T r a n s f e r

C o n s t a n t s

P o l y m e r s ,

C a t a l y s t s

S o l v e n t s S u l f u r

a n d

t o a n d

I n i t i a t o r s ,

A d d i t i v e s ,

C o m p o u n d s

R a d i c a l

M o n o m e r s ,

i n

a n d F r e e

P o l y m e r i z a t i o n

A. Ueda Osaka Municipal Technical Research Institute, Osaka, Japan S. Nagai Plastics Technical Association, Osaka, Japan

A. Introduction B. Tables Table 1. Transfer Constants Table 2. Transfer Constants Table 3. Transfer Constants Initiators Table 4. Transfer Constants Additives Table 5. Transfer Constants Compounds C. Remarks D. References A.

to Monomers to Polymers to Catalysts and

11-97 11-98 II-98 11-103 11-106

to Solvents and 11-110 to Sulfur 11-150 11-157 11-159

INTRODUCTION

The transfer reaction in radical polymerization describes a process in which the polymer radical reacts with another molecule (monomer, polymer, catalyst, solvent, modifier, etc.) forming a dead polymer and new radical. This new radical can continue the kinetic chain:

If it is assumed that (a) all new radicals X# react only by formation of growing polymer radicals; (b) all polymer radicals have equal reactivities independent of their size; (c) all rate constants are independent of solvent; (d) the consumption of monomer by initiation and transfer is negligible compared with propagation; (e) a steady-state concentration of polymer radicals is quickly established (d[P#]/dr = 0). The application of these assumptions to the common reaction scheme results in the following relationship of ideal kinetics (Ref. 145):

P n , p n 0 = number-average degree of polymerization obtained in the presence or absence, respectively, of transfer agent X. [M], [X] = concentration of monomer or transfer agent, respectively.

The dimensionless transfer constant is defined by the ratio

where kv is the rate constant of propagation. Based on the tables in the third edition, by K. C. Berger and G. Brandrup.

The left-hand side of this equation is obtained by measuring the number average molecular weight of polymer at different concentrations of the transfer agent X, all other variables being kept constant. In many cases the degree of polymerization was determined by measurement of viscosity (Remark R). It should be noted that the ratio of

viscosimetric to number average molecular weight shows a considerable dependence on the molecular weight distribution. The first term P n 0 of the right-hand side of this equation is the number average molecular weight measured in the absence of transfer agent X. This is limited to cases where the transfer agent is a modifier. In all other cases, Pno is calculated by combination of several kinetic expressions and used with its numerical value:

This decrease of the transfer agent concentration with increasing monomer conversion is important in practice because very reactive transfer agents are used up preferentially, giving a broad molecular weight distribution if they cannot be replenished. In analogy to quickly decomposing initiators with their criterion of "half-life", one can define, in addition to the transfer constant Cx, a "half-conversion" U\/2 as that monomer conversion where the transfer agent is half consumed:

Initiation Termination Propagation Number-average molecular weight where ku fct,d, and k^c are the rate constants of termination, termination by disproportionation, and termination by combination, respectively.

The second term of the right-hand side of the above equation is given by the following expression:

where Cp is the constant of chain transfer with added polymer before starting polymerization. The transfer constant of very reactive molecules can be determined from the rate of disappearance of both transfer agent and monomer:

The following table demonstrates (with some examples for a calibration curve) that the "half-conversion" IZ1^2 decreases with increasing transfer constant Cx: The "Half-Conversion" of Transfer Agents Cx

U1/2(%)

Cx

Ul/2(%)

0.1 0.2 0.5 1 2

99.9 96.8 75.0 50.0 29.3

5 10 20 50 100

13.0 6.7 3.4 1.4 0.7

The transfer agent must be replenished at this monomer conversion at the latest, if polymerization is to proceed, still yielding a narrow molecular weight distribution. Numerous examples are known of polymerization systems that possibly do not satisfy basic assumptions: retardation (Remark J), induced decomposition and primary radical termination by peroxide or hydroperoxide initiation (Remarks C and B), diffusion control of termination (Remark X), electron donor/acceptor complexes (Remarks JJ), etc. Corresponding data in this table have to be used with caution.

B. TABLES OF TRANSFER CONSTANTS TABLE 1. TRANSFER CONSTANTS TO MONOMERS Monomer

T( 0 C)

Acetic acid, allyl ester

80

Acrylamide

25

Acrylamide, AT,iV-dimethylAcrylic acid, benzyl ester

50 60 60 50 55 60 60 60

- , butyl ester

C M (xlO 4 ) 170 700 0.12 0.16 0.2 0.2 0.558 0.651 0.6 1.5 0.883 0.905 0.333 1.05

Remarks

D E C2, F13, LL C2, F13, LL E

Cl, H, KK Cl, H, KK

Refs. 29 27 92 74 75 103 560 560 103 272 291 291 561 561

TABLE 1. cont'd Monomer Acetic acid, butyl ester (cont'd) -,ethyl ester

T( 0 C) 60 65 50 60 65 70

- , - 2 ethylhexyl ester - , methyl ester

70 80 50 55 60 65

70

75 -, tetrahydrofurfuryl ester -, 2-chloro-, ethyl ester - , thio-, methyl ester Acrylonitrile

40 60 60 20 25 30 40 50 60

Allyl bromide Ammonium chloride, A^-diallyl-MJV-diethyl- , Ar,Ar-diallyl-AW-dimethylAnisole, p-\iny\ Anthranilic acid, vinyl ester Benzoic acid, vinyl ester

1,3-Butadiene, 2-chloro- , 1,1,2-trichloro1-Butene 2-Butene, cis- , trans3-Butene-2-one, 3-methyl-

60 60 60 60 60 60 0 60 70 60 80 95 50 25 40 50 60 40 50 60 40 50 60 80

C M (xlO 4 )

Remarks

1.25 0.955 0.193 0.90 0.41 0.579 0.332 0.351 0.789 6.28 3.79 0.80 0.275 0.036 0.325 0.10 0.11 0.11 0.37 0.01 0.072 0.16 0.18 0.405 0.224 0.25 0.25 4.0 3.0 560 0.18 0.105 1.5 0.17 0.050 0.27 8.2 0.26 0.3 0.333 0.57 1.02 30 18 7 0.198 0.74 80 6.0 7.0 2.0 4.0 2.32 16 3.1 5.1 7.3 3.2 4.9 11.2 3.0 5.2 10.8 4.00

Cl, H, KK

F7 C, F17, R C, F17, R C, F17, R C, F17, R C, F17, R F7 C,AA B, AA C, AA C,AA CFlO CAA C, AA CFlO B, AA CAA C AA C, AA CAA C, FlO C AA C, F2 E F8 F18 F17 F16 Cl, H, KK Cl, H, KK Cl, H, KK C, R, HH Cl, F30 Cl, F30

F2 E

C

Refs. 561 291 306 510 512 512 306 306 512 512 512 510 221 221 221 221 123 221 221 322 221 221 221 221 221 123 221 319 342 140 299 284 196 284 410 376 362 95 23 561 561 561 505 538 538 13 53 139 321,393 26 321 213 153 230 334 334 334 334 334 334 334 334 334 84

Remarks page 11-157; References page 11-159

TABLE 1. cont '6 Monomer Butyric acid, vinyl ester Carbamic acid, vinyl-, ethyl ester Carbazole, A^-vinyl-7H-benzo(2)Decanoic acid, vinyl ester Ethylene

T( 0 C) 50 80 60 70 50 60

70

26.7 22.3 0.25 11 45.5 0.4 1.4 4.2 5.0 5.32 1.1 3.5 9.0 0.0 1.6 4.7 11.2 5 3.2 3.2 7.0 6.25 19.4 50 6.4 7.8 8.5 11 13.5 10.8 12.3 12.8 23.8

60

42

83 110

130

- , chloro-

50-70 20 25 30 40 50

60

Glutaramic acid, MA^-diisobutyl-, vinyl ester - , AW-diisopentyl-, vinyl ester

Hexanoic acid, vinyl ester 5-Hexen-3-yn-2-ol, 2-methylIsobutyric acid, vinyl ester Laurie acid, vinyl ester Maleic anyhydride Maleic anhydride/methyl methacrylate Maleimide, A^-(3-dimethylamino-6-methyl-phenyl) Methacrylamide Methacrylic acid, bornyl ester - , butyl ester

-, -, -, -, -, -,

tert-butyl ester o-r-butylphenyl ester /?-?-butylphenyl ester n-dodecyl ester 2,3-epoxypropyl ester ethyl ester

-, -, -, -, -,

0-ethylphenyl ester p-ethylphenyl ester glycidyl ester hexadecyl ester isobornyl ester

C M (xlO 4 )

60 70 80 80 60 80 50 75 60 50 60 60 50 60 70 60 60 60 60 45 60 80 90 60 60 60 70 60

51 51 51 36 5.0 46 45.5 750 100 720 10 x 105 2.85 0.54 120 x 105 0.14 0.35 30.41 2.01 80xl05 0.59 0.248 0.259 0.456 0.442 3.63 1.36 45 x 105 0.14 1.85

Remarks

Refs.

F4 Y

71 200 117 522 71 102 102 102 204 205 102 102 102 259 102 102 102 218 94 315 425 58 463 246 379 379 379 392 58 379 379 379 58

C, FlO

106

C, FlO C, FlO CFlO

107 107 107 200 226 200 71 175 367 542 515 162 233 515 264 9 550 550 515 198 193 193 193 193 550 550 515 138 162

R, F2 W5 W4, W5 W4 D, W D, W W4, W5 W4, W5 W4 C, F21,W5 W4, W5 W4, W5 W4 W3

Y F5 F3 F4 C, F26 Y F3

C F2 JJl

JJl

C C JJl CC CC CC CC C C JJl

TABLE 1. cont'd Monomer Methacrylic acid, isobutyl ester

- , n-nonyl ester - , phenyl ester - , o-tolyl ester - , p-tolyl ester Methacrylonitrile

Methyl methacrylate

J( 0 C) 35 50 60 80 100 60 27 60 60 60 25 60 70 80 0 30

40 50

60

65 70

75

80

Naphthalene, 1-vinyl1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoroPhernol, o-vinyl2-Picoline, 5-vinyl1-Propene, 2-chloro-, 2-methylPropionic acid, vinyl ester

90 100 120 50 60 70 110 70 70 80 40 50 60 50

C M (xlO 4 ) 0.189 0.179 0.14 0.165 0.224 0.301 0.382 105 x 105 400 0.61 1.13 1.06 2.08 5.81 8.00 10.05 0.128 0.148 0.117 0.260 0.15 30 x 105 242 x 105 0.10 0.15 0.477 241 x 105 0.85 0.07 0.10 0.103 0.18 240 x 105 0.20 0.17 0.20 0.23 0.265 0.29 0.30 0.45 0.807 1.37 240 x 105 0.27 0.33 0.60 0.70 0.25 0.40 0.10 0.38 0.58 290 310 300 500 130 6.7 1600 2.5 4.4 6.9 3.6 48.9

Remarks DD DD F2 DD DD DD JJl R C C C Z Z Z Z

D JJ2 JJl F2 D JJl

C JJO CFlO

C, F17 D JJl CFlO C CFIl C, F2

WlO

Refs. 193 193 264 264 193 193 193 515 534 550 550 550 125 125 125 125 69 18 69 224 508 525 528 147,327 145 224 528 69 274 34,290,317 316 145 556 123 123 267 145 440 123 123 104 224 459 528 123 123 123 123 145 123 147 145 145 216 216 216 68 186 11 27 334 334 334 158 71

Remarks page II-157; References page II-159

TABLE 1. cont'd Monomer Pyridine, 2-vinyl- , 4-vinyl2-Pyrrolidinone, 1-vinylStearic acid, vinyl ester Styrene

T( 0 C) 15-35 25 20 50 O 25 27 30 45 50

60

67.8 70

75

80 80.3 90

99 100

110 117 132

Styrene, p-boromo-, o-chloro-

50 30 50

C M (xlO 4 ) O 6.7 4.0 69.8 O

Remarks D

BB 0.108 0.279 0.358 0.31 0.2 0.32 0.3 0.35 0.40 0.50 0.6 0.62 0.65 0.78 0.07 0.6 0.6 0.6 0.75 0.79 0.85 0.92 1.1 1.37 20 x 10 5 1.0 O 0.6 0.6 0.8 0.96 1.16 1.35 2.0 O 1.6 5.0 5.00 0.7 0.75 1.00 4.0 0.85 1.25 1.47 1.79 1.5 1.72 1.8 1.83 2.80 1.40 2.45 3.0 3.4 5.33 23 0.25 0.25 0.28

A BB BB H F2 C, H C A, K B, C, H A C C BB A A, F

C JJl CFlO BB B, H A A C, F2 C,F10 C C, F2 CFIl BB BB CF A A A A, F A A A A, F A A

C C, H

Refs. 38 283 59 71 360 17,69 69,245 17 145 318,360 245 360 354,355 318,327 388 145 145 388 146 467 34,171,223 145,240 318,360 467 145 145 447 53 234 515 34 123 104 360 388 67 145 145 123 123 123 123 123 98 360 318 34 360 145 145 145 98 145 145 145 145 318 145 145 145 145 192 62 60 60

TABLE 1. cont'd Monomer Styrene, p-iodoSuccinimide, JV-vinylValeric acid, 4-methyl-, vinyl ester Vinyl acetate

T( 0 C) 50 55 80 -60 -40 -20 -20 O 20 25

40 45 50

60

65 70 Vinylidene chloride

50 60

C M (xlO 4 )

Remarks

Refs.

1.9 0.55 24.8 1.9 0.40 0.60 0.70 0.30 0.50 0.90 0.96 0.94 0.90 1.3 1.45 2.4 10.7 1.29 1.32 2.0 0.25 0.41 0.54 0.61 1.29 2 4.55 20 1.75 1.8 1.9 1.91 1.93 2.0 2.1 2.4 2.5 2.5 2.6 2.8 2.1 2.4 2.9 22 38

Fl C

113 R R

56 93 200 158 464 464 464 241 241 86 464 328 241 86 86 202 69 12 328 51 466 265 265 265 12 552 71 225 12 466 124 328 348 231 145 294 86 167 167 80 466 403 86 541 541

C P (xlO 4 )

Remarks

Refs.

D D D D D 14 D D 17 17 D

W14 W15 C

112 C

C C

TABLE 2. TRANSFER CONSTANTS TO POLYMERS Polymer Acrylamide, N,N-dimethylPoIy(N, Af-dimethylacrylamide) Acrylic acid, ethyl ester Poly(methyl methacrylate) - , methyl ester Poly(isoprene) - , chlorinated Poly (methyl acrylate) Poly (methyl methacrylate) Acrylonitrile Cellulose

T( 0 C) 50

0.61

272

60

12800

M6

120

75 60

12.6 0.5 1.0 18000

C, F2 L L M6

308 212 105 120

1.0 11 20

L, N L, M4 L, M5

361 361 361

60 60

Remarks page 11-157; References page 11-159

TABLE 2. cont'd Polymer Acrylonitrile, (cont'd) Poly(acrylonitrile) Poly(methyl methacrylate)

Poly(sarcosine) 1,3-Butadiene PoIy(1,3-butadiene) Ethylene

-, chloro Poly(vinyl chloride) Hexanoic acid, vinyl ester Poly(oxyethylene), dodecyl ether Methacrylic acid, butyl ester Poly(methyl methacrylate) -, dodecyl ester Poly (methyl methacrylate) -, ethyl ester Poly(isoprene), chlorinated Poly (vinyl chloride) Methyl methacrylate Poly(ethylene) Poly(isoprene), chlorinated Poly(methyl methacrylate)

T(0C)

50 60 60

60

Poly(vinyl chloride) Poly(vinyl urethane) Rubber, natural 2-Pyrrolidinone, 1-vinyl-dextran Dextran

376 135 25 25 25 25 23

C, C, C, C, C, C, C, C, C, C,

50

5

L

60

780

60

7700

M6

120

60

12800

M6

120

C, F2 C, F28

308 308

70 70

18.3 21.0

50 80 40

0.6 23.4 1.5 360 0.22 1.5 1.5 360 360 1000 0.1 1.5 2.1 360 2.48 0.22 1000 0.04 1.0 0.42 0.75 2.20 2.95 2.0 2.8 11 10.0 17 10.9 11.0

80 90

Poly(vinyl acetate)

F14 L N M2 M3 M

Refs.

11 108.40 150.70 194.81 214.46 337.31 256.85 195.81 199.89 155.78 348.46

60

Poly(styrene)

4.7 3.5 0.2 240 900 1270 400

Remarks

50 174.8 201.6 215.0 231.2 230.3 229.2 230.3 230.4 230.5 256.0

50

Poly(propylene)

C P (xlO 4 )

50 130 50 60 80 60 80 70 50 50 50

5 5.87

W20, F32 W20, F32 W20, F32 W20, F32 W22, F32 W21, F32 W20, F32 W19, F32 W18, F32 W20, F32

142 540 540 540 540 540 540 540 540 540 540 211 278

C, F17 N M N N M M N M N M N M C

C, F28 C, F8 C

209 307 326 326 147 326 327 326 327 147 105 326 262 326 262 147 147 292 209 292 148 262 262 263 263 250 308 157 258 258 333 203

TABLE 2. cont'd Polymer Styrene Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene) Poly(oxyethylene) - , dodecyl ether Poly(oxythexamethyleneoxy sebacoyl) Poly(methyl methacrylate)

T( 0 C)

60 70 70 60 80 50

60

Poly(propylene)

Poly(styrene)

80 100 60 66 130 50

55 60

73.5 85 90 100 110

Poly(vinyl acetate) Poly(vinyl chloride) Poly(2-vinylpyridine) Vinyl acetate Poly(oxyethylene) - , dodecyl ether Poly (methyl methacrylate) Poly(styrene) Poly(vinyl acetate)

130 154 100 130 50 60 60 60 75 40 60 75 -15 0 11 21 31 40 50

C P (xlO 4 ) 4.05 19 14 20 13 0.4 104 6000 >4xlO5 6303 4 1230 2300 2600 34760 700 9.0 10.0 10.5 3.4 2.26

Remarks

C

C F2 C C C C C C, J J C,J C C J C, J A, R A, R A, R A, R F2 C J J J J C C

C C J J D, S C C C C F2, J J C

Refs.

80

145,232 328 86 420 390 86 390 389 389 389 389 390 86 390 390 86 71 86 86 390 539 539 539 539 86 208 442 232 71 338 338 338 338 289 390 289 71 145,232 420 86 86 390 86 86 71 86 86 338 39 39 39 389 86 389 86 86 389 45 5 5 5 190 145,231

Remarks page II-157; References page 11-159

TABLE 4. cont'd Solvent/Additive

T (0C)

Vinyl acetate (cont'd) Methanol (cont'd) Naphthacene Naphthalene

70 50 50

- , decahydroNaphtho[l,2,3,4-def]chrysene Nonanoic acid, ethyl ester 2,6-Octadiene, 2,7-dichloro- , 2,6-dimethyl-

70 60 50 50 50 60

Octanoic acid, ethyl ester Oleic acid, methyl ester

50 60

Oxalic acid, diethyl ester - , dimethyl ester

90 30 60 60

Paraldehyde Pentane, 2,2,4-trimethyl2,4-Pentanedione 1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro2-Pentanone, 4-methyl3-Pentanone

70 50 60 60 60 60

Pentyl acetate

70 75 75 50 50

Orthoformic acid, trimethyl ester

Pentyl alcohol Perylene Phenanthrene

Phenol

70 45 50 60

- , m-chloro-,p-chloro- , p-nitro- , 2,3,4,6-tetramethylPhenol-D -,m-chloro-,p-chloro-,2,3,4,6-tetramethylPhosphorus trichloride Propane, 2-bromo-2-methyl- , 2-chloro-2-methyl 1-Propanol, 2,2,3,3-tetrafluoro1-Propene, 3-chloro- , 3-chloro-2-methylPropionaldehyde

45 45 50 45 45 45 45 45 60 60 60 60 60 60 60

Propionic acid, ethyl ester - , methyl ester

70 50 60

Pyrene Pyrocatechol, 4-(l,l,3,3,-tetramethylbutyl)Pyrogallol Salicylic acid Silane, dimethylphenyl-

50 50 50 70 60

C s (xlO 4 )

4.3 6.0 5.5 8.62 x 106 1150 1457 1715 48 1.35 x 105 80 3200 430 700 70 217 1000 358 7.6 8.0 4.0 1.0 2.0 136 8.0 10 26.1 34.52 10.0 114.39 7.2 87.0 56 2.88 x 105 870 5600

3380 215 120 600 205 400 8.86 x 104 1.13 x 104 35 70 80 800 1.5 x 104 150 26 7.11 3100 400 950 1000 457 40 23 26 11500 11000 50000 296 2200

Remarks

J J C,J J C F2 C J

C F2 19 C C C J J

C,J J J J J J J J J J C, D F2 J J F2 C C J J J C A, R

Refs.

320 86 320 370 370 15 390 86 41 71 152 324 7 71 441 86 441 345 346 86 86 145,232 390 208 86 442 289 145 289 390 184 184 41 370 15

390 51 15 86 51 51 15 51 51 51 51 51 214 86 86 442 86 86 86 86 390 71 232 420 370 338 338 390 539

TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Silane, methyldichloro- , trichloro- , triethyl- , triphenylStearamide, N-allylStearic acid, ehtyl ester - , methyl ester Succinic acid, diethyl ester - , dihexyl ester - , dimethyl ester m-Tolualdehyde p-Tolualdehyde Toluene

T( 0 C)

60 60 60 60 90 50 60 60 60 60 60 60

75 80 50 70 70 60 70 75 50 50 50 50 50 50 60 50 60 50 70 75 60 60 60

280 290 400000

Q(3) Q(3) Q(3)

511 511 511

50 60

20 20

R R

541 541

60 60 60 60 60

5400 8600 12000 2000 4000

A, R A, R A, R A, R A, R

539 539 539 539 539

C, Q(I-2)

572

60 70

Triphenylene Veratraldeyhyde Xylene Vinyl chloride Carbon tetrachloride Chloroform Bromotrichloromethane Vinylidene chloride Af-Methylpyrolidone 2-Vinylpyridine Silane, diethylchloro- , Methyldichloro-,trichloro-,triethyl-,triphenylVinyltrimethylsilane Bromoform

Refs.

A, R A, R A, R A, R C, J C

60

Toluene, p-nitrop-Toluidine -, N,Ar-dimethyl-, AT-methylToluonitrile Triethylamine

Remarks

5800 8800 1200 2700 620.1 140 38.2 41 40 31 570 440 3.3 12.0 14.9 100 123 17.8 20.75 20.89 21.6 34 35 49.0 69.0 21.1 21.8 29.2 66 91.6 20.6 92.86 195 450 584 118 106300 750 380 830 38.3 360 370 160 550 14.9 278 166

50

- , bromo- , o-chloro-,p-chloro- , a-chloro-

C s (xlO 4 )

1200000

J J R C R C J F2 W15 R C C C C J C C F2 F2 F2 F2 J J J C C

539 539 539 539 173 71 441 420 420 420 86 86 158 15 357 71 71 357 80 21,59,289 357 86 86 265 265 357 390 357 184 273 15 389 389 86 389 184 15 154 154 154 15 154 24,145 370 86 15 390 184

Remarks page 11-157; References page 11-159

TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS Modifier Acrylamide, A/-octadecyl-/acrylonitrile (1:1 mol ratio) 1-Dodecanethiol Acrylic acid 1-Dodecanethiol - , methyl ester 1-Butanethiol

J( 0 C)

Cx

Remarks

Refs.

60

0.539

C, F24

174

45

1.9

C, F31

549

Ethanethiol

30 60 50

2-Propanethiol

60

1.53 1.69 0.78 0.94 ±0.07 1.65 ±0.12 1.57 ±0.09 1.57 ±0.18 1.79 5.00 0.544 0.668 0.700 0.656

A A Ql Ql Q2 Q3 Q4 Q2 Q3 Ql Q2 Q3 Q4

Acrylonitrile 1-Dodecanethiol Hydrogen sulfide Methyl sulfoxide

Methyl tetrasulfide p-Toluenethiol Acrylonitrile/1,3-butadiene (10-90%) 1-Hexanethiol, - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol, - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (20-80%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (30-70%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/styrene (38.5-61.5 mol%) 1-Pentanethiol - , 1,1,3,3,4-pentamethylButadiene Xanthogendisulfide, dibutyl- , diethyl- , di-2-ethylhexyl- , di-isopropyl1,3-Butadiene 1-Butanethiol, 1,1,3,3-tetramethyl1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl1-Tetradecanethiol 1,3-Butadiene/styrene 1-Dodecanethiol Formic acid, thio-, dithiobis_, _, _, ao'-dibutyl ester

50 50 20 30 40 50 80 50 5

0.73 0.13 0.1 0.47 0.0000812 0.11 0.29 0.795 0.69 0.97

C, F8 E

J

397 69,397 330 478,507 478,507 508 330,509 330 330 477 477 477 477 378 378 248 196 458 404 197 375 85 378

1.5

C, H

380

53.3

C, H

380

5

1.2

C, H

380

5

2.1

C, H

380

5

1.1

C, H

380

5

1.8

C, H

380

50

1.02

C, H

380

60 60 60 60

6.9 8.1 7.5 8.3

J J J J

532 532 532 532

5 50 5 50

5.3 3.7 21.8 16.0 19.0 3.0 19.5

H H H H H H H

242 242 242 242 243 242 242

50 50 5

0.66

B, H, J

384

5

2.42

B, H, J

383

TABLE 5. cont'd Modifier

T( 0 C)

1,3-Butadiene/styrene {cont'd)

- , - , ao'-diisopentyl ester

-5 50 5 -5 5 50 5 -5 50 5 50 5 50 5 -5 50 5

- , - , - , 0,O'-diisopropyl ester

-5 50 5

- , - , - , O,O'-di-sec-butyl ester - , - , - 0,O'-dicyclohexyl ester _, _, _, 0,0'-diethyl ester - , - , - , 0,O'-diheptyl ester - , - , - , 0,6>'-dihexyl ester - , - , - , 0,O'-diisobutyl ester

- , - , - , 0,O'-dimethyl ester - , - , - , 0,O'-dineopentyl ester - , - , - , 0,0'-dioctyl ester - , - , - , 0,O'-dipentyl ester - , - , - , 0,0'-dipropyl ester 1-Heptanethiol - , 1,1,3,3,5,5,6-heptamethyl1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Octanethiol - , 1,1,3,5,5,7,7-octamethyl/7-Dioxin, 2,3-dihydro/maleic anhydride 1-Butanethil Ethylene 1-Butanethiol Ethyl sulflde Methyl sulfoxide 2-Propanethiol, 2-methylSulfur hexafluoride Methyl methacrylate Acetic acid, dithiodi-, diethyl ester - , mercapto-, methyl ester Acetophenone, 3'-mercapto- , 4'-mercapto-

-5 50 5 -5 50 5 50 5 50 5 -5 50 5 -5 50

Cx 1.75 5.34 1.65 1.565 1.78 3.71 8.43 4.23 16.04 0.41 1.12 0.74 1.78 1.87 1.573 6.43 1.21 7.0 1.85 4.38 2.83 3.4 12.5 0.40-1.31 0.80-3.01 1.40-3.70 1.80-3.50 1.80-6.0 9.78 1.185 9.78 16.43 15.86 27.04 1.01 3.40 0.23 0.64 1.45 1.70 3.20 4.42 1.815 9.20

Remarks H C, H, J B, H, J H B, H, J C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J B, H, J H C, H, J B, H, J B, H, J B, H B, H, J, B, H, J, B, H, J, B, H, J, B, H, J,

Refs. 180 382

H C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J H C, H, J

180 383 383 383 180 382 383 382 383 382 383 180 382 383 341 180 382 383 341 100 100 100 100 100 100 179 180 382 383 180 382 383 382 383 382 383 180 382 383 180 382

GG4 GG3 GG2 GGl GG5

5

0.64

B, H, J

384

5

1.22 4.1 2.7-4.7

B, H, J H H

384 54,55 54

5

0.34

B, H, J

384

R

169

C, W5 C, W5 C, F21, W5 C, W5 C, F21, W5

457 454 259 457 259

60 130 130 130 130 130 60 60 45 45

6300 5.8 0.027 12 15.0 0.0000 0.00065 0.63 4.2 2.6

86 274 30 30

Remarks page II-157; References page 11-159

TABLE 5. cont'd Modifier Methyl methacrylate {cont'd) Anisole, 4,4'-dithiodip-Anisoyl disulfide Benzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , m-bromo- , /7-bromo- , m-chloro-,p-chloroBenzoyl disulfide Benzyl disulfide Benzyl sulfide

J( 0 C) 50 60 60

0.0044 0.0052 14.6

60 60 45 60 70 45 45 45 45 60 25 50 60 25 50

0.00365 0.0196 4.7 2.7 15 3.8 5.6 3.5 4.6 10.0 0.134 0.016 0.00627 0.0183 0.0098 0.0098 0.00154 0.0040 0.0039 0.084 0.021 0.66 0.67 0.008 0.22 0.09 0.35 0.33 0.21 0.13 0.55 0.00007 0.00258 16.7 0.0046 0.0098 10.0 0.0072 0.0117 290 0.0115 694 0.0176 0.0508 0.0127 0.0193 0.7 0.55 0.42 0.33 0.17 0.15 0.43 0.62 0.40 0.00013

Benzyl sulfone Benzyl sulfoxide Benzyl tetrasulfide Benzyl trisulfide 1-Butanethiol

60 50 50 50 50 60

Carbanilide, thio-

50

_, _, 4,4/-bis(dimethylamino)- , - , 4,4'-dichloro- , - , 3,3/-dimethoxy-, -, 3,3'-dimethyl- , -, 4,4'-dimethyl- , - , 3,3'-dinitroCarbon disulfide 2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxyDisulfide, bis(p-bromobenzoyl)- , bis (p-bromophenyl)-

50 50 50 50 50 50 60 79.5 60 50 60 60 50 60 60 70 60 50 60 50 60 60 70 80 90 50 70 50 60 70 60

- , bis(p-chlorobenzoyl)- , bis(p-chlorophenyl)-, -, -, -,

bis(p-cyanobenzoyl)bis(dimethylthiocarbamoyl)bis(p-nitrobenzoyl)bis(onitrophenyl)-

- , bis(/?-nitrophenyl)1-Dodecanethiol

Ethanethiol, 2-amino-, hydrochloride Ethanol, 2-mercaptoEthyl disulfide Formamidine, A^Af'-diphenyl- , - , U'-dithiobisMethyl sufoxide

Cx

50 60

0.22 0.0000071

Remarks

Refs. 285 285 369

A

F2 D F2

F2, J F2, J A F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 A

F7 F7 F2 F2 C, F2 A

490 491 30 274 566 30 30 30 30 369 368 354 368 368 252 354 368 252 252 354 354 274 69,397 251 251 251 251 251 251 251 251 288 474 369 285 285 369 285 285 369 104 369 285 285 285 285 573 573 573 573 473 473 473 274 473 310 251 438

TABLE 5. cont'd Modifier Methyl methacrylate (cont'd) 2-Naphthalenethiol 1-Penthanethiol Phenyl disulfide

Phenyl disufone Phenyl sulfide Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-[l,3,3,3-tetramethyl-l-(trimethylsiloxy)disiloxanyl]- , 3-(trimethoxy)2-Propanethiol - , 2-methylPropionic acid, 3-mercaptoSulfide, benzoyl dimethylthiocarbamoyl Sulfur Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester - , - , sodium salt - , S-phenyl ester - , - , compound with pyridine - , - , potassium salt - , S-propyl ester - , - , sodium salt m-Toluenethiol p-Toluenethiol a-Toluenethiol p-Toluoyl disulfide p-Tolyl disulfide Styrene Acetic acid, dithiodi-, -, -, -, -, -,

-, -, -, -, -, -,

diethyl ester dimethyl ester mercaptobutyl ester ethyl ester methyl ester

- , phenyl- , - , /?,/?'-dithiodi- , thio Aniline, 2,2' dithiodi-

-, 4,4'-dithiodi- , N-dodecyl-, 4,4'-dithiodiAnisole, 2,2'-dithiodi- , 4,4'-dithiodi- , p-methyl-, a,a'-dithiobis-

T( 0 C) 45 60 50 25 50 60

Cx

Remarks

Refs.

60 25 50 60 50 50 79.5 79.5 60 60 50 70 20 60 44.1 50

1.3 3.1 0.8 0.0174 0.0038 0.0007 0.00176 0.0085 0.0110 0.0003 0.00554 0.0064 0.00132 0.0006 0.0013 0.128 0.693 0.38 0.18 0.39 0.38 5.5 0.08 1.3 0.075 0.106

60

0.00226

490

60

0.00167

490

60 60

0.374 0.00537

490 490

60 45 45 50 60 50 60

0.00190 4.7 7.4 0.027 11.0 0.0031 0.0044

490 30 30 354 369 285 285

50 99 60 99 99 50 60 60 99

< 0.005 0.2 0.015 0.1 >14.0 26.0 58.0 0.63 27.6

50 99 25 50

0.24 >14.7 3.8 3.0 3.4 3.0 0.24 0.21 3.0 0.18 0.021

75 50 50 50 50 99

H D

A A D

F2 F2 D A C F2, J

F2, J

J, R A A

J

30 274 344 368 285 310 368 285 491 491 368 252 368 252 252 474 474 274 274 473 473 280 280 118 194 354

297 96 86 96 96 146 126 323 96 89 96 297 297 297 297 89 89 89 89 96

Remarks page 11-157; References page 11-159

TABLE 5. cont'd Modifier Styrene {cont'd) /7-Anisoyl disulfide Anthranilic acid, 4,4'-dithiobisArylbenzene thiolsulfonate - , /?-chloro - , p-methoxy- , p-methylBenzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , o-ethoxy-,p-ethoxyBenzene thiosulfonate - , aryl-p-chloro- , aryl-p-methoxy- , aryl-p-methyl 2-Benzimidazolethiol Benzoic acid, 2,2/-dithiodi- , - , diethyl ester - , -,dimethyl ester -, 4,4'-dithiodi- , - , diethyl ester - , o-mercapto- , -, methyl ester -,thioBenzothiazole, 2,2/-dithiobis-

- , 2,2'-thiobis2-Benzothiazolethiol Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)Benzoyl disulfide

Benzyl alcohol, ^o'-dithiobis-,/vAdithiobisBenzyl diselenide Benzyl disulfide

T( 0 C) 60 50 60 60 60 60

96.0 3.0 0.95 2.22 1.872 1.237

60 50 60 99 99 99

0.00617 1.60 1.67 0.08 25.1 0.13

60 60 60 99 50 50 99 50

2.597 1.475 1.099 0.21 0.01 < 0.005 0.2 0.11 0.17 0.11 >14.7 17.0 6.23 2.3 2.1 2.3 2.4 2.73 < 0.005 0.03 0.26 0.011 < 0.005 0.010 0.0107 36.0 0.11 0.58 0.09 2.0 0.02 0.03 0.00878 0.01 0.011 0.548 0.069 0.00335 0.052 0.051 5.4 13.2 21.0 22.0 25 15.0 17.0 15.4

50 99 99 99 25 50 75 99 50 50 99 60 50 60 99 50 50 60 50 60

Benzyl sulfide Benzyl sulfone Benzyl sulfoxide 1-Butanethiol

Cx

99 25 50 60 50 50 25 60

70 80 99

Remarks

R, F2 R, F2 R, F2 R, F2 A A

R, F2 R, F2 R, F2

J

A

A D

D, Ql D A A A A

Refs. 369 89 544 544 544 544 490 491 491 96 96 96 544 544 544 96 89 89 96 297 89 89,297 96 96 96 297 297 297 297 96 297 297 96 419 89 545 304 369 96 89 297 128 89 297 368 128 96 368 252 368 252 252 340 340 395 69,397 131 395 395 96

TABLE 5. cont'd Modifier Styrene (cont'd) 1-Butanethiol, 1,1,3,3-tetramethyl-

1-Butanethiol-D

Butyl disulfide

sec-Butyl disulfide tert-Butyl disulfide Butyl sulfide tert-Butyl sulfide Carbanilic acid, /?,/?'-dithiodi-diethyl ester Carbon disulfide Carbonic acid, dithio- , - , S,S'-bis(carboxymethyl)ester - , trithio- , - , S,S'-bis(carboxymethyl) ester 1-Decanethiol 2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxyDiphenyldisulfide Disulfide, bis(/?-bromobenzoyl) - , bis(a-bromo-o-tolyl) - , bis(/?-chlorobenzoyl) - , bis(chlorobenzyl) - , bis(2-chloroethyl) - , bis(a-chloro-o-tolyl) - , bis(>-cyanobenzoyl) - , bis(diethylthiocarbamoyl) - , bis(dimethylthiocarbamoyl)

T( 0 C)

5 50 60 70 80 25 55 60 99 150 50 50 60 60 60 50 60 50 50 80 80 79.5 60 60 50 60 50 50 50 60 60 60 70 80 95 115 130

- , bis(2-ethylhexyl) - , bis(A^ethyl-A^phenylthio-carbamoyl) - , bis(l-methylheptyl) - , bis(morpholinothiocarbonyl) - , bis(l-naphthylmethyl) - , bis(/?-nitrobenzoyl - , bis(o-nitrophenyl) - , bis(l-phenylethyl) - , bis(P-(2-pyridyl)ethyl) - , bis(2,3,5,6-tetramethylphenyl) - , bis(2,4,6-triisopropylphenyl) 1-Dodecanethiol

50 60 99 60 99 60 50 50 50 50 50 60 70 70 90 100 110

Cx

5.5 6.4 4.3 5.2 4.0 7.0 0.00079 0.00154 0.0024 0.0068 0.022 < 0.005 < 0.005 0.00014 0.0022 0.025 0.24 0.00066

Remarks

H H H A A A

A

A

0.36 0.21 4.3 4.2 0.0118 0.147 745 1.0 196 < 0.005 0.01 1.3 3190 0.724 1.11 0.0136 0.568 0.620 0.780 0.860 0.939 1.035 0.984 1.150 < 0.005 1.75 0.0104 6.1 0.033 6650