Polymer

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 2t[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
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
67966
6.40.6
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

Solvent: benzene 1.76M
kt \p\; kt for pressure p (bar),
kt [l] = 3.5x 106
Solvent: anisole 2.00M
Solvent: chlorobenzene 2.00M
Solvent: benzonitrile 2.00 M
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
- , 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
- , 2-butoxy-, methyl ester
298
184
8
-
60
60
C
C
- , 2-butyroxymethyl-, methyl ester
360
1.4
60
19
0.51
60
8.6
1.6
300
21
1.8
1.1
60
60
60
C
C
C
11
0.08
50
0.57
0.11
60
0.76
1.4
60
- , 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
- , 2-pivaroxymethyl-, methyl ester
230
0.59
60
- , trans-2-vinyl-, methyl ester
125
60
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 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
Solvent: benzene LOOM, MAIB
0.050 M
Bulk MAIB 0.05 M, kp and kt
Bulk AIBN 0.10M
Bulk AIBN 0.10M
MAIB 0.050 M
Solvent: benzene 2.22 M, kp and kt
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
MAIB 0.05 M
Bulk 5.9 M, MAIB 0.05 M
MAIB 0.05 M
MAIB 0.01 M
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
231
MAIB 0.05 M, kp and kt
145
Optimum value
123
Optimum value
123
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
- , 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: formamide: 1,4-dioxane
(3:1 (v/v))
Solvent: formamide: 1,4-dioxane
(3:1 (v/v)), NaCl 0.1 M
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
106.430.26
xexp[(-297001500)//?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) - (247229)/T
jfcp = 3.44 x 10 6 exp(- 23300/RT)
1576
9.74
350
14
p
1O7.4o.4
30
25
9
_66

(with 0.22MNaOH)
pH=13.6
kp and kt also given as a

function of viscosity
AIBN 0.05 M
Pressure: 5.0 x 10 7 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[-(27.72.5)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
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
570
3.1
60

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

AIBN 0.05 M
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 = (15.110.17)-(275355)/r
390
lnfcp = (14.720.13)-(259042)/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
18050
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: fluorobenzene 4.69 M
Solvent: chlorobenzene 4.69 M
Solvent: anisole 4.69 M
Solvent: bromobenzene 4.69M
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
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
995 83
506 48
450 3 3
45629
448 47
498 39
61443
427 38
290
1020
530
550
43.6 4.9
35.6 3.9
42.0 3.0
43.82.0
47.2 6.6
42.9 4.7
39.93.3
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
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: C 6 D 6 2.0M
Solvent: fluorobenzene 2.0M
Solvent: benzonitrile 2.0M
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
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
BlO
5.8
0.017
BlO
kt(m,n) = 1.22 x W2(n x m)~ 0075
25
A3
21
70
B5
0.034
50
0.16
50
- 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
3138.1
794.0
815.0
957.0
394
62.4
51.6
38.2
25(3)
25
60
Fl
B5
60
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
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
1768
1809
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
2.060.21
2.160.19
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

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

MAIB 0.02 M
Refs.
213
182
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
- , di-n-butyl ester
3.5
1.59 x l O " 2
60
13
0.11
50
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
5.3
8.5 x l O " 2
50
5.9
0.053
50
- , di-sec-butyl ester
0.6
4.0 x 10 ~3
60
- , di-terf-butyl ester
0.2
5.6 x 10~3
60
- , dicyclohexyl ester
2.3
1.4xlO" 3
60
- , diethyl ester
7.7
0.24
50
3.7
6.41 x l 0 ~ 2
60
- , diisobutyl ester
2.7
1.56 x 10~2
60
- , diisopropyl ester
1.1
5.0xl0~~ 3
60
- , dimethyl ester
5.2
0.36
60
10
0.59
50
- , a-ethyl-P-hexarluoropropyl ester
5.0
0.28
60
- , 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
Monomer
Methyl N-phenyl-itaconamate
Remarks
Solvent: hexane 1.03 M
Solvent: cyclohexane 1.03 M
Solvent: toluene 1.03 M
Solvent: ethyl acetate 1.03 M
Solvent: THF 1.03 M
Solvent: acetone 1.03 M
MAIB 0.05 M
Solvent: benzene 1.5 M, kp and kt
MAIB 0.02 M
Solvent: cyclohexane 1.33 M,
MAIB 5.00 x 10~2 M, kp and kt
Solvent: n-hexane 1.33 M
Solvent: methyl benzoate 1.33 M
Solvent: acetone 1.33 M
Solvent: acetonitrile 1.33 M
AIBN 0.05 M kt also given
by other [M]
MAIB 0.05 M
MAIB 0.05 M
MAIB 0.02 M
MAIB 0.02 M
MAIB 0.02 M
MAIB 0.05 M
MAIB 0.02 M
MAIB 0.02 M
MAIB 0.02 M
MAIB 0.02 M
MAIB 0.05 M
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
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

AIBN
MAIB
AVN (2,2'-azobis-2,4dimethylvaleronitrile),
ACN (l.l'-azobiscyclo-hexane1 -carbonitrile)
ACN, scavenger TPV
(1,3,5-triphenylverdazyl),
sovent: benzene
ACN, scavenger TPV,
solvent: benzene
MAIB 0.100 M, kp and ^ t
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
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
11310
48 5
97 10
61 9
37 5
8 1
637 101
78
#
31961
35154
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: C 6 D 6 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
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
26733
451 6 5
Monovinyl ether of ethylene glycol

Monovinyl ether of diethylene glycol
Monomer
Styrene
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: fluorobenzene 1.01 M
Solvent: ethyl benzoate 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
40
50
50
D
D
D
139
223
206
115
2.79
5.96
2t = 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
238
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
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 = 107-10-5
xexp[-(293)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
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
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.
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
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

AIBN 1.39 x 10" 2 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
- , Af-(2,6-dimethylphenyl)-
14
0.034
60
- , AH4-ethylphenyl)-
1200
3.9
60
- , #-(2-methylphenyl)-
190
0.59
60
- , 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
400
0.07
50
B9
Monomer
- , iV-octadecylOligotetramethylene glycol dimethacrylic

ester (MW 600)
Method
Remarks
Solvent: benzene 1M,
AIBN 5 x 10- 3 M
AIBN 5 x 10- 3 M
AIBN 5 x 10- 3 M
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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P r o p a g a t i o n

The rate constants kv and kt have usually been assumed to

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

where P^ is a propagating chain of any length n and M is

By combining the separately determined ratios, k^/kt and

Figure 1. Arrhenius plots of all bulk polymerization data for

The two monomers styrene and methyl methacrylate

Method F uses pulse laser photopolymerization (PLP)

Method C uses electron spin resonance (ESR) for the

Method E refers to recalculated values

B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS

3.9 (7.8) x 102

Calalyst system: diisopropylbenzene,

References page 11-15

TABLE 3. ACRYLIC DERIVATIVES

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

- , 2-chloro-, ethyl ester

- , 2-fluoro-, ethyl ester

Solvent: Water, pH 7.9,

Pressure 5.0 x 107 Pa

Solvent: benzene 2.69 M

- , 2-acetyloxy-, methyl ester

- , 2-benzoyloxy-, ethyl ester

- , 2-butoxy-, methyl ester

- , 2-butyroxymethyl-, methyl ester

- , 3-methyl, dimethyladamantyl ester

- , 3-methyl, terf-butyl ester

- , 2-naphthoyloxymethyl-, ethyl ester

- , 2-pivaroxymethyl-, methyl ester

- , trans-2-vinyl-, methyl ester

Primary radical termination in a

References page 11-15

3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate

TABLE 4. METHACRYLIC DERIVATIVES

Solvent: water, pH 8.0

kp and kt also given as a

Solvent: benzene LOM,

Solvent: toluene 0.2M

Solvent: benzene LOM,

Solvent: ethyl acetate

References page 11-15

kp= 4.92 XlO 5

w p (weight fraction of polymer)

At high conversions ( ~ 65%)

Termination by combinat. using

(*J= 790 300)

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

fcp = 106 694 exp(- 23940/RT)

Solvent: ethanol (50%) 4.67 M, kv

Values from Chem. Abstr.

30% MMA in benzyl alcohol

30% MMA in NMP

particle size 260 nm, kp

Emulsion polymn., n-butyl aery late:

kt[p]\ kt for pressure p (bar),

Solvent: benzene 1.0M,

TABLE 5. ITACONIC DERIVATIVES

Solvent: benzene 0.5M

References page 11-15

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

Solvent: THF 0.44 M,

TABLE 6. FUMARIC DERIVATIVES

Solvent: benzene l.OM