A statistical calculation of the gel point and of the molecular size distribution is made for cross‐linked high polymers of arbitrary initial size distribution. The weight‐average polymerization degree of the cross‐linked polymer depends only on the weight‐average polymerization degree of the initial polymer and the degree of cross linking. The results obtained also apply to certain vinyl‐divinyl copolymers. Polymerization degrees can be estimated from observations of the gel point.

1.
P. J.
Flory
,
J. Am. Chem. Soc.
63
,
3083
(
1941
).
2.
P. J.
Flory
,
J. Am. Chem. Soc.
63
,
3091
(
1941
).
3.
P. J.
Flory
,
J. Am. Chem. Soc.
63
,
3096
(
1941
).
4.
P. J.
Flory
,
J. Phys. Chem.
46
,
132
(
1942
).
5.
W. H.
Stockmayer
,
J. Chem. Phys.
11
,
45
(
1943
), hereinafter called I.
6.
Vulcanization processes are obviously of this type. For several other examples, see
B. S.
Garvey
, Jr.
,
C. H.
Alexander
,
F. E.
Küng
, and
D. E.
Henderson
,
Ind. Eng. Chem.
33
,
1060
(
1941
).
7.
F. T.
Wall
,
J. Am. Chem. Soc.
63
,
1862
(
1941
).
8.
W. H.
Stockmayer
and
H.
Jacobson
,
J. Chem. Phys.
11
,
393
(
1943
).
9.
C. S.
Marvel
and
G. L.
Schertz
,
J. Am. Chem. Soc.
65
,
2054
(
1943
).
10.
H. M.
James
and
E.
Guth
,
J. Chem. Phys.
11
,
455
(
1943
).
11.
P. J.
Flory
and
J.
Rehner
, Jr.
,
J. Chem. Phys.
11
,
512
(
1943
).
12.
H.
Staudinger
and
W.
Heuer
,
Ber.
68
,
1618
(
1935
).
13.
R. G. W.
Norrish
and
E. F.
Brookman
,
Proc. Roy. Soc.
A163
,
205
(
1937
).
14.
For recent concepts of the mechanism of addition polymerization, consult:
J.
Abere
,
G.
Goldfinger
,
H.
Mark
, and
H.
Naidus
,
Ann. N.Y. Acad. Sci.
44
,
267
(
1943
);
C. C.
Price
,
Ann. N.Y. Acad. Sci.
44
,
351
(
1943
); ,
Ann. N.Y. Acad. Sci.
H. M.
Hulburt
,
R. A.
Harman
,
A. V.
Tobolsky
, and
H.
Eyring
,
Ann. N.Y. Acad. Sci.
44
,
371
(
1943
).,
Ann. N.Y. Acad. Sci.
15.
G. V.
Schulz
,
Zeits. f. Physik. Chemie
B44
,
227
(
1939
).
16.
P. J.
Flory
,
J. Am. Chem. Soc.
61
,
3334
(
1939
).
17.
R. G. W.
Norrish
and
R. R.
Smith
,
Nature
150
,
336
(
1942
).
18.
W.
Kauzmann
and
H.
Eyring
,
J. Am. Chem. Soc.
62
,
3113
(
1940
).
19.
E. F. G.
Herington
and
A.
Robertson
,
Trans. Faraday Soc.
38
,
490
(
1942
).
20.
G. V.
Schulz
,
A.
Dinglinger
, and
E.
Husemann
,
Zeits. f. Physik. Chemie
B43
,
385
(
1939
).
21.
If the termination process is a disproportionation of two radicals which leaves a double bond in one chain, or if a solvent takes part in chain transfer, slight modifications are required. At all significant degrees of polymerization, however, these effects are negligible.
22.
Experiments are now in progress in this laboratory.
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