayes and S. Futamura,J. Polym. Sci. Polym. Chem. Ed., 19,985 (1981).

Received September 19,1980 Revised November 13,1980 Accepted November 13,1980