P r o p a g a t i o n i n

F r e e

a n d

T e r m i n a t i o n

R a d i c a l

C o n s t a n t s

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

M. Kamachi Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan B. Y a m a d a Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan A. Introduction B. Tables of Propagation and Termination Constants Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. ltaconic Derivatives Table 6. Fumaric Derivatives Table 7. Vinyl Halides Table 8. Vinyl Esters Table 9. Vinyl Ethers Table 10. Styrene Derivatives Table 11. Vinyl Heteroaromatics Table 12. Aldehydes Table 13. Others C. References

11-77 11-79 II-79 II-79 II-80 II-82 II-85 U-87 II-87 II-87 II-88 II-88 II-90 II-90 II-90 11-91

The rate constants kv and kt have usually been assumed to be independent of chain length. In this chapter termination constants depending on the length of the polymer radicals are also reported. In American literature the right hand side of (A4) is written as 2£t[P#] . In this chapter the definition given in Eq. (A4) has been used. Simultaneous determination of absolute values of both kv and kt from a single experiment has not been reported. In practice, the ratio k^/kt is determined from measurements of molecular weight as a function of rate of polymerization for a low conversion polymerization or from measurements of initiation rate and polymerization rate in a low conversion. The ratio kp/kt is determined from nonsteady-state measurements of the average lifetime, r, of the growing polymer chain in a photochemically initiated polymerization. This lifetime may be defined by noting that the concentration of chains present must be related to their average lifetime and rate of disappearance by (A6)

A.

INTRODUCTION

In free radical polymerization the propagation and termination rate constants describe the reactions

which, from (A3) and (A4), yields (A7)

(Al) dead polymer

(A2)

where P^ is a propagating chain of any length n and M is the monomer. The rate constants are defined by the following equations:

By combining the separately determined ratios, k^/kt and kp/kt, the individual propagation and termination rate constants may be calculated. Alternatively, the rate of initiation, R[, may be measured as the rate of initiator disappearance and equated to R1. This gives (from (A6) and (A3))

(A3) (A4) where (A5)

(A8) There is a large degree of imprecision inherent in measuring r and in combining data from different experiments, which helps to explain the scatter in the data tabulated here.

/Ct(XiO"6)

kp

/C1(XiO-6)

Figure 1. Arrhenius plots of all bulk polymerization data for styrene for kp (•) and /ct (+). Solid lines are least squares obtained by assuming all points to be of equal value.

The two monomers styrene and methyl methacrylate have been so extensively studied that their data are presented as Arrhenius plots (Figs. 1 and 2). Because of the influence of solvents on the rates, only data of bulk polymerizations are shown. It remains a wide scatter, which should serve as a warning against casual acceptance of any single number. Solid lines are the least squares that have been calculated assuming all points to be of equal value. For the termination rate of methyl methacrylate the leastsquares line results in a positive slope and is not shown. In this case a temperature-independent kt could be a better representation of the experiments. The pulse laser polymerization (PLP) method has been developed as a new method of obtaining kp. In the PLP method, the value of kp can be estimated from the degree of polymerization of polymer formed, vp, a knowledge of the monomer concentration, [M], and tf the time between pulses: (A9) The reproducibility of the PLP method has been recognized by an IUPAC Working Party on Modeling of Kinetic and Process of Polymerization, which is establishing a critical review of the literature values of kp.

K9

1000 T Figure 2. Arrhenius plots of all bulk polymerization data for methyl methacrylate for /cp (•) and /ct(+). Solid lines are least squares obtained by assuming all points to be of equal value. The line for kx is not shown since a horizontal line for a temperature independent kt could be a better representation. Classification of the methods for the determination of rate constants The tabulated data refer to seven different methods. Method A uses the following four methods for the measurement of the lifetime r: Al -rotating sector or a "flashing" laser A2 - flow through a tube with spatially separated light and dark sections A3 - spacial intermittent polymerization (SIP) A4 - intermittent illumination method Method B effectively measures only a single decrease (increase), in the radical concentration by the following methods: B l - dilatometry B 2 - dielectric constant B 3 - interferomety B4 - temperature change B5 - viscosity B6 - light scattering B7 - monomer pressure

B 8 - cathetometer B9-inhibitor BlO-scavenger

Method F uses pulse laser photopolymerization (PLP) method

Method C uses electron spin resonance (ESR) for the determination of the radical concentration Method D refers to values obtained in emulsion polymerization by application of the Smith-Ewart theory

Fl - PLP F2 - PLP-GPC (MWD) F3 - PLP-MALDI TOF (-GPC) Method G refers to the method of measuring molecular weight (MW) and molecular weight distribution (MWD) by Gl - gel permeation chromatography (GPC) G2 - high performance liquid chromatography (HPLC)

Method E refers to recalculated values

B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS TABLE 1. DIENES Monomer 1-Acetoxybutadiene Butadiene

k9 (1/mol/s)

M x I O " 6 ) (l/mol/s)

Temp. (0C)

Method

18.0 &p = 1 . 2 x l 0 8 x exp(- 39000/RT) 150 ± 4 0

281

25 10

Al D

152 23

kt = 1.13 x l O 4 xexp(-711/r)

5 45-60

C Gl

223 202

50

Fl

221

-

50

Fl F2

Solvent: chlorobenzene Solvent: chlorobenzene

-

40

D D

Quoted in Ref. 86

l n * p = l n (3.873 x 1010) - 53400/RT 111.6 kp = 8.05 x 107 xexp(-35710//?7) Chloroprene 220 fcp = 2 . 9 x l 0 9 x exp(-41000/^7) *p = 1.95 x l O 7 x exp(- 26630/RT) 2,3-Dimethyl-l,3-butadiene &p = 8 . 9 x l 0 7 x exp(- 38000//?7) Ethyl 4-ethoxy-2,4-pentadienoate 9.9 Ethyl 4-methyl-2,4-pentadienoate 29.7 Ethyl pentadienoate 30.9 1,3-Hexadiene 20 ± 1 0 2,4-Hexadiene 16 ± 1 2 Isoprene 2.8

2-Methyl-l,3-pentadiene

Remarks

Refs.

221 187 59 84

Fl

198

D

71 152 152 152 223 223 24

9.3 23 19 -

25 25 25 5 5 5

Al Al Al C C D

125 ± 3 0 35 ± 10

-

5 5

C C

k p (1/mol/s)

M x I O 6 ) (1/mol/s)

Temp. (° C)

Method

1050 ± 5 0 455 ± 5 0 200

83 -20.01 130

Al Al Al

3.9 (7.8) x 102 1.99 x 102 -

130 190 230

Al C Fl

3.2 x 103

190

Fl

Calalyst system: diisopropylbenzene, monohydroperoxidetetraethylenepentamine

223 223

TABLE 2. OLEFINS Monomer Ethylene

Propylene

470 ± 3 0 18.6 ± 2 5400 £ p = 4.8x 107 x exp[(- 4450 + 3.Ix 10~6p)/T] 1.2 x 104 1.09 x 104 3.08 x 104

&p = 2 x l 0 6 x exp(- 32000/RT)

50-150

Remarks Solvent: benzene Pressure 1.8 x 10 8 Pa Pressure (5-17.5) x 10 7 Pa, using results of Ref. 141 Pressure 1.9 x 108 Pa Initial pressure 2.27 x 108 Pa Pressure 2.55 x 108 Pa, at low or moderate conversion Pressure 2.50 x 108 Pa, at conversion 0 Radical telomerization

Refs. 53 66 139 142 135 151 167 167 129

References page 11-15

TABLE 3. ACRYLIC DERIVATIVES Monomer

kp (1/mol/s)

kt (xlO~ 6 ) (1/mol/s)

Acrylamide

6000 ± 1000 18000 ±1500 8200 220 (7.9 ±0.5) x 10 4 (4.3 ±0.2) x 104 (3.3 ±0.2) x 104 (2.3 ±0.1) x 10 4 fcp=7xl06 x exp[(- 21000 ± 2000)/RT]

3.3 ±0.6 14.5 ±2.0 5.5 1.0 660 ± 4 0 350 ± 2 0 230 ± 2 0 160 ± 1 0

650

2.6

3150

2.6

Temp. (0C)

25 19 26 30 30

Method Al, Bl Al A A Al Al Al Al Fl

Remarks Solvent: water, pH 5.5 Solvent: water Solvent: water Solvent: DMSO Solvent: water 0.38M H 2 O : DMSO (90:10) H 2 O:dioxane (90:10) H 2 O : THF (92:8)

Refs. 79 41 89 89 126 119 119 119 197

Acrylic acid

-,butyl ester

- , cyclohexyl ester -,ethyl ester

6600 2.7 13 0.018 2100 330 1977 3.84 679±66 6.4±0.6 log 10 fcp = 6.0123-748.4/7 ln[(*t[p]/(1.00 + OMp)] = l n * t [I]-0.6Op 1360 1.28 963 1.18 1320 1.07 360 0.36 2722 ±248 3.2 ±0.3 800 1.76 12.39 x 10 3 139.2

- , 2-ethylhexyl ester - , methyl ester

23

Al Al

30 25-80 30

Al Al B4 Al Al Fl B5

30

Al

30 50 50

Al Al Al

25 25

155 1300

0.233 75

50 15

Al Al

880

260

15

Al

25 25

Al Bl Al

1580 580 fcp = 1 . 0 x l 0 8 x exp(- 30000/RT) 1000 11680 21300 (1.5 ±0.2) x 10 4 (3.7 ±0.6) x 104 6.3 x 104 (1.4 ±0.2) x 104

55 6.5 fct = 2.8xl0n x exp(- 22000/RT) 3.5550 194 -

60

Al Al Al G2

-

60 60 60

G2 G2 G2

- , 2-(acetoacetoxy-methyl)-, ethyl ester - , 2-cyano-, ethyl ester

300 1622 1610 1613 1607

1.0 411 404 411 404

60 30 30 30 30

C Al Al Al Al

- , 2-chloro-, ethyl ester

1660 1408 1120 978 350

333 244 4.8 x 102 435 2.1

30 30 30 30 60

Al Al Al Al C

- , 2-fluoro-, ethyl ester - , 2-acetoxymethyl-, methyl ester

Solvent: Water, pH 7.9, (with 1.2MNaOH) Solvent: water, pH 7.9 (with 1.5NNaCl) Solvent: water, pH 11

Pressure 5.0 x 107 Pa Solvent: benzene 1.76M kt \p\; kt for pressure p (bar), kt [l] = 3.5x 106 Solvent: anisole 2.00M Solvent: benzene 2.00M Solvent: chlorobenzene 2.00M Solvent: benzonitrile 2.00 M Solvent: benzene 1.76M Solvent: toluene 1.84 M Solvent: benzene x\ molar fractions of monomer, x = 0.401, kp and kt also given by other [M] Solvent: toluene 1.94M From unpublished results of Ross and Melville From unpublished results of Matheson

99 99 99 10 57 107 137 201 122 138 138 138 138 137 108 171

108 22 22 19 48 21

Solvent: benzene 2.69 M Primary propagating step (jfcpl), Ph-MA* PhCO 2 -MA' tert-BuO-MAm Secondary propagating step (kp2), Ph-MA-MA*, PhCO 2 -MA-MA', tert-BuO-MA-MA* Solvent: benseme AcOH 7 wt.% 1,3-propanesulfone 0.5 wt.% Optimum value, solvent: AcOH Optimum value Solvent: propanesulfone AIBN 4.88 x 10" 2 M Optimum value Optimum value Solvent: benzene LOOM, MAIB 0.050 M

50 144 144 190 190 190

170 143 143 123 123 140 123 146 123 225

TABLE 3. cont'd Monomer

fep

(1/mol/s)

fct(x..l0-6)

(l/mol/s)

Temp. ( 0 C)

Method

- , 2-acetyloxy-, methyl ester

430

-

60

C

- , 2-benzoyloxy-, ethyl ester - , 2-(benzyloxymethyl)-, methyl ester

990 182

2.9 1.6

60 60

C C

- , 2-[2,2-bis(carbomethoxy) ethyl], methyl ester

4.0

0.038

60

C

- , 2-butoxy-, methyl ester

298 184

8 -

60 60

C C

- , 2-butyroxymethyl-, methyl ester

360

1.4

60

C

19

0.51

60

C

8.6 1.6 300

21 1.8 1.1

60 60 60

C C C

11

0.08

50

C

0.57

0.11

60

C

0.76

1.4

60

C

- , 3-methyl, dimethyladamantyl ester

0.41 0.71

0.081 1.1

60 60

C C

- , 3-methyl, terf-butyl ester

0.90 LO

2.3 4.7

60 60

C C

- , 2-naphthoyloxymethyl-, ethyl ester

320

0.37

60

C

- , 2-pivaroxymethyl-, methyl ester

230

0.59

60

C

- , trans-2-vinyl-, methyl ester

125

-

60

C

3000-5000 127 52 51 20000 24

12.2 5 1.8

OD 25 25 25 40 50

B4 B4 B4 D

1960 15400 28000 1910 382 ±230 3300 ± 300 3200 ±400 3000 ± 600 (6.5 ± 1.3) x 103 28.2

782 2700 3700 290 47.6 ± 2 2 1200 ± 170 300 ± 5 0 240 ± 70 4700± 1300 0.20

60 25 25 25 25 50 50 50 50 60

Al Al Al Al Al Al Al Al Al C

273 273 8267

17.9 11.9 2200

30 30 30

Al Al Al

- , 2-(2-carbomethoxy)- ethyl-, methyl ester - , 2-ethyl-, methyl ester - , 2-ethyl-, cyclohexyl ester - , 2-isobutyroxymethyl-, methyl ester -,-2-(methoxycarbonylmethyl)-, phenetyl ester - , 3-methyl, adamantyl ester

Acrylonitrile

Ar-Acryloyl-2,2-dimethyl5 (R)-phenyl-l,3-dioxazoline 7V-Acryloylpiperidine N-Acryloylpyrrolidine

23

Remarks Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene 1.56M Solvent: benzene 2.0M, AIBN 5 ^ x IQ^ 3 M Bulk AVN 0.05 M, Ic p and kt also given by other temp. Solvent: benzene 2 M Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene LOOM, MAIB 0.050 M Bulk MAIB 0.05 M, kp and kt also given by other temp. Bulk AIBN 0.10M Bulk AIBN 0.10M Solvent: benzene LOOM, MAIB 0.050 M Solvent: benzene 2.22 M, kp and kt also given by other temp. and [M] Bulk 4.8 M MAIB 0.05 M Solvent: benzene 2.4 M, MAIB 0.05 M, kp also given by other [M] Bulk 4.0 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Bulk 5.9 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene LOOM, MAIB 0.01 M Solvent: benzene LOOM, MAIB 0.005 M Solvent: benzene LOM, AIBN 0.25 M

Solvent: DMF

Refs. 224

172 206 228

176 224

225 229 230 230 225 157

232 232

232 232 232 232 226 225 227 42 49 63 75 42 35

Primary radical termination in a precipitating medium Solvent: DMF 43 Solvent: water 54 Solvent: water 55 Solvent: DMSO 70 Solvent: DMF 68 Solvent: DMF 3.8 M 88 Solvent: DMSO 3.8 M 88 Solvent: Ethylene carbonate 3.8 M 88 Solvent: Mg (C1O4)2 • 12H2O 3.04M 88 Solvent: benzene 1.08 M, 231 MAIB 0.05 M, kp and kt also given by other temp. 145 Optimum value 123 Optimum value 123

References page 11-15

TABLE 3. cont'd Monomer

kp (1/mol/s)

ifetCxlO"6) (1/mol/s)

Temp. (0C)

Method

JVW'-Dimethylacrylamide

11000 27200 29198 15 x 10 3 2330 ±230

38 3540 4080 0.540 ±0.053

50 30 30 25 30

Al Al Al Fl A4

2760 ±342

0.452 ±0.056

30

9.9 x 10 3

-

25

Fl

kp (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

79.6 ±5.6 1.1 x 10 3 ~21 26

16.5 ± 1 . 4 ~27 21

25 25 30 25

Al Fl Al

670

2.1

23

Al

1950 1410 110 895 1250 510

2.25 41.9 80 40 41.9 2.87

30 32.5 32.5 30 20

Al Al C C Al Al

- , bornyl ester

580

3.3

60

C

- , n-butyl ester

369 573 360 lnfcp = 6 . 1 3 + 6.33 x 10 ~9 p lnfcp = 15.8-2751/7

10.2 18.0 10

30 30 30 30 12-93 70 30

Al Al Al F2 F2 B5 B5

10-90

Fl Fl A3 Al

3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate

N-Methylacrylamide

Remarks

Optimum value Solvent: water, pH 1.4 Solvent: formamide: 1,4-dioxane (3:1 (v/v)) Solvent: formamide: 1,4-dioxane (3:1 (v/v)), NaCl 0.1 M Solvent: water, pH 1.9

Refs. 74 121 123 197 192 192 197

TABLE 4. METHACRYLIC DERIVATIVES Monomer Methacrylamide Methacrylonitrile £p

Remarks Solvent: water Solvent: water, pH 1

Refs. 69 197 26 39

106.43±0.26

=

xexp[(-29700±1500)//?n Methacrylic acid

- , benzyl ester

- , terf-butyl ester

2.6 In [(kt\p]/(\M + 0.0lp)] = InJt1[I] - 0.73/7 ln*p = (14.41 ±0.09) - (2472±29)/T jfcp = 3.44 x 10 6 exp(- 23300/RT) 1576 9.74 350 14 £p

=

1O7.4±o.4

30 25 9

_66

Solvent: water, pH 8.0 (with 0.22MNaOH) pH=13.6

kp and kt also given as a function of viscosity Solvent: benzene 1.0 M, AIBN 0.05 M Pressure: 5.0 x 10 7 Pa

Pressure 1.0 x 10 8 Pa 77=1.92cp kt \p]\ kt for pressure p (bar), kt[l] = 13.4 x 10 6

99 99 101 153 153 87 103 193 27 106 109 216 216 212 122 219 169 225 52 203

F 1

xexp[-(27.7±2.5)x IO3/RT] - , trans-4-tert-buty\cyclohexyl ester

- , cetyl ester - , p-Ip-(cetyloxy)benzoyloxy]phenyl ester - , 2-chloroethyl ester - , 2-cyclohexylethyl ester - , cyclohexyl ester - , 2-decahydronaphthyl ester

550

1.9

60

C

510 570 ± 1 0 300 ± 9 0 300

1.9 0.5-2.3 0.16 ±0.04 0.25

60 60 30 50

C C Al Al

170 254 1190

0.30 6.71 32.8

50 30 30

Al Al Al

510

5.4

60

C

570

3.1

60

C

Solvent: benzene LOM, AIBN 0.05 M, trans 100% trans 28.9% Solvent: benzene Solvent: dioxane 0.2 M

Solvent: toluene 0.2M

Solvent: benzene LOM, AIBN 0.05 M Solvent: benzene LOM, AIBN 0.05 M

194 194 210 109 97

97 87 87 193 193

TABLE 4. cont'd Monomer - , 2,6-dimethylphenyl ester - , dodecyl ester -,ethyl ester

- , hexadecyl ester - , isobornyl ester - , isobutyl ester - , isopropyl ester - , lauryl ester

- , 2-methoxyethyl ester - , methyl ester

kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

68

2.1

30

Al

72 126

2.4 0.6 7.35 10

30 70 30 70

Al B5 Al B5 Fl

0.16 3.5

10-90 70 60

Fl B5 C

10-90 30 30

Fl Al Al Fl

219 87 109 169

30 23.6

Al Al Al

87 9 7

32.5 40 50 -30 20

C Bl E Bl Al

* p = 1.50 XlO 6 x exp(- 20460/RT) ln* p = (15.11±0.17)-(2753±55)/r 390

lnfcp = (14.72±0.13)-(2590±42)/7 121 4.52 460 ±140 0.6 ±0.2 kp = 2.93 x l O 5 x exp(- 16190/RT) 249 9.30 310 ± 2 0 66 ± 4 fcp = 5 . 1 3 x l 0 6 kt = 1.36 x l O 3 x exp(- 26400/RT) x exp(- 11900/flT) 187 72.1 404 17.6 410 24 13.2 0.488 390 517 527 28 260 270 280 285 310 330 340 240 335 270 330 250 240 280 320 390 ± 4 0 410 ± 40 410 ± 4 0 180±50

37 23 4.4 21 21 19.5 17.5 17 17 17 11.5 9 22 16 29 25 14 28 42 ± 4 29 ± 3 26 ± 3 20 ± 6

10 10 10 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20

Bl Bl Bl Al Al Al Al Al Al B5 B5 B5 B5 B5 B5 B5 B5 B5 Al Al Al E

500 ±250 41.6 62 200 128 364

63 ± 3 2 2.69 8.44 41.8

20 0 5 20 22 22.5

B6 B5 D B6 Bl B4

512.6 410

46.6 42.7

25 25

Al Al

248 141 106 140

22.7 11.6 5.7 -

30 30 32 40

Al A B4 D

Remarks

Refs. 120

Optimum value r? = 3.96cp

123 212 87 212 169

7^ = 0.91 cp

rj = 7.52cp Solvent: benzene 1.0 M, AIBN 0.05 M

Solvent: ethyl acetate Using results of Ref. 7 Solvent: ethyl acetate kp also given as a function of temp. and of viscosity for other solvents Solvent: methanol Solvent: pyridine Solvent: DMF Solvent: benzene 4.69 M Solvent: fluorobenzene 4.69 M Solvent: chlorobenzene 4.69 M Solvent: anisole 4.69 M Solvent: bromobenzene 4.69M Solvent: benzonitrile 4.69 M Solvent: methyl benzoate 4.69 M Solvent: methylphenyl acetate 4.69 M Solvent: dimethyl phthalate 4.69 M Solvent: dimethyl carbonate 4.69 M Solvent: diethyl oxalate 4.69 M Solvent: methyl formate 4.69 M Solvent: methyl propionate 4.69 M Solvent: diethyl succinate 4.69 M Solvent: acetonitrile 4.69 M Solvent: methanol 50% by vol. Solvent: n-octane 5% by vol. Solvent: «-nonane 20% by vol. DP = (2-8) x 10 3 using results of Ref. 86 DP = ( 3 - 5 ) x l 0 4 Assuming biradical initiation Jfcp found as a linear function of Mw Rate of initiation; 1.20 x 10 " 8 (moles/1/s) kp and kt also given as a function of viscosity for other solvents

219 212 193

153 51 62 72 92 94 94 94 85 85 85 85 85 85 90 90 90 90 90 90 90 90 90 104 104 104 96 96 11 65 91 29 60 30 93 14 87 58 65

References page 11-15

TABLE 4. cont'd Monomer

A:p (1/mol/s)

M x l O ~ 6 ) (1/mol/s)

Temp. (0C)

Method

0.224 573

2.0

45 60

D E

573

11.9

60

E

995 ± 83 506 ±48 450 ± 3 3 456±29 448 ±47 498 ± 39 614±43 427 ±38 290 1020 530 550

43.6 ± 4.9 35.6 ±3.9 42.0 ±3.0 43.8±2.0 47.2 ±6.6 42.9 ± 4.7 39.9±3.3 30.9 ±3.7 21 292 55 68

80 30

kp= 4.92 XlO 5 x exp(- U210/RT) 315

kt = 9S x exp(- 2930/RT) 33.9

15-30

A2

25

A2

336 ± 9 0 441 fcp = 2 . 5 x l 0 6 x exp[(- 23000 ± 2500)/RT] kp=k® (0.33 < Wp < 0.84) = ££exp[-29.8(Wp-0.84)] (0.84 < w p < 0.99)

28 ± 12 19.7 720

25 30 25-60

Al Al C

50

C

w p (weight fraction of polymer)

150

At high conversions ( ~ 65%) Special evaluation from steady-state and Mn Solvent: toluene

148 134

30 60

Al Al Al Al Al Al Al Al Al Al Al

Remarks

Refs.

Termination by combinat. using results of Refs. 7 and 31 Termination by disprop. using results of Refs. 7 and 31 Solvent: benzene 4.7 M Solvent: anisole 2.0M Solvent: benzene 2.0M Solvent: C 6 D 6 2.0M Solvent: fluorobenzene 2.0M Solvent: chlorobenzene 2.0 M Solvent: benzonitrile 2.0M Solvent: benzene 1.0 M Addition of 1 x 10 " 3 mol pyridine Addition of 1 x 10" 3 mol acetone Addition of 1 x 10 " 3 mol triethanolamine P n = IO4 kp and kt also given as a function of P n Pressure 5.0 x 106 Pa Pressure 5.0 x 10 7 Pa

67 33 33 111 133 133 133 133 133 133 133 118 118 118 118 114 110 127 105 45

(*J= 790 ±300) 130 705.6

20.7 ±1.0 25

0 60

Al

170 306 292

-

0.2 25 25

F3 Fl Fl

60 20-90

C Fl

30

B5

670 ± 3 0 22 InATp = 14.69-2670/7+ 0.201/7x(1.0x 1 0 " 5 P - I ) \nkt[p] = InA:t[l] -0.57/7 26.6

1.4

5

BlO

5.8

0.017

5

BlO

kt(m,n) = 1.22 x W2(n x m)~ 0075

25

A3

21

70

B5

0.034

50

D

0.16

50

D

- 1 to - 70 60

Fl C

- 8 30

F3 Fl

fcp = 106 694 exp(- 23940/RT) lnJfcp (VmoVmin) = ln*p,-(3.86 [AIBME]0 + 0.8) x (l-(f>m)- 1.6 (l-cj)m)60

131 680- 820

-

690-810

-

Fl

222 196

Solvent: ethanol (50%) 4.67 M, kv also given by other [M] and solvents 175 207 kt\p\\ kt for pressure/? (bar), fct[l] = 15.4x 106 Scavenger DPPH, solvent: DMF, blank polymn. Scavenger DPPH, solvent: DMF, template polymn., template; it-MMA n: n-mer; m: m-mer, coupling with rt-mer and m-mer 77 = 0.53 cP No addition of chain-transfer agent, Time 7.5-20.5 min. Addition of 2% CBr4, Time 7.5-20.5 min. AIBME (dimethyl 2,2'azodiisobutyrate) 0.0434M, m; monomer volume fraction £pX) = 700(l/mol/min) Benzoin 7 x 10 " 4 M Solvent: toluene, pressure 1.0 x 108 Pa, k p also given by other pressures Solvent/2-butanone, pressure 1.OxIO 8 Pa

122 115 115

147 212 149 149 217 158

199 208

208

TABLE 4. cont'd Monomer

kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

313±8.1 794.0 815.0 957.0

39±4 62.4 51.6 38.2 25(±3)

25 60

Fl B5

60

C

21 ± 2 45 50

60 25 40

C Al

191 160 160

-

25 50

Fl Fl C

198 220 184

510 ±100 299 431 )tp = 2.39 x 106 x exp(- 22000/#D 359 12

135 292 200 135 ± 5 0 170

-, octyl ester

35 2960 *p = 1.9068 x 106 xexp(-21181.07//?D kp = 1.2169 x 106 x exp(- 25203.59//?D kp = 3.0598 x 107 x exp(-28008.18/RT) 35 1710 240 ± 8 0

0 25 28 0 50

29.1

50 30

Al Fl Bl Al C

Values from Chem. Abstr.

159 164 83 165 155

30% MMA in benzyl alcohol

227

Fl

30% MMA in NMP

227

p.s. 500 nm Pressure 5.0 x 10 7 Pa

155 113 109 122

30 30 30 60

Al Al Al Al Al Al Al Al Al Al C

26 1470 ±170

0.301 0.499 ±0.058

32.5 30

C A4

2760 ±342

0.452 ±0.056

30

185

0.034

20

B8

230

0.053

20

B8

kp (1/mol/s)

£ t ( x l 0 ~ 6 ) (1/mol/s)

Temp. (0C)

Method

1.7 3.9

2.5 x 10" 3 3.4xl0~3

60 60

C C

Polyhydroxytetramethylene-a, co-methacrylate of MW = 700

particle size 260 nm, kp also given by other particle sizes kp; average value

Fl

411 230 ± 1 5 176±8 180±9 223 ±11 235 ± 8 273 ± 8 228 149 467 590

30 30

Emulsion polymn.,

161 204 204 204 166

A3 Fl

50 30 30

Solvent: benzene 3 M Solvent: chlorobenzene 3 M Solvent: benzonitrile 3 M

Refs.

Emulsion polymn., n-butyl aery late: MMA: methacrylic acid (8:91:1), particle size (p.s.) 50 nm, kp also given by other temp, and particle sizes p.s. 500 nm 155 225 227

62.6 2.6 ±0.9 ln[(fct[p]/(1.00- 0.19)] = \nkt[l]-l.01p 11.9 2.02 ±0.22 2.06±0.21 2.16±0.19 2.26 ± 0.22 1.72 ±0.11 1.96 ±0.12 1.88 0.813 45.1 2.6

-, phenyl ester

- , 2-phenylethyl ester - , 3-phenylpropyl ester - , rc-propyl ester - , 3-tetracyclo-[4.4.02'5.l7'10]dodecyl ester -, triphenylmethyl ester 3-Dimethyl-(methacryloyloxy-ethyl) ammonium propane sulfonate

25.6 -

Remarks

Al Al B5

kt[p]\ kt for pressure p (bar), ikt[l] =40.0 x 106 Solvent: Solvent: Solvent: Solvent: Solvent: Solvent:

anisole 2.00M benzene 2.00M fluorobenzene 2.00M chlorobenzene 2.00M bromobenzene 2.00M benzonitrile 2.00M

Solvent: benzene 1.0M, AIBN 0.05 M

87 116 116 116 116 116 116 87 87 28 193

153 Solvent: formamide: 192 1,4-dioxane (3 :1 (v/v)) Solvent: formamide: 192 1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M Calcd. from nonstationary 125 state kinetics Calcd. from stationary state kinetics 125

TABLE 5. ITACONIC DERIVATIVES Monomer Itaconic acid - , bis (4-terf-butyl-cyclohexyl) ester - , bis (cyclohexyl-methyl) ester

Remarks

Solvent: benzene 0.5M Solvent: benzene 1.5M, MAIB 0.02 M

Refs.

213 182

References page 11-15

TABLE 5. cont'd kp (1/mol/s)

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

- , bis (3,5-dimethyl-l-adamantyl) ester - , bis (2-ethylhexyl) ester

0.92 6.8 3.4 2.0 2.1 2.2 2.1 2.1 1.4 3.0

0.32 x 10~3 0.001

60 50 50 50 50 50 50 50 50 50

C C C C C C C C C C

- , diadamantyl ester

0.56

0.30 x 10~3

60

C

- , di-n-butyl ester

3.5

1.59 x l O " 2

60

C

13

0.11

50

C

11 6.8 9.4 6.7 3.4 3.2

0.13 0.07 0.11 0.083 0.068 0.13 1.0 x l O " 3

50 50 50 50 50 50 50

C

5.3

8.5 x l O " 2

50

C

5.9

0.053

50

C

- , di-sec-butyl ester

0.6

4.0 x 10 ~3

60

C

- , di-terf-butyl ester

0.2

5.6 x 10~3

60

C

- , dicyclohexyl ester

2.3

1.4xlO" 3

60

C

- , diethyl ester

7.7

0.24

50

C

3.7

6.41 x l 0 ~ 2

60

C

- , diisobutyl ester

2.7

1.56 x 10~2

60

C

- , diisopropyl ester

1.1

5.0xl0~~ 3

60

C

- , dimethyl ester

5.2

0.36

60

C

10

0.59

50

C

- , a-ethyl-P-hexarluoropropyl ester

5.0

0.28

60

C

- , a-methyl-P-isopropyl ester - , a-methyl-P-tert-butyl ester - , a-isopropyl-P-methyl ester - , a-fm-butyl-P-methyl ester AT(2,6-dimethylphenyl)itaconimide

3.4 4.2 1.9 0.91 26

0.06 0.051 0.07 0.056 0.082

60 60 60 60 50

C C C C C

15

0.29

60

C

Monomer

Methyl N-phenyl-itaconamate

Remarks Solvent: benzene 1.5 M Solvent: hexane 1.03 M Solvent: cyclohexane 1.03 M Solvent: toluene 1.03 M Solvent: benzene 1.03 M Solvent: chlorobenzene 1.03 M Solvent: ethyl acetate 1.03 M Solvent: THF 1.03 M Solvent: acetone 1.03 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, kp and kt also given by other [M] Solvent: benzene 1.5M, MAIB 0.02 M Solvent: cyclohexane 1.33 M, MAIB 5.00 x 10~2 M, kp and kt also given by other temp. Solvent: n-hexane 1.33 M Solvent: chlorobenzene 1.33 M Solvent: methyl benzoate 1.33 M Solvent: benzene 1.33 M Solvent: acetone 1.33 M Solvent: acetonitrile 1.33 M Solvent: benzene 0.794M, AIBN 0.05 M kt also given by other [M] Solvent: benzene 0.794M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M, kp and kt also given by other [M] and temp.

Solvent: THF 0.44 M, AIBN 0.05 M, J^p andfct also given by other [M] Solvent: DMF 1.4 M, AIBN 0.05 M, jfcp andfct also given by other [M] and temp.

Refs. 213 185 185 185 185 185 185 185 185 177 213 182 162

162 162 162 162 162 162 154

154 177 182 182 182 177 182 182 182 195 177 233

195 195 195 195 234

235

TABLE 6. FUMARIC DERIVATIVES Monomer Fumaric acid - , bis (2-methoxy-ethyl) ester - , bis (2-chloro-ethyl) ester - , tert-butyl methyl ester - , tert-buty\ isopropyl ester

- , di-terf-butyl ester - , dicyclohexyl ester - , diethyl ester

- , diisopropyl ester

- , dimethyl ester - , dineopentyl ester Ethyl o-formylphenyl fumarate

TABLE 7.

M x l O " 6 ) (1/mol/s)

Temp. (0C)

Method

0.19 0.26 0.23 0.51 0.35 0.39 0.61 0.60 0.21 0.015

330 x 10~6 320 x 10~6 150xl0~6 26xlO"6

60 60 60 60 60

C C C C C

1.75 x l O - 5 30 x 10~6 40 x 10~6 (510-560) x 10" 6 1.64 x l O - 4

60 60 60 30

C C C Al

0.029 ±0.003

8 xlO-6

30

BlO

0.46 0.31 ±0.07

(80-100) x 10~6 0.84 x l O - 6

60 30

C BlO

0.058 0.028 4.0

430 x 10~6 44xlO~6 1.4

60 60 60

C C C

k p (1/mol/s)

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

7400

7.4xlO"5

40

22.7 570 kp = 3.3 x 106 x exp(- 15000/RT) 11000 3130 8.6 kp = 10 9 x exp(- 4540/7)

92 385 kt = 1.3 x 106 x exp(- 4200/RT) 2100 2300 0.175 kt = 106 x exp(- 2670/7)

-30 20

kp (1/mol/s) 4600 795 556-586 670-770 700 559 1100 1000 895 kp = 2.43 x l O 8 x exp(- 30600/RT) 9500-19000 (15-26) x 102

Remarks

Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AIBN MAIB Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AVN (2,2'-azobis-2,4dimethylvaleronitrile), ACN (l.l'-azobiscyclo-hexane1 -carbonitrile) ACN, scavenger TPV (1,3,5-triphenylverdazyl), sovent: benzene Solvent: benzene l.OM ACN, scavenger TPV, solvent: benzene Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene 1.16 M, MAIB 0.100 M, kp and ^ t also given by other [M]

Refs.

211 211 211 211 181 181 211 211 211 173

179

211 180 211 211 236

VINYL HALIDES

Monomer Tetrafluoroethylene

Vinyl bromide Vinyl chloride

Vinylidene chloride

TABLE 8.

kp (1/mol/s)

Remarks Large active chain end concentration measured by addition of inhibitor in aqueous solution polymn.

Al

Refs. 81

Al

80 44 32

25 25 25 22-75

Al Al Al Al

56 77 18 117

M x I O " 6 ) (1/mol/s)

Temp. (0C)

Method

220 46 2860-3040 2500-3100 2600 51.8 80 59 24 kt =4.16 x 105 x exp(- 21900/RT) 380-760 25

25 15 15.9 15.9 15.9 20 25 25 25

B5 Bl Al Al Al B4 Al Al B4 Al

60 50

E Al

Quoted in Ref. 80

Solvent: N-methylpyrrolidone 2.0M

VINYL ESTERS

Monomer Vinyl acetate

Remarks

Solvent: «-hexane

At 4% conversion

Using results of Refs. 8 and 15

Refs. 13 47 1 3 4 37 2 15 36 8 64 128

References page 11-15

TABLE 8. cont'd Monomer

Vinyl benzoate

TABLE 9.

kv (1/mol/s)

£ t (xIO~ 6 ) (1/mol/s)

Temp. (0C)

Method

Remarks

117zb 12 113±10 48 ± 5 97 ± 10 61 ± 9 37 ± 5 8± 1 637 ± 101 78 #

319±61 351±54 239 ± 4 5 311 d= 59 266 ± 7 5 412 ± 104 258 ± 76 94.2 ± 23.7 -

30

Al Al Al Al Al Al Al Al

32.5 32.5 32.5 32.5 30 15-60

Al C C C Al C

Solvent: benzene 2.00M Solvent: C 6 D 6 2.00M Solvent: anisole 2.00M Solvent: fluorobenzene 2.00M Solvent: chlorobenzene 2.00M Solvent: ethyl benzoate 2.00M Solvent: benzonitrile 2.00M Solvent: ethyl acetate 2.00M Solvent: ethyl acetate: ethyl benzoate (1:1 (v/v)) Solvent: benzene Solvent: benzene 5.41 M Solvent: ethyl acetate 5.43 M

120 310 530 630 1900 280 1400 4435 64.4 £ p = 2.0 XlO 6 27.5 x exp[(- 19000 ± 2900)/RT] Jcp = 2 . 1 x l O 8 x exp(- 27820//?7) ln[(*t|>]/(1.00-0.07/?)] = lnJfct[l]-0.50p 106 ± 1 4 253 ± 6 3 185 ± 8 402 ± 3 2 245 ± 13 522 ± 48 168 ± 18 383 ± 76 69 ± 13 257 ± 72 33 ± 3 299 ± 4 4 267±33 451 ± 6 5

Monovinyl ether of ethylene glycol Monovinyl ether of diethylene glycol

Monomer Styrene

Pressure 5.0 x 10 7 Pa

Fl 30

B5

30

Al Al Al Al Al Al Al

130 130 130 130 130 130 130 130 130 153 153 153 153 112 45 209

kt\p]; kt for pressure p (bar) £ t [l] = 52.0x 106 Solvent: anisole 1.01 M Solvent: benzene 1.01 M Solvent: fluorobenzene 1.01 M Solvent: chlorobenzene 1.01 M Solvent: ethyl benzoate 1.01 M Solvent: benzonitrile 1.01 M Solvent: ethyl acetate 1.01 M

122 116 116 116 116 116 116 116

VINYL ETHERS

Monomer

TABLE 10.

Refs.

k p (1/mol/s)

kt (x 10 6 ) (1/mol/s)

5.0 ±1.0 3.0 ± 0.8

1.5 ±0.3 1.4 ± 0.3

Temp. ( C )

Method

50 50

Al Al

Refs. 136 136

STYRENE DERIVATIVES k p (1/mol/s)

kt (x 10 ~6) (1/mol/s)

Temp. (0C)

Method

40 ± 20 24

80 ± 40 14

15 20

Al Al

51.9 108 106 102 390 209 18.7 39.5 £p = 2 . 1 6 x l 0 7 x exp(- 32500/RT) 22

10.5 32.5 108 -

30 30 30 40 50 50 25 25

Al Al Al D D E B5 Bl Al

5

D

40 50 50

D D D

139 223 206

115 2.79 5.96 2£t = 2 . 5 9 x l 0 3 x exp(- 9920/RT) -

Remarks Dimension of kp and kt: kg/mol/s From copolymn. data with sulfur dioxide

Quoted in Ref. 86 Using results of Ref. 20

Catalyst: cumene hydroperoxidetriethylenetetramine Catalyst: persulfate

Refs. 46 25 16 38 78 59 5 61 6 17 20 24 24 40 67

TABLE 10. cont'd Monomer

kp (1/mol/s)

M x l O " 6 ) (l/mol/s)

Temp. (0C)

* p = 2.24 XlO 14 xexp(-73510//?r) 50 80 64 370 915 25 ± 3 9 ± 1.5 35 ± 7 19 ± 4 35 ± 5 19 ± 3 29 ± 7 15 ± 4 23±8 11 ± 2 27 ± 4 31 ± 0.4 *p = 1.09 XlO 7 * t = 1.703 x l O 3 x exp(- 31380/K7) x exp(- 9489/RT) 66.6 22.4 66.5 £ p = 2.4 XlO 8 x exp(- 38000 ± 11OO)/RT 187.1 29.4

84

-,p-bromo-,/?-chloro-,/7-cyano-,p-fluoro-,/7-methoxy-

25 60

D Al

25 25 25 25 25 25 15-30

Al Al Al Al Al Al A2

65 118 Addition of 1 x 10 " 3 mol pyridine 118 Solvent: dodecane 40% by vol 104 100 Solvent: bromobenzene 20% by vol 100 Solvent: diethyl malonate 20% by vol 100 Solvent: diethyl phthalate 20% by vol 100 Solvent: dinonyl phthalate 60% by vol 100 DP = 2500 114

30 25 50-90

Al C

60 F2 Fl

25 25 40 70

Fl Fl Fl C

16.6-17.0

100

C

190 -

50 25

C Gl

kt (m,/i) = 1.97 x 102 (n x m) " ° 1 2

30

A3

5 30-90

C Fl F2

25 25 60

Fl Fl B5

91.2 25 30 25 25 28

Gl Al Fl Fl Fl Bl Fl

180 ± 1 0 £ p = 1.99xl0 7 exp(-30780//?D In kp = 17.14-1.873 x 10" 9 p - 3748/r + 2.02 x 10 " 6 p/T 77 ±4.1 79 ±5.1 187.0 201.0 167.0 641 ±48 89 107 92 78 23 In kp = 16.09-28950//?r (overall) = 16.47-3003/KT (chain length > 4) * p = 107-1±0-5 xexp[-(29±3)xlO3/*r] fcp = 1.8861 x 107 x exp(- 30737.52//?r) kp = 4.2060 x l O 8 x exp(- 37468.93/RT) kp = 4.2458 x 108 xexp(-39014.90//?7) 186 150 219 112 2.92 71

-

78 ± 1 2 96 ± 9 63.2 51.1 37.9 132 0.6

46 77 35 127 1.06 33

Refs. 73

-

256 107

Remarks

Bl

kp = 107-630 x exp(- 32510/RT) - 1 2 - 93 25

76 70 380 ±110 480 ± 1 0

Method

30 30 30 30 0 30

Pressure 5.0 x 10 7 Pa

102 98 98

Special evaluation from steady-state kinetics and Mn

134

215 kp also given by other [M] and 196 solvents Solvent/ethanol(25%)6.52M 196 Solvent: methanol (25%) 6.52 M 196 Pressure 2.0 x 108 Pa 186 Over a range of degree of polymn. 188 of the polymer radical from 40 to 410 Conversion 0-20% 174 TBP (terf-butyl peroxide) kp and kt also given by other temp. 189 Laser-flash-initiated polymn. by 156 benzoin n: n-mer, m: m-mer, 147 coupling with n-mer and m-mer 223 169 Pressure 1 x 10 5 -2.8 x 108 Pa 214

Solvent: Solvent: Solvent: Solvent: Solvent:

toluene 50% (v/v) benzene 3 M chlorobenzene 3 M benzonitrile 3 M toluene

kp also given by other temp.

Solvent: benzene 4.33 M

161 161 204 204 204 178 160 198 220 164 83 200

Bl

131

Fl

227

Fl

30% styrene in benzylalcohol

227

Fl

30% styrene in NMP

227

Al Al Al Al B5 Al

Solvent: dimethylacetamide

78 78 78 78 12 78

References page 11-15

TABLE 10. cont'd Monomer

kv (l/mol/s) kp = 1.67 x 1 0 n x exp(- 58240/RT) 84 kp = 2.27 XlO 7 x exp(- 32060/RT) kp = 10 5 7 7 x exp(- 23.0/RT) &p = 3 . 6 3 x l 0 7 x exp(- 31500/RT)

- , o-methyl- , p-methyl-

Styrene-d8

TABLE 11.

A: t (xl0~ 6 ) (l/mol/s)

66

Temp. (0C)

Method Bl

73

30

Al Bl

78 73

24-55

Fl

£t = 2 . 5 5 x l 0 4 x exp(- 14200/7?7)

Solvent: toluene 2M

Al

kp (l/mol/s)

Ict (x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

6.0 186 96.6 12 47 122

0.306 33 8.9 3 3.5 66

10 25 25 25 25 20

Al Al B4 B5 B4 Bl

209 17.3 953 22000 ± 4000

43 1.2 65 600 db 200

20 20 20 25

Bl Bl B4 Al

k p (l/mol/s)

M x 10 ~6) (l/mol/s)

Temp. (0C)

Method

-

(7-10) x 10 ~3

—190

B4

kp (l/mol/s)

kt(x 10~ 6 ) (l/mol/s)

Temp. (0C)

Method

Maleimide - , N-tert-amyl- , N-tert-butyl-

69 100

0.048a,0.017b 0.021 a ,0.023 b

60 60

C C

-, -, -, -,

120 23 120 49

0.20a 0.027 a ,0.015 b 0.15 a ,0.23 b 0.054

60 60 60 50

C C C C

55

0.069

W-Vinylcarbazole 2-Vinylpyridine 4-Vinylpyridine 5-Vinylpyridine - , 2-methyl-

Af-Vinylpyrrolidone

226 168

Remarks

Refs. 80 76 76 34 75 94

Solvent: methanol 1.95 M, kp also given as a function of [M] Solvent: 50% (molar) aqueous methanol 94 Solvent: acetic acid 94 82 Solvent: water 132

ALDEHYDES

Monomer Formaldehyde

TABLE 13.

Refs.

VINYLHETEROAROMATICS

Monomer

TABLE 12.

Remarks

Remarks Solid monomer, gamma irradiation

Refs. 95

OTHERS

Monomer

A^m-butyl-dimethylsilylN-tert-octylN-trimethylsilylN-cyclohexyl-

Remarks

Solvent: benzene 1M (a) Determined from steady-state equation kt = (2kdf[l])/[P']2, AIBN 0.005 M; (b) determined from second order plot of the decay curve of the radical concentration, ATMP (2,2 '-azobis-(2,4,4-trimethylpentane)) 0.02 M, for tert-BMl, ATMP 0.01 M

Solvent: benzene 0.559 M, AIBN 1.39 x 10" 2 M Solvent: benzene 0.698 M, AIBN 1.00 x 10~2 M, kp and kt also given by other [M] and [I]

Refs.

205 205

205 205 205 163 163

TABLE 13. cont'd A: p (1/mol/s)

Jt t (xl0" 6 ) (1/mol/s)

Temp. (0C)

- , AH2,6-diethylphenyl-

2.0

0.0078

60

C

- , Af-(2,6-dimethylphenyl)-

14

0.034

60

C

- , AH4-ethylphenyl)-

1200

3.9

60

C

- , #-(2-methylphenyl)-

190

0.59

60

C

- , Af-(2-carboethoxyphenyl)- , N-dodecyl-

96 54 104 175 80 128 149

0.10 0.12 0.45 1.0 0.40 0.064 0.17

60 50 50 50 50 50 50

C C C C C C C

386 250 235 196

0.55 -

50 50 50 50

C C C C

33

0.10

50

C

400

0.07

50

B9

Monomer

- , iV-octadecylOligotetramethylene glycol dimethacrylic ester (MW 600)

Method

Remarks Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene MAIB 0.005 M Solvent: benzene MAIB 0.01 M Solvent: toluene MAIB 0.01 M Solvent: anisole MAIB 0.01 M Solvent: chlorobenzene MAIB 0.01 M Solvent: bromobenzene MAIB 0.01 M Solvent: methyl benzoate MAIB 0.01 M Solvent: THF, MAIB 0.01 M Solvent: dioxane, MAIB 0.01 M Solvent: ethyl acetate MAIB 0.01 M Solvent: methyl ethyl ketone MAIB 0.01 M Solvent: benzene AIBN 0.20M, kp and k[ also given by other [I]

Refs. 183 183 183 183 237 238 238 238 238 238 238 238 238 238 238 239 124

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