SUBSTANCES A BASE DE POLYENES-POLYTHIOLS IMIDISABLES, PHOTODURCISSABLES

PHOTOCURABLE IMIDIZABLE POLYENE-POLYTHIOL COMPOSITIONS

Abrégé anglais

Abstract of the Disclosure
This invention relates to polyenes containing at
least two ethylenically unsaturated bonds per molecule
formed by reacting in substantially stoichiometric
amounts, (1) a primary diamine, (2) a member of the
group consisting of a benzenoid-containing dianhydride,
acid anhydride and anhydride acid halide and (3) an
ethylenically unsaturated alcohol. The thus formed amide-
acid polyene either per se or after being cured in
combination with a polythiol in the presence of a free
radical generator will, upon heating, imidize.

Revendications

The embodiments of the invention in which an exclusive property
or privilege is claimed are defined as follows:
1. An amide-acid polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k.and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10.
2. An imide-containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
57

Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10.
3. A method of preparing an amide-acid polyene which
comprises reacting in an inert atmosphere under anhydrous
conditions in substantially stoichiometric amounts (1) at least
one primary diamine having the structural formula: H2N-R-NH2
wherein R is a divalent organic moiety containing at least 2
carbon atoms, the two amino groups of said diamine each
attached to separate carbon atoms of said divalent organic
moiety with (2) at least one anhydride-containing member of the
group consisting of
<IMG>
<IMG> and
<IMG>
wherein R' is an aromatic residue attached to at least 3
carboxyl groups at least two of which groups are attached to
adjacent carbon atoms on the aromatic residue and X is a halide
radical and (3) an ethylenically unsaturated alcohol of the
formula: <IMG>
58

wherein
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; and m and d are 1 to 10 at a
temperature in the range 20 to 100°C in an organic solvent for
the amide-acid polyene product.
59

4. The method according to Claim 3 wherein the anhydride-
containing member is a dianhydride.
5. The method according to Claim 3 wherein the anhydride-
containing member is an acid anhydride.
6. The method according to Claim 3 wherein the anhydride-
containing member is an anhydride acid halide and the
halide formed from reacting the anhydride acid halide with
the ethylenically unsaturated alcohol is removed prior
to reaction with the primary diamine.
7. The process of imidizing the amide-acid polyene
of Claim 1 which comprises heating said polyene at a
temperature in the range 50-250°C for a time sufficient
to cause imidization.
8. The process according to Claim 7 wherein the
imidization is carried out in an inert solvent for the
amide-acid polyene at a temperature in the range 50-150°C.

9. A photocurable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d
are 1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator.
10. A photocurable composition comprising
(A) an imide-containing polyene of the formula:
<IMG>
61

wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d
are 1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator.
11. The process of forming a solid cured amide-acid
containing polythioether which comprises admixing
(A) a polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
62

(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the
range from about 94 to 20,000 of the general formula: R8-(SH)n
where n is at least 2 and R8 is a polyvalent organic moiety,
the sum of m and n being greater than 3, the polyene/polythiol
mole ratio being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator
and, thereafter, exposing the mixture to U.V. radiation.
12. The process of forming a solid cured imide containing
polythioether which comprises (1) admixing
(A) a polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1, m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
63

of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator, then in either
order (2) exposing said admixture to U.V. radiation and (3)
heating the admixture at a temperature in the range 50-250°C for
a time sufficient to imidize the amide-acid in the polyene.
13. The process of forming a solid cured imide containing
polythioether which comprises admixing
(A) a polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and (C)
0.01-5% by weight of (A) and (B) of a pinacol of the general
formula:
64

<IMG>
wherein R1 and R3 are members independently selected from the
group consisting of substituted and unsubstituted aromatic
radicals, R2 and R4 are members independently selected from the
group consisting of substituted and unsubstituted aliphatic and
aromatic radicals and X and Y are members independently selected
from the group consisting of hydroxyl, alkoxy and aryloxy and,
thereafter, heating the admixture in the range 50-250°C.
14. The process of forming a solid cured imide containing
polythioether which comprises admixing
(A) an imide containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety,
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"-CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum

of m and n being great than 3, the polyene/polythiol mole ratio
being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator
and, thereafter, exposing the mixture to U.V. radiation.
15. The process of forming a solid cured imide containing
polythioether which comprises admixing
(A) a polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"-CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and (C)
0.01-5% by weight of (A) and (B) of a pinacol of the general
formula:
66

<IMG>
wherein R1 and R3 are members independently selected from the
group consisting of substituted and unsubstituted aromatic
radicals, R2 and R4 are members independently selected from the
group consisting of substituted and unsubstituted aliphatic and
aromatic radicals and X and Y are members independently selected
from the group consisting of hydroxyl, alkoxy and aryloxy and,
thereafter, heating the admixture in the range 50-250°C.
16. A photopolymerizable composition comprising
(A) an imide-containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10; and
(B) a photocuring rate accelerator.
17. An article comprising the composition of Claim 9 as
a coating on a substrate.
18. The article according to Claim 17 wherein the substrate
is an electrical conductor.
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19. An article comprising the composition of Claim 10 as
a coating on a substrate
20. The article of Claim 19 wherein the substrate is an
electrical conductor.
21. An article comprising a cured imide containing
polythioether of Claim 14 as a coating on a substrate.
22. The article according to Claim 21 wherein the
substrate is an electrical conductor.
23. The article according to Claim 22 wherein the elec-
trical conductor is a wire.
24. The process of coating a substrate which comprises
(1) applying to a substrate a curable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"-CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
68

of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, then in
either order (2) exposing said curable composition under ambient
conditions to a free radical generator to form a solidified,
69

cured polythioether coating on said substrate and
(3) heating said cured composition in the range 50-250°C
to imidize the polyene.
25. The process according to Claim 24 wherein the
curable composition contains 0.005 to 50% by weight of
the polyene and polythiol of said curable composition
of a photocuring rate accelerator and the free radical
generator is U.V. radiation.
26. The process according to Claim 24 wherein the
free radical generator is high energy ionizing radiation.
27. An article comprising the cured composition of
claim 24 as a coating on a substrate.
28. The article of claim 27 wherein the substrate
is an electrical conductor.

29. A process for forming a continuous flexible adherent
cured coating on the surface of an electrical conductor selected
from the group consisting of wire and cable which comprises (1)
immersing said electrical conductor in a bath of a liquid
radiation curable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group cons sting of -CR"=CH2, -O-
(CH2)d-CR"-CH2, -?OCH2CR"=CH2 and O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10,
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and
(C) a photocuring rate accelerator, thus coating said
electrical conductor with said composition, (2) passing said
coated electrical conductor through a die, then in either order
(3) exposing said coated electrical conductor to U.V. radiation
for a time sufficient to cure said coating on said electrical
71

conductor under ambient conditions and (4) heating said coated
electrical conductor in the range 50-250°C to imidize the
polyene.
30. A photopolymerizable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; and m and d
are 1 to 10 and p is 0 to 10, and
(B) a photocuring rate accelerator.
31. The process of coating a substrate which comprises
applying to a substrate a curable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
72

R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, and there-
after exposing said curable composition under ambient conditions
to a free radical generator to form a solidified, cured
73

polythioether coating on said substrate.
32. The process according to Claim 31 wherein the
curable composition contains 0.005 to 50% by weight of
the polyene and polythiol of said curable composition
of a photocuring rate accelerator and the free radical
generator is U.V. radiation.
33. The process according to Claim 31 wherein the
free radical generator is high energy ionizing radiation.
74

34. A process for forming a continuous flexible adherent
cured coating on the surface of an electrical conductor selected
from the group consisting of wire and cable which comprises
immersing said electrical conductor in a bath of a liquid radi-
ation curable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole ratio
being in the range 0.2 to 8.0:1, respectively, and thereafter
exposing

said curable composition under ambient conditions to
a free radical generator to form a solidified, cured
polythioether coating on said substrate.
35. The process according to Claim 34 wherein
the curable composition contains 0.005 to 50% by weight of
the polyene and polythiol of said curable composition
of a photocuring rate accelerator and the free radical
generator is U.V. radiation.
36. The process according to Claim 34 wherein the
free radical generator is high energy ionizing radiation.
76

37. The process of coating a substrate which comprises
applying to a substrate a polymerizable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10 and exposing said compositions under
ambient conditions to a free radical generator to form a
solidified coating on said substrate.
38. The process according to Claim 37 wherein the compos
tions contains 0.005 to 50% by weight of the polyene of a
photocuring rate accelerator and the free radical generator is
U.V. radiation.
39. The process according to Claim 37 wherein the free
radical generator is high energy ionizing radiation.
40. A process for forming a continuous flexible adherent
coating on the surface of an electrical conductor selected from
the group consisting of wire and cable which comprises immersing
said electrical conductor in a bath of a liquid polymerizable
composition comprising
(A) an amide-acid containing polyene of the formula:
77

<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, exposing said composition under
ambient conditions to a free radical generator to form a
solidified coating on said substrate.
41. The process according to Claim 40 wherein the
composition contains 0.005 to 50% by weight of the polyene of
a photocuring rate accelerator and the free radical generator
is U.V. radiation.
42. The process according to Claim 40 wherein the free
radical generator is high energy ionizing radiation.
43. The process of coating a substrate which comprises
applying to a substrate a polymerizable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
78

wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and then in either order (2) exposing
said curable composition under ambient conditions to a free
radical generator to form a solidified, adherent coating on
said substrate and (3) heating said cured composition in the
range 50-250°C to imidize the polyene.
44. The process according to Claim 43 wherein the compos-
ition contains 0.005 to 50% by weight of the polyene of a
photocuring rate accelerator and the free radical generator is
U.V. radiation.
45. The process according to Claim 43 wherein the free
radical generator is high energy ionizing radiation.
46. A process for forming a continuous flexible adherent
coating on the surface of an electrical conductor selected
from the group consisting of wire and cable which comprises
immersing said electrical conductor in a bath of a liquid
photopolymerizable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
79

wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and
(B) a photocuring rate accelerator, thus coating said
electrical conductor with said composition, (2) passing said
coated electrical conductor through a die, then in either order
(3) exposing said coated electrical conductor to U.V. radiation
for a time sufficient to photopolymerize said coating on said
electrical conductor under ambient conditions and (4) heating
said coated electrical conductor in the range 50-250°C to
imidize the polyene.
47. The process of coating a substrate which comprises
(1) applying to a substrate a curable composition comprising
(A) an amide-acid containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form amide
linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;

A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2 and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10, and
(B) a polythiol having a molecular weight in the
range from about 94 to 20,000 of the general formula: R8-(SH)n
where n is at least 2 and R8 is a polyvalent organic moiety,
the sum of m and n being greater than 3, the polyene/polythiol
mole ratio being in the range 0.2 to 8.0:1, respectively, and
thereafter (2) exposing said curable composition under ambient
conditions to a free radical generator to form a solidified,
81

cured imide-containing polythioether coating on said
substrate.
48. The process according to Claim 47 wherein
the curable composition contains 0.005 to 50% by
weight of the polyene and polythiol of said curable
composition of a photocuring rate accelerator and
the free radical generator is U.V. radiation.
49. The process according to Claim 47 wherein the
free radical generator is high energy ionizing
radiation.
82

50. A process for forming a continuous flexible adherent
cured coating on the surface of an electrical conductor
selected from the group consisting of wire and cable which
comprises (1) immersing said electrical conductor in a bath of
a liquid radiation curable composition comprising
(A) an imide containing polyene of the formula:
<IMG>
wherein ? denotes isomerism, R is a divalent organic moiety
remaining after a secondary diamide has reacted with adjacent
carboxylic acid groups to form imide linkages;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
(CH2)d-CR"=CH2, -?OCH2CR"=CH2; and -O-?-CR"=CH2;
R" is hydrogen or methyl; k and h are 0 or 1; m and d are
1 to 10 and p is 0 to 10
(B) a polythiol having a molecular weight in the range
from about 94 to 20,000 of the general formula: R8-(SH)n where
n is at least 2 and R8 is a polyvalent organic moiety, the sum
of m and n being greater than 3, the polyene/polythiol mole
ratio being in the range 0.2 to 8.0:1, respectively, thus
83

coating said electrical conductor with said composition,
(2) passing said coated electrical conductor through
a die, and thereafter (3) exposing said coated electrical
conductor to radiation having an energy greater than 3
electron volts for a time sufficient to cure said
coating on said electrical conductor.
51. The process according to Claim 50 wherein the
curable composition contains 0.005 to 50% by weight of
the polyene and polythiol of said curable-composition
of a photoinitiator and the radiation is U.V. radiation.
52. The process according to Claim 50 wherein the
radiation is high energy ionizing radiation.
84

Description

3L~5i
This invention relates to a polyene composition, procedures
for making same and cured products resulting therefrom. More
particularly, this invention relates to an amide-acid polyene,
a method of preparing same, as well as curing the polyene with
a polythiol in the presence of a free radical generator to solid,
cross-linked, solvent-insoluble materials, which on heating will
imidize resulting in improved high temperature properties.
I~ is known that polyenes are curable by polythiols in the
presence of free radical generators such as actinic radiation
] to solid polythioether-c~ntaining resinous or elastomeric products.
See U. S. 3,661,744. However, high temperature characteristics
of the cured product are somewhat lacking due to the aliphatic
nature of the polyenes employed. For example, in the wire coat-
ing ield present day commercially available polyenes because
of their aliphatic structure fail the NEMA specified heat shock
and cut-through tests at the upper temperature limits at which
these tests are run, thereby negating their operability for this
end use. Thus, a coating having good high temperature properties
after curing is a desirous element.
In accordance with this ~nvention,
An amide-acid polyene of the formula:
O ~ / O O \ O O
-
(HOC)k C-NH-R / ~ 1 > \~
(Y~-~A~-OC COHHOC COH / HOC Co-~At-~Y)
m ,. \ " "
O ~ \O O / O O
~ / P
- 2 -

wherein ~ denotes isomerism, R is a divalent organic moiety
remaining after a primary diamine has reacted to form.amide
linka~es;
R' is an aromatic residue attached to at least 3 carbonyl
groups at least two of which groups are attached to adjacent
carbon atoms on the aromatic residue;
A is an alkylene group having from 1 to 10 carbon atoms;
Y is a member of the group consisting of -CR"=CH2, -O-
o o(CH2)d-CR"=CH2, -COCH2CR"=CH2 and -O-~-CR"=CH2
R" is hydrogen or methyl; k and h are O or l; m and d
are 1 to 10; and p is O to lO is obtained by reacting in sub-
stantially stoichiometric amounts (1) a primary diamine, ~2)
a member of the gxoup consisting of a benzoid-containing dian
hydride, acid anhydride and anhydride acid halide and (3) an
ethylenically unsaturated alcohol.
The thus formed polyene, on heating can be imidized per se
to form a polyene with improved high temperature properties of
the formula:
O ~ /0 0 \ o O
.(HOC ~ / C ¦ C\ / C\ /C\ ~(COH)h
~ R ~ N-RtN / R' N-R N R ~ + (2~2p)H20
(Y ~ A)-OC C \ C C C CO-(A) ~Y)m
O o \O O ~ O O
whe~ein R is a di~alent organic moiety remaining after the di-
secondary amide has reacted with adjacent carboxylic aci.d groups
to form imide linkages and R', R"l A,Y, k, h, m, d and p are as
hereinbefore set forth. Acrylic terminated polyenes, whether
imidized or of the amide-acide type, are photopolymerizable per
se by U,V. light, preferably in the
-- 3 --

s
presence of a photoinltiator as will be shown by an example
hereinafter, Additionally, any of the polyenes herein in
combination with a polythiol on exposure to a free radical
generator forms a cured polythioether. Imidization which
results in improved high temperature properties can be
carried out prior concurrent with or subsequent to radiation
curing. This polyene and polythiol mixture is a highly
reactive composition which is capable of being photocured
when exposed to actinic radiation in the presence of a U.V.
sensitizer to insoluble polythioether-con-taining materials.
Additionally, on following the photocure, the cured poly-
thioether can be heated preferably in the range
50-250C to imidize the amide-acid thereby irnproving
the high temperature properties of the cured material.
Further, in accord with the instant invention, there
are provided me-thods of preparing an amide-acid polyene
which comprises reacting in substantially stoichiometric
amounts (1) at least one primary diamine having the
structural formula: H2N-R-NH2
wherein R is a divalent organic moie~y containing at
least 2 carbon atoms, the two amino groups of sald diamine
each attached to separate carbon atoms of said divalent
organic moiety with (2) at least one anhydride-containing
member of the group consisting of
O O
~C~ ~.C,
\C/ \C/,
O O
O
/ C\
EIOC-R' /O
O C

()
/c\
XC-R \ /O
wherein R' is an aromatic residue attached to at least
3 carboxyl groups at least two of which groups are
attached to adjacent carbon atoms on the aromatic residue
and X is a halide radical and (3) an ethylenically
unsaturated alcohol of the formula: IIO-~A-~Y)m
. wherein
A is an alkylene group having from 1 to lO carbon
atoms;
Y is a member of the group consisting of -CR"=CH2,
O O
( 2)d 2' -COC112CR"=CH2 and -O-C-CR"=CH2;
R" is hydroyen or methyl; and m and d are l -to lO.
If desired, when using a dianhydride, a polyamide
acid structure containing up tolO repeating-uni-ts can be
obtained by reacting sufficient diamine with the dianhydride
prior -to reacting the thus formed polymer with
the ethylenically unsaturated alcohol.
The procedure for forming the amide-acid from
the primary diamine and the anhydride-containing member
is well known and conventional. That is, the amide-acid
is prepared by mixing at least one primary diamine
with at least one anhydride-containing member preferably
in an inert organic solvent for at least the product
and preferably one reactant under essentially anhydrous
conditions for a time preferably of at least 2 minutes and
at a temperature not hlgher than 1~0C to provide at
least 70% of the corresponding amide-acid. It should be
understood that it is not necessary that the resultant

prod~ct be totally amide-acid and tllat it is dcsirable
that the product contain not morc than 30g~ by wcight of
imide, the remainder being the amide-acid. Thus, while
the aforementioned conventional process for preparing
amide-acid should be conducted pref~rably below 50C
to p-ovide substantially 1006 by wei~ht of the amide-acids,
higher temperatures will still provide a product containiny
subs~antial amounts of the amide-acid.

In practicing the instant invention all synthesis
reactions are carried out in the presence of an iner-t gas
(e.g., nitrogen, argon or helium) blanket. Additionally,
although all the synthesis reactions can be carried out in
the presence of a solvent some of -the reactions can also be
carried out in the absence of solvents. The solvents useful
for synthesizing the polyenes of the instant invention are
organic solvents which do not chemically react with either
of the reactants (the amines or the anhydrides) or the final
amide-acid product. Additionally, besides being inert to
the reaction system and being a solvent for the product, the
organic solvent should be a solvent for at least one of the
reactants and, preferably, for both of the reactants. The
normally liquid organlc solvents of the N,N-dialkylcarboxyl-
amide class are useful as solvents in the process of the
instant invention. Preferred solvents are low molecular
weight members of this class, particularly N,N-dimethyl-
formamide and NjN dimethylacetamide. The solvents are
readily removed from the amide-acid by evaporation, displace-
ment or diffusion. Other useful solvents include, but are
not limited to, N,N-dlethylformamide; N,N-diethylacetamide;
N,N-dimethylmethoxyacetamide; N-methyl captolactam; dimethyl-
sulfoxide; N-methyl-2-pyrrolidone; tetramethyl urea; pyridine;
dïmethylsulfone; hexamethylphosphoramide; tetramethylene-
sulfone; formamide; N-methylformamide; N-acetal-2-pyrrolidone;
and the like. The solvents can be used alone, in a combination
of the aforesaid solvents or in combination with poorer
solvents such as toluene, benzonitrile, dioxane, butyrol-
actone , xylenes, chlorobenzenes and cyclohexane.
-- 7 --

2~
.
More specifically, the reaction conditions for
forming the various polyenes dependlng on which anhydride-
con-taining member is employed are as follows.
To form the dianhydride amide-acid from a dianhydridc
and a diamine, each reac-tant is put into solution prior
to mixing together. The admixture during reaction is
maintained at a temperature in the range from 25~ up to but
preferably below 100C. Preferably, the diamin~ is added
to the dianhydride but the reaction is operable if the
sequence is reversed. In either sequence, the reactants
are added to each other slowly to restrict the formation
of very high molecular weight polymers. The mole ratio
of the dianhydride to the diamine is 2:1 for monomeric
amide-acids. A mole ratio of 1:1 can be employed should
polyamide~acid be desired. Any mole ratio ~etween
these ratios is operational. The amide-acid polyene is
formed by addiny an unsaturated alcohol which can be,
but need not be, in solution prior to its addition.
The reaction is carried out at temperatures between room
temperature and below 100C, preferably 60-80C for
periods ranging from 2 minutes to 3 hours. The resultant
product is worked up by repeatedly washing the reaction
mlxture with a large excess of water while vigourously
agitating the admixture. The wa-ter layer is discarded
and the resulting viscous gum is then dried by dissolving
it in an alcohol/benzene azeotropic mixture and azeotroping
off the water. The azeo-tropic solvent used alone or
as a mixture of solvents can be of any kind as long as
it dissolves the gum and has an azeotropic boiling point
below about 100C.
. _ ........................................... .
.

,5
To form a dicarboxylic amide-acid from a diamine and
an acid anhydride, the reaction can be carried out in the
presence or absence of the aforementioned solvent. If no
solvent is used, the reactants are mi~ed in the flask and
the flask is heated until the reactants react vigorously
at a temperature ranging from 25C up to 180C, preferably
150-175C. If a solvent is employed, the diamine solution
is preferably added to the anhydride but the reverse of
the sequence is operable. The temperature range of the
reaction when a solvent is employed is usually between ~
25C to 100C~ The dicarboxylic acid amide-acid solution
is Yigorously washed with water and the resulting viscous
gum is then dried by dissolving it into an alcohol~benzene
azeotropic mixture and azeotroping-off the water. To form
the~ ami~de-acid polyene ~rom this amide-acid, a co~ventional
esterific~tion reaction ~s performed. The unsaturated
alcohol can act as a solvent per se or additional solvents
such as benzene, toluene, isoprp~l alcohol~benzene can be
employe~ ~ catalyst such as those well ~nown~ i~ the esteri-
fication art, e.g., p-toluene sulfonic acid, methane sulfonic
acid, sulfuric acid, phosphoric acid, hydrochloric acid,
BF3-etherate, camphor sulfonic acid, organic tin compounds,
and the like, may be employed. The solvent and/or unreacted
alcohol is stripped off to recover the amide-acid polyene
product. With these reactants it is desirable and oftentimes
preferable to esterify the acid anhydride with the unsaturated
alcohol firstly in the absence of a solvent at a temperature
in the range of 100-255C and thereafter react the anhydride
groups with the diamine also in the,absence of a solvent at
a temperature in the range oE 60-190C.
g

^~ 2~
When the anhydride-containing member is an anhydride
acid halide, it is preferable to form the ester anhydride
from the reaction of the anhydride acid halide and the
unsaturated alcohol prior to reaction with the diamine.
The ester anhydride is formed by putting preferably the
anhydride acid halide in solution prior to admixing same
with the unsaturated alcohol. The reactants are added in
a mole ratio of approximately 1:1. The unsaturated alcohol
is added slowly to the anhydride acid halide while the
reaction solution is sparged vigorously with a dry inert
gas (e.g., nitrogen, argon or helium) to remove the hydrogen
halide. The reaction is carried out at slightly below,
preferably 10C below, refluxing temperature. After the
addition of all the alcohol is complete, the reaction is
continued until all the hydrogen halide has been removed.
The diamine with or without a solvent, is added to the ester
anhydride (at a diamine to anhydride ratio of 1:2) while
maintaining the reaction mixture in a range between 25
to about lOO~C, preferably between 50 and 80C, until the
IR absorption bands of the anhydride carbonyl groups disappear.
The amide-acid polyene produc-t is recovered by distilling
off the solvent at low pressure using a temperature
of pceferably not greater than 100C.
~ The diamines operable in the instant invention
are primary diamines having the structural formula
H2N-R-NH2 wherein R is a divalent organic moiety dcrived
from or containing an aromatic, ali~hatic, cycloalil~hatic,
heterocyclic or a combination of aromatic and aliphatic
groups containing at least 2 carbon atoms, the 2 amino
groups of said diamine are each attached to separate
carbon atoms of said divalent organic moiety.
- 10 -

Diamines which are operable in the instant invention
include, but are not limited to, 4,4'-diamino-dipllenyl
methane; benz.idine; 3,3'-dichlorobenzidine; 4,4'-cliamino-
diphenyl sulfide; 3,3'-diamino-diphenyl sulfone; ~,4'-
diamino-diphenyl sulfone; 4,4'-diamino-diphenyl ether;
30 1,5-diamino naphthalene; meta-phenylenediamine; 4,4'-
diamino-diphenyl propane;
para-phenylene-diamine; 3,3'-dimethyl-4,4'-biphenyl
diamine; 3,3'-dimethoxy benzidine; 2,4-bis(beta-amino-t~
butyl)toluene; bis-(para-beta-amino-t-butyl-phenyl)
ether; bis-(para-beta-methyl-del-ta-amino-pentyl)l~enzene;
bis-para-(l,l-dimethyl-S-amino-pentyl)benzene; l-isopropyl-
2,4-metaphenylene diamine; m-xylylene diamine; p-xylylene
diamine; ~li(para-amino-cyclohexyl) methane; hexamethylene
diamine; hepta-methylene diamine; octa-methylene diamine,
nonamethylene diamine, decamethylene diamine;
3-aminomethyl-3,5,5-trlmethylcyclohexyl amine; 3-methylheptam-
ethylene diamine; 4,4-dimethylheptamethylene diamine; 2,11-
diaminododecane; 1,2-bis-(3-aminopropoxy ethanc);
2,2-dimethyl propylene diamine; 3-methoxy-hexamethylene
diamine; 2,5-dimethylhexamethylene diamine; 2,5-dimethyl-
heptamethylenediamine; 3-methylheptamethylene diamine;
5-methylnonamethylenediamine; 2,17-diamino-eicosadecane;
1.,4-diamino-cyclohexane; l,10-diamino-1,10-dimethyl-
decane; 1,12-diamino-octadecane; 2,4 toluene diamine;
2,6 toluene diamine; 1,3-bis(aminomethyl)cyclohexane;
N,N'-bis (3-aminopropyl) dim~thyl hydantoin; 112N
~I N(C~12) 3(Cll2)2o(cH2) 3NH2; E12N(C112) 3 2 3 2
2 (C112) 3N(C113) (CH2) 3NH2 and mixtu~res thereof.
The anhydride-containing member useful for forming
polyenes in the instant invention is a men~er of the group
consisting of: .

3s
o o
ll ll
O / \ R~ \ O
C \C
.. ..
O ,0
O
~OC-R~ \ O
O \C/
... _ . ... , . . O
,' O
~ ~ r.~ . ,
0 /C\
. : - XC-R \ jO
~ o C
. .
.' ' O
wherein R' is an aromatlc residue a~tached to at least
3 carboxyl groups at least two of which yroups are
attached to adjacent carbon atoms on the aromatic resldue
and X is a halide radical- ~nhydride-containing members
... . . .. . . _ . _ . . .. . . .. . .. .. .. . .. .
operable in the instant invention to form amide-acid
polyenes include, but are not limited to, pyromelli-tic
dianhydride; 2,3,6,7-naphthalene tetracarboxylic dianhydride;
3,3',4,4'-diphenyl tetracarboxylic dianhydride; 1,2,5,6-
naphthalene tetracarboxylic dianhydride; 2,2',3,3'-diphenyl
tetracarboxylic dianhydridei 2,2-bis(3,4-dicarboxyphenyl)
propane dianhydride; bis(3,4-dicarboxyphenyl)sulfone
dianhydride; perylene 3,4,9,10-tetracarboxylic acid
dianhydride; bis(3,4-dicarboxyphenyl)ether dianhydride;
,,, ",,,,, , , .. . ~ .. _ .. _ .. ...... . . . .. . . . .. ... . . . . .. .. . . .... . ..... .
, . .
~-. bis!(3,4-dicarboxyphenyl) sulfone dianhydride, ethylene
,. tetracarboxylic acid dianhydride; trimelli-tic anhydride
~ acid halide, e. g. trimellitic anhydride acid chloride
;,
. benzophenone~etracarboxylic anhydride; trimellitic
- . 30 anhydride and the like.;
,~ .
;~ . .
- 12 -
,, ~ , ,.
.

~ 38~
Lthylenically unsa-tura-ted alcohols suitable ~or use
in the instant invention to form amide-acid polyenes
are those of -the formula: HO-~A-~Y)m
wherein
A is an alkylelle cJroup having ~rom 1 to 10 carbon
atoms;
Y is a men~er of tlle group consistiny of -CR"=CH2,
O O
O-(CIE ) -CR"=C~ , -COC112CR =C112;and -O-C-CR"=CH2;
R" is hydrogen or methyl; and m and d and 1 to 10.
10Illustrative of the operable reactive unsaturated
alcohols which react with the amide-acid to give the
desired polyene include, bu-t are not limited to, allyl
and methallyl alcohol, crotyl alcohol,~-undecylenyl
alcohol, 2 vinyloxyethanol, vinylhydroxyethyl sulfide,
propargyl alcohol, l-allylcyclopentanol, 2-methyl 3-butene-
- 2-ol, dially malate and hydroxyl substituted organic ester
of acrylic acid or methacrylic acid including, but not
limited to, 2-hydroxyethyl acrylate, 1 (or 2) hydroxy
propyl acrylate, 1 (or 2) hydroxybutyl acrylate and the
corresponding methacrylates thereof. Reactive unsa'~urated
derivatives of polyhydric alcohols such as glycols, triols,
-tetraols, etc., are also suitable. Representative examples
include trimethylolpropane or trimethylolethane diallyl
ethers, pentaerythritol triallyl ether and the like.
Mixtures of various reactive unsaturated alcohols are
operable as well. Additionally, a suitable ethylenically
unsaturated alcohol can be prepared by reacting one mole of
a polyvinyl alcohol containing 10 hydroxyl groups with 9
moles of allylchloride to obtain an alcohol having 9
ethylenically unsaturated sites.

2~1~5
- The aimide-acid L~olycnes of thc installt inv~ntion
- can be imidized per se by heatiny the polyene in the
range 50-250C. Ileating periods at thci low ~nd of the
tempera~ure range are necessarily of longer dul-ation than
~3~ those at ~he high end of the range to affect imidization.
The polyenes of the instant invention can also be
imidized and cured in combination with a polythiol
in the presence of a free radical generating agent.
In some instances the polyene/polythiol composition
is cured by adding a photosensitizer to the composition
and exposing it to U.V. radiation followed by heating
to effect imidization. In other instances the same
formulation is heated first to cause imidization and,
thereafter, subjected to U.V. radiation to effect curing.
Additionally, both imidization and curing can be effected
in one step by adding a chemical free radical generating agent,
- e.g. benzpinacol to the polyene/polythiol composition,
and thereafter, heating to effect both imidization
and curing. Additionally, the polyene per se can be
imidized by heating and, thereafter, admixed with a
polythiol and photosensitizer for U.V. curing. These
methods will be shown in the examples hereinafter.
. ~ ; , ,~ ` .
., . , ' .
, ' t ' . ' . '
.
'.: , . ~ .; '
. i '
` '~
.. ..
`~
",. . .
' . ' , , , ij `; .' ., .
,` ;`'~ "'.

31.~ L35
Polythiol as used herein referssto simple or complex
organic compounds having a multiplicity of pendant or terminally
positioned -SH functional groups per average molecule.
On the average the polythiol must contain 2 or more ~SH
groups/molecule and have a viscosity range of essentially 0 to
20 million centipoises (cps) at 70 C as measured by a Brookfield
Viscometer either alone or when in the presence of an inert
solvent, aqueous dispersion or plasticizer. Operable polythiols
in the instant invention usually have molecular weights in the
range about 94 to about ?0, 000, and preferably from about 100 to
about 10,000.
The polythiols operable in the instant invention may be
exemplified by the general formula R8~ SH)n where n is at
least 2 and R8 is a polyvalent organic moiety. Thus R8 may
contain cyclic groupings and he~ero atoms such as N, P or O and
primarily contains carbon carbon, carbon-hydrogen, carbon-
oxygen, or silicon-o~ygen containing chain linkages.
One class of polythiols operable with polyenes to obtain-
essentially odorless polythioether products are esters of thiol-
containing acids of the formula HS-Rg-COOH where Rg is an organic
moiety with polyhydroxy compounds of structure Rlo~OH)n where
Rlo is an organic moiety and n is 2 or greater. These components
will react under suitable conditions to give a polythiol having
the general structure:
'' . . ,
Rlo~OC-Rg-SH)n
where Rg and Rlo are organic moieties and n is 2 or greater.
Certain polythiols such as the aliphatic monomeric poly-
thiols (ethane dithiol, hexamethylene dithiol, decamethylene
dithiol, tolylene-2,4-dithiol, etc. and some polymeric poly-
thiols such as a thiol-terminated ethylcyclohexyl dimercaptan
polymer, etc. and similar polythiols which are conveniently and
- 15 -
.

Z~ 5
ordinarily synthesized on a commercial basis, although having
obnoxious odors, are operable in this invention but many of the
end products are not widely accepted from a practical, commercial
point of view. Examples of the polythiol aompounds preferred
for this invention because of their relatively low odor level
include but are not limited to esters of thioglycolic acid
(HS-CH2COOH), ~-mercaptopropionic acid (HS-CH(CH3)-COOH and
~ -mercaptopropionic acid (HS-CH2CH2COCH) with polyhydroxy com-
pounds such as glycols, triols, tetraols, pentaols, hexaols, etc.
Specific e~amples of the preferred polythiols include but are not
limitèd to ethylene glycol bis (thioglycolate), ethylene glycol
bis (~3 -mercaptopropionate), trimethylolpropane tris (thiogly-
colate), trimethylolpropane tris (~ -mercaptopropionate),
pentaerythritol tetrakis (thioglycolate) and pentaerythritol
tetrakis (~ -mercaptopropionate), all of which are commercially
available. A specific example of a preferred polymeric poly-
thiol is polypropylene ether glycol bis ( ~ -mercaptopropionate)
which is prepared from polypropylene-ether glycol (e.g. Pluracol
P2olo~ Wyandotte Chemical Corp.) and ~? -mercaptopropionic acid
by esterification.
The preferred polythiol compounds are characterized by a
low level of mercaptan-like odor initially, and after reaction,
give essentially odorless polythioether end products which are
commercially attractive and practically useful resins or elas*
tomers for both indoor and outdoor applications.
Prior to curing, the photocurable polymer may be formu-
lated for use as 100% solids, or disposed in organic solvents,
or as solutions, disperions or emulsions in aqueous media.
` The photocurable polymer compositions prior to curing may
readily be pumped, poured, siphoned, brushed, sprayed, doctored,
or otherwise handled as desired. Following applica~ion, curing
in place to a solid resin or elastomer may be effected either
- 16

2~35
very rapidly or extremely slowly as desired by manipulation of
the compounding ingredients and the method of curing.
To obtain the maximum strength, solvent resistance, creep
resistance, heat resistance and freedom from tackiness, the
reactive components consisting of the polyenes and polythiols
are fomulated in such a manner as to give solid, crosslinked,
three dimensional network polythioether polymer systems on curing.
In order to achieve such infinite network formation, the individ-
ual pol~enes and polythiols must each have a functionalit~ of at
leas~ 2 an~ the sum of the functionalities of the polyene and
polythiol components must always be greater than 4. ~lends and
mixtures of various polyenes and various polythiols containing
said functionality are also operable herein.
Functionality as used herein refers to the average number
of ene or thiol groups per molecule in the polyene or polythiol,
respectively. For example, a triene is a polyene with an average
of three reactive carbon to carbon unsaturated groups per molecule,
ancl thus has a functionality (f) of three. A dithiol is a poly-
thiol with an average of two thiol groups pèr molecule and thus
has a functionality (f) of two.
The term reactive unsaturated carbon to carbon groups means
groups which will react under proper conditions as sèt forth
herein with thiol groups to yield the thioether linkage (-C-S
C-), as contrasted to the term unreactive carbon to carbon
unsaturation. which means -C=C- groups found in aromatic nuclei
(cyclic structures exemplified by benzene, pyridine, anthracene,
and the like) which do not under the same conditions react with
thiols to give thioether linkages. For purposes of brevity,
this term will hereinafter ~e referred to generally as reactive
unsaturation or a reactive unsaturated compound~
As used herein, the term polyvalent means having a valence
of two or greater.

2~L~c5
Prior to curing, the polyene and polythiol components are
admixed in a suitable manner so as to form a homogeneous curable
mixture~ Thus, the polyene and polythiol reactants can ~e
admixed without the necessity of using a solvent at room temper-
ature or slightly elevated temperatures up to about 80C or, if
desired, the reactants may be dissolved in a suitable solvent
and, thereafter, the solvent can be removed by suitable means
such as evaporation.
The compositions to be cured in accord with the present
invention may, if desired, include such additives as antioxidants,
accelerators, dyes, inhibitors, activators, fillers, thickeners,
pigments, anti-static agents, flame-retardant agents, surface-
active agents, e~tending oils, plasticizers, thixotropic agents`
and the like within the scope of this invention. Such additives
are usually pre-blended with the polyene or polythiol prior to or
during the compounding step. The aforesaid additives may be
present in quantities up to 500 or more parts based on 100 parts
by weight of the polyene-polythiol curable compositions and
preferably 0.005-300 parts on the same basis.
The polythioether-forming components and compositions,
prior to ~uring, may be admixed with or blended with reactive
diluents t other monomeric and polymeric materials such as thermo-
plastic resins, elastomers or thermosetting resin monomeric or
polymeric compositions.
Non-limiting reactive diluents operable herein include
ethylene glycol diacrylate, ethylene glycol dimethacrylate, di-
ethylene glycol diacrylate, diethylene glycol dimethacrylate,
trimethylol propane triacrylate, trimethylol propane trimeth-
acrylate, pentaerythxitol tetracrylate, pentaerythritol tetra-
methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimeth-
acrylate, pentaerythritol triacrylate, neopentyl glycol di-
acrylate and mixtures thereof. The resulting blend may be
- la-

~ t5
subjected to conditions for curing or co-curing of the various
components of the blend to give cured produc-ts having unusual
physical properties.
Although the mechanism of the curing reaction is not
completely understood, it appears most likely that the curing
reaction may be initiated by most any free radical generating
source which disso~iates or abstracts a hydrogen atom from an
SH group, or accomplishes the e~uivalent thereof. Generally,
the rate of the curing reaction may be increased by increasing
the temperature of the composition at the time of initiation of
cure. In most applications, however, the curing is accomplished
conveniently and economically be operating at ordinary room
temperature conditions.
Operable curing initiators or accelerators include
radiation such as actinic radiation, e.g., ultraviolet light,
lasers; ionizing radiation such as gamma radiation, x-rays,
corona discharge, etc.; as well as chemical free radical gener-
ating compounds such as azo, ~perox~idici~ etc., compounds.
Azo or peroxidic compounds (with or without amine accel-
erators) which decompose at ambient conditions are operable as
free radical generating agents capable of accelerating the
curing reaction include benzoyl peroxide, di-t-butyl peroxide,
cyclohexanone peroxide with dimethyl aniline or cobalt naph-
thenate as an accelerator; hydroperoxides such as hydrogen
peroxide, cumene hydroperoxide, t-butyl hydroperoxides; peracid
compounds such as t-butylperbsnzoate, peracetic acid; persulfates,
e.g., ammonium persulfate; azo compounds such as azobis-
isobutyronitrile and the like.
These free radical generating agents are usually added in
amounts ranging from about 0.001 to 10 percent by weight of the
curable solid polyene-poly~hiol composition, preferably .01 to
5 percent.
-- 19 --

2~3s~
Additionally, substituted or unsubstituted pinacols such
as those set out in U. S. Patent No. 4,020,233 are also
operable as free radical generators to form imide-containing
cured polythioethers. That is, the amide-acid polyene, poly-
thiol and pinacol can be heated to form an imide-containing,
solid, cured polythioether as will be shown in an example here-
inafter.
The substituted or unsub~tituted pinacols operable herein
have the general formula:
1l 13
R2 - C - I R4
X Y
wherein Rl and R3 are the same or different substituted or
unsubstituted aromatic radicals, R2 and R4 are substituted or
unsubstituted aliphatic or aromatic radicals and X and Y which
may be the same or different are hydroxyl, alkoxy or aryloxy.
Pre~erred pinacols are those wherein Rl, R2, R3, and R4
are aromatic radicals, especially phenyl radical and X and Y
are hydroxyl.
Examples of this class of compouncls include but are not
limited to benzopinacol, ~,4'-dichlorobenzopinacol, 4,4'-
dibromobenzopinacol, 4,4'-diiodobenzopinacol, 4,4',4"~,4"'-
tetrachlorobenzopinacol, 2,4-2',4'-tetrachlorobenzopinacol,
4,4'-dimethylbenzopinacol, 3,3'-dime~hylbenzopinacol, 2,2'-
dimethylbenzopinacol, 3,4-3',4'-tetramethylbenzopinacol, 4,4'-
dimethoxybenzopinacol, 4,4' t 4",4"'-tetramethoxybenzopinacol,
4,4'-diphenylbenzopinacol, 4,4'-dichloro-4",4"'-dimethylbenzo-
pinacol, 4,4'-dimethyl-4",4"'-diphenylbenzopinacol, xanthon-
pinacol, fluorenonepinacol, acetophenonepinacol, 4,4'-dimethyl-
acetophenone-pinacol, 4,4'-dichloro-acetophenonepinacol, 1,1,2-
triphenyl-propane-1,2-diol, 1,2,3,4-tetraphenylbutane-2,3-diol,
1,2-diphenylcyclobutane-1,2-diol, propiophenone-pinacol,
20 -

, L3~
4,4'-dimethylpropiophenone-pinacol, 2,2'-ethyl-3,31-dimethoxy-
propiophenone-pinacol, 1,1,1,4,4,4-hexafluoro-2,3-diphenyl-
butane-2,3-diol.
As further compounds according to the present invention,
there may be mentioned: benzopinacol-mono methylether, benzo-
pinacol-mono-phenylether, benzopinacol monoisopropyl ether,
benzopinacol monoi-sobutyl ether~ benzopinacol mono (diethoxy
methyl) ether and the like.
The pinacol is added to the composition in amounts ranging
from 0.01 - 5% preferably 0.1 - 3~ bv weight based on the weight
of the ethylenically unsaturated compound and the polythiol.
The curing period may be retarded or accelerated from less
than 1 minute to 30 days or more.
Conventional curing inhibitors or retarders which ma~ be
used in order to stabilize the components or curable compositions
so as to prevent premature onset of curing may include hydro-
quinone; p-tert-butyl catechol; 2,6-di tert-butyl-p-methylphenol;
phenothiazine; N-phenyl-2-naphthylamine; phosphorous acid;
pyrogallol and the like.
The preferred free radical generator for the curing
reaction is radiation.
The curing reaction can be initiated by radiation having
an energy greater than 3 electron volts, i.e., either U.V.
radiation or high energy ionizing radiation. The U.V. radiation
can be obtained from sunlight or special light sources which
emit significant amounts of U.V. light having a wavelength in
the range of about 2,000 to about 4,000 Angstrom units. Any
type of U.V. light from any source may be used in carrying out
the method of this invention. For li~uid photocurable compo-
sitions, it is preferred that the light emanate from a point
source or in the form of parallel rays, but divergent beams are
also operable as a source of radiation.

3S
Various light sources may be used to obtain sufficient
U.V. radiation to practice the method of this invention. Such
sources include carbon arcs, mercury arcs, fluorescent lamps
with special ultraviolet light emitting phosphors, xenon arcs,
sunlight, tungsten halide lamps, argon glow lamps, photographic
flood lamps, lasers and the like.
When U.V. radiation is used for curing, a photoinitiator
is added to the composition to increase the curing rate.
Various photoinitiators, ~.e., photocuring rate acceler-
ators are operable and well known to those skilled in the art.Examples of photoinitiators include, but are not limited to,
be~zophenone o-methoxybenzophenone, acetophenone, o-methoxy-
acetophenone, acenaphthene-quinone, methyl ethyl ketone, valero-
phenone, hexanophenone, ~-phenylbutyrophenone, p-morpholino-
propiophenone, dibenzosuberone, 4-morpholinobenzophenone,
benzoin, ben20in methyl ether, 4'-morpholinodeoxybenzoin, p-
diacetylbenzene, 4-aminobenzophenone, 4'-methoxyacetophenone,
benzaldehyde, o-methoxybenzaldehyde, ~-tetralone, 9-acetyl-
phenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-
acetylphenanthrene, 3-acetylindole, 9~fluorenone, l-indanone,
1,3,5-triacetylbenzene, thioxanthen-9-one, xanthene-9-one, 7-M-
benz[dc]anthracen-7-one, l-naphthaldehyde, benzoin tetrahydro-
pyranyl ether, 4,4'-bis ~dimethylamino)benzophenone, fluorene-
9-one, l'-acetonaphthone, 2'-acetonaphthone, triphenylphosphine,
tri-o-tolylphosphine, acetonaphthone and 2,3-butanedione,
benz[a]anthracene 7,12 dione, 2,2-dimethoxy-2-phenylacetone,
diethoxyacetophenone, dibutoxyacetophenone, etc., which serve
to ~ive greatly reduced exposure times and thereby, when used
in conjunction with various forms of energetic radiation, yield
very rapid, commercially practical time cycles by the practice
of the instant invention.
- ~2 -

2,~5
These photocuring rate accelerators may range from about
0.005 to 50 percent by weight of the photocurable polyenepoly-
thio composition, preferably 0.05 to 25 percent.
The mole ratio of the ene/thiol groups for preparing the
curable composition i5 from about 0.2/1.0 to about 8/1.0, and
preferably from 0.5/1.0 to about 2/1.0 group ratio.
The radiation curable compositions of the instant invention
can also be cured by high energy ionizing irradiation. A
preferred feature of the ionizing irradiation operation of the
instant invention is treatment with high energy particle irradi-
ation or by gamma-rays or X-rays. Irradiation employing part-s
icles in the instant invention includes the use of positive ions
(e.g., protons, alpha particles and deuterons), electrons or
neutrons. The charged paxticles may be accelerated to high
speeds by means of various voltage gradient mechanisms such as
a Van de Graaff generator, a cyclotron, a Cockroft Walto~
accelerator, a resonant cavity an accelerator, a betatron, a
G. E. resonant transformer, a synchroton or the like. Further-
more, particle irradiation may also be supplied ~rom radio-
- active isotopes or an atomic pile. Gamma rays or X-rays may
be obtained from radioisotopes ~e.g., cobalt 60) or by particle
bombardment of suitable target material ~e.g., high energy
electrons on a gold metal target)~
The dose rate for the irradiation operable to cure the
coating in the instant invention is in the range 0.00001 to
1,000 megarads/second.
The amount of ionizing radiation which is employed in
curing the radiation curable material in the instant in~ention
can vary between broad limits. Radiation dosages of less than
a megarad up to 10 megarads or more for electrons are operable,
preferably 0.02 to 5 megarads energy absorbed are employed.
For gamma-rays or X-rays, radiation dosages in the range
- 23 -

~2~3t~
0,0001 to 5.0 megarads energy absorbed are operable. The
irradiation step is ordinarily performed under ambient temper-
ature conditions but can be performed at temperatures ranying
from below room temperature up to temperatures of 90C.
When using ionizing radiation, the depth of penetration is
dependent upon the density of the material to be penetrated.
If such penetration is not sufficient to cure the coating to
the entire depth desired when,-)beaming the rad~ation from one
direction only, one may use multiple radiation sources beaming
simultaneously or intermittently from diametrically opposite
sides of the coating. Furthermore, shielding can also be
employed to increase penetration of the coating on the opposite
side away from the radiation source.
The curable amide-acid polyene or imide polyene and poly-
thiol compositions are used in preparing solid, cured cross-
linked insoluble polythioether polymeric products having many
and varied uses, examples of which include, but are not limited
to, coatings; adhesives films, molded articles; imaged
surfaces, e.g. photoresists; printing plates; e.g. offset,
lithographic, letterpress, gravures, etc., silverless photo-
graphic materials and the like.
Since the cured materials formed from the polyenepolythiol
composition possessvarious desirable properties such as resist-
ance to severe chemical and physical environments and have good
high temperature properties on imidization, they are particu-
larly useful for preparing coatings.
A general method for preparing coatings, comprises coating
the curable composition on a solid surface of a substrate such
as plastic, rubber, glass, ceramic, metal, paper and the like;
exposing directly to radiation, e.g., U.V. light until the
curable composition cures and crosslinks in the exposed areas.
The resulting products are cured coatings on suitable substrates
or supports.

In forming the composition comprised of the polythiol
and the polyene, it is desirable that the photocurable compos-
ition contain a photocuring rate accelerator from about 0.005
to 50 parts by weight based on 100 parts by weight of the afore-
mentioned polyene and polythiol.
It is to be understood, however, that when energy sources,
e.g., ionizing radiation, other than visible or ultraviolet
light, are used to initiate the curing reaction, photocuring
rate accelerators (i.e., photosensitizers, etc.) are not required
in the formulation.
When U.V. radiation is used, an intensity of 0.0004 to
60.0 watts/cm2 in the 240-400 nanometer region is usually
employed.
The following examples will aid in explaining, but should
not be deemed limiting, the instant invention. In all cases
unless otherwise noted, all parts and percentages are by weight.
The termal shock and thermoplastic flow test were carried
out in accord with the procedure set out in National Electric
Manufacturers Association (NEMA) standards publication/No. MW
1000-1973.
In all examples herein, unless otherwise noted, the U.V.
radiation from the Addalux lamp had a surface intensity of
13,400 microwatts/cm2 and from the pulsed xenon lamp a surface
intensity of 22,000 microwatts/cm2.
- 24a -

3~
~XAMPL~ 1
To a 3-necked, 300 ml round bottom flask equipped
with stirrer, addition funnel and reflux condenser was
charged under a ni-trogen blanket 40.62 g of pyromellitic
dianhydride (PMAn) and 75 ml of freshly distilled N-methyl-2-
pyrrolidone (NMP). To the addition funnel was added 22.11 g
of N,N'-bis-~3-aminopropyl)dimethylhydantoin and 25 ml
of NMP. The PM~n was ~irst dissolved in the NMP and
then, while the temperature was kept between 40-60C,
the diamine was added slowly, dropwise, during a period
of 1.5 hours. When the addition was completed, the
temperature of the reaction mixture was raised to and
kept at between 70-80C while adding 38.71 g of trimethylol-
propane dially~ ether during a period of about 20 minutes.
Some more NMP was added to the reaction mixture after
addition of each reagent. Once the alcohol was added,
the mixture was kept between 70-80C for one hour,
after which time it was cooLed and worked up as follows:
The very viscous reaction mixture was dropped in-to
a large quantity of water and shaken vigorously. After
discarding the water layer, vigorous agitation with
water was repeated three more times. The viscous gum
was then dissolved in methanol, and the solu-tion was
transferred into a round bottom flask, provided with
stirring, Dean-Stark trap and a reflux condenser.
130 ml of benzene was then added and the solution was
- then boiled vigorously whil.e ais-tilling out most of the
methanol alollg wi~h most of the waL~er. The remaining water,
methanol and benzene were then distilled off under
reduced pressure at a maximum temperature of 80C.
. - 25 -

2~
The brown very viscous product weig11ed ~5 cJ. I'he IR
spectra indicated that at.least 75~ of this product
was of the formula:
C~13
O O ~ C1-13~ ~
HOC\ ~ /C-NH-~C11 ~-N N-~C11 ) -N11
CH2=cE-lcll2ofH2 ~ 2 3 ~,~ 2 3
C~13CH2C-CH2-OC CO1l
'' CH2=CHCH20CH2
1 0 ~
. O O
ll ll
-C ~ ~CO11
¦ o J o Cl~2C~I2CH=C~l2
HOC CO-c~12-CCE~2~H3
CH20CH2C~I=CH2
will hereinafter be referred to as Polyene A.
~XAMPL~ 2
To a 3-necked, 300 ml round bottom flask equipped
with stirrer and reflux condenser, was added under a
nitrogen blanket 25.67 g of 1,3-bis(aminomethyl)cyclo~
hexane and lO0 ml of dimethylformamide. I`he mixture
was heated to approximately 125C and while maintaining
the temperature constant, 69.97 g. of trimellitic anhydride
(TM~n) was added in three equal por-tions. The reaction
was allowed to proceed for 1.-5 hours and thcn was cooled
to room temperature. The product was worked up by
dropping the reaction mixture.into a large volume of
v1gorously stirred water. The water layer was then
disc.arded and the vigorous agitatio~ of the yun~ly product
with water was repeatecl. After discarding the water
. - ~6 -
. J. '4 ~,

3S
again, 25 ml of acetone was used to break up the cJum
while it started solidifying. To this slurry was added
500 ml of chloroform. The solid product was then filtered
and reslurried in benzene. This slurry was then dried
by azeotropic distillation, the whi-te solid amide-acid
was filtered and was th~nkept in a vacuum dissicator
containin~ P2O5. To a 3-necked, 300 ml round bottom flask
equipped with stirrer, reflux condenser and Dean-Stark
trap, was added ~.0 g of the white solid amide-acid
supra 50 ml of allyl alcohol and 0.1 g of concentrated
H2SO4. The mixture was boiled and while allyl alcohol
was distilled out of the flask in increments of about
10 ml, fresh allyl alcohol was added to the flask to
replace the removed alcohol. This procedure was continued
for several hours until sufficient esterification had
occurred. Solids in the reaction mixture were then filtered
off and the allyl alcohol in the filtrate was s-tripped
under vacuum. The product was a liyht brown, very
viscous liquid of the formula:
C-NHCH2
" I I' 2NHC~
CH2=C~ICH2OC ~ COH O ¦ "
O ~IOC- ~ `CC~2C~I=C~12
O
which will be referred to hereinafter as Polyene B.
~X~MPL~ 3
To a 3-necked, 300 ml round bot-tom flas]c equipped with
- stirrer, reflux condenser and a m~dified Dean-Stark -trap, was
added under a ni-trogen blanket 10.31 g. of trimelletic anhydride
(TMA~ and 6.37 g. of N,N'-bis(3-aminopropyl)dimethylhydantoin.
'''.J,

2~5
While the mixture was purged through with nitrogen, it was
heated to about 160-180C~ Soon after the fairly fast reaction
occurred, the reaction product was cooled to about 80C. 50 ml
of allyl alcohol, 0.009 g. of hydroquinone and 0.224 g. of
concentrated H2SO4 was then added to the pot and the Dean-
Stark~ trap was filled with alumina so that the alcohol could
be recirculated to the reaction flask while being dried by
the alumina. The reaction mixture was refluxed for about one
hour. Upon completion of the reaction, the excess allyl
alcohol was stripped off under vacuum. The final product of
the formula:
CH3 / O
CH3 ~ ~ O
ll ll
C-NH-~CH2~ N~"~N-~CH2)3 ~
" OH HOC CO-CH2-CH=CH2
CH2=CH--CH2-OC ,, O
was a yellow-brown viscous material and will be referred to
hereinafter as Polyene C.
EXAMPLE 4
To a 3-necked, 300 ml round bottom flask equipped with
stirrer, reflux condenser and a modified Dean-Stark trap, was
added under a nitrogen blanket 10.31 g. of TMAn and 6.37 g.
of N,N'-bis(3-aminopropyl)dimethylhydantoin. While the mixture
was purged through with nitrogen, it was heated to about
160-180C. Soon after the fairly fast reaction occurred, the
reaction product was cooled
- 28 -

~L6~ s5
to about 80C. 43.0 g. of allyl alcohol, and 5.56 g. of
trimethylolpropane diallyl ether, 0.0009 g. o~ hydroquinone
and 0. 224 g. of concentrated H2SO4 was then added to the pot
and the Dean-Stark trap was filled with alumina so that the
alcohol could be recirculated to the reaction flask while being
dried by the alumina. The reaction mixture was refluxed for
about one hour. Upon completion of the reac-tion, the excess
allyl alcohol was stripped off under vacuum. The final product
of the formula:
CH3
o CH3 ~
CH2=CHCH2OICH2 O ~ C-NH ~CH2~--3N~"~N (CH2) 3 .
CH3CH2C-CH2-OC COH
CH2=
Lo
C
HOC~\CO--cH2cH=cH2
was a yellow-brown viscous material and will be referred to
hereinafter as Polyene D.
EXAMPLE 5
To a 3-neck, 5-liter, round bottomed flask equipped with stirrer,
addition funnel, thermometer, reflux condenser and a nitrogen
sparge tube ~gas disperse system) was added under nitrogen
322.4 g. of trimellitic anhydride acid chloride (TMAn. Cl) and
791 g. benzene. The misture was heated until all the TMAn. Cl
dissolved in the benzene. To this solution was added very
slowly (via a
- 29 -

2i'~
dropping funnel) a 43% solution of trimethylo:Lprol?ane
diallyl ether in benzelle (311.70 g. in 413 g. benzene)
while the temperature oE the contents in the reaction
flaslc was kept just below 80C with continuous N2-sparging
- into the reaction solution. Once all the trimethylol-
propane diallyl ether was added, the N2-sparge was continued
to remove all the IIC1 in the reaction mixture. 650 g.
cf benzene was then distilled out of the reaction vessel.
The temperature of the reaction mixture was then lowered
to about 60C at which time a 49% solution of N,N'-bis
(aminopropyl)dimethylhydantoin, in benzene (176.23 g.
in 185 g. benzene) was added at a rate sufficient to sustain
a temperature of about 55-70C. Once all the N,N'-bis
(aminopropyl)dimetllylhydantoin was added, the reaction
mixture was kept a-t 60C until the IR absorption bands of
the anhydride carbonyl groups disappeared. Allalysis for
unreacted amine groups showed that the amine content
was less than 0.2 meq/g. The resultan-t product was
obtained by distilling off the benzene under vacuum. The
product (741 g) contained 24~ by weight imide and an amide-
acid polyene of the formula:
- Cll3
C113~
~ ~C-NII~CII ~N ,N~CII ) -Nll--
cll2=cllcl~2o~ll2 ~ 2 ~ ~o 2 3
C113C112('-C112-0C ~COII
cll2=cllc~l2~cll2
-CO~
,
~ C1 1120C1l2cll=cll2 ' '
110(` CO C112 CIC112C113
cil2Ocll2cll=cll2
_ . ~ . . . , . , . .. _ _ _ _ _ _ _
which will be referred to hereillafter as Polyene ~.
- 30 -

Z~;~5
~`X~MPI.~ 6
To a 3-necked, 300 ml round bottorn flask eguipped
with s-tirrer, addition funnel and reflux condenser
was charged under a nitrogen blanket 43.44 g. of pyromellitic
dianhydride (PMAn) and 75 ml of freshly distilled N-metllyl-2-
pyrrolidone (NMP). To the addition funnel was added 16.50 g.
of isophorone diamine, i. e. 3-aminomethyl-3,5,5-trimethyl-
cyclohexylamine and 25 ml of NMP. The PM~n was firs-t
dissolved in -the NMP and then, while the temperature was
kept between 40-60C, the diamine was added slowly, drop-
wise, during a period of 2.0 hours. When the addition was
completed, the temperature of the reac-tion mix-ture was
raise~ to andkept at between 70-80C while adding 41.41 y.
of trimethylolpropane diallyl ether mixed with 9 ml of NMP
during a period of about 5 minutes. Some more NMP was
added to the reaction mixture after addition of ~ach
reagent. Once the alcohol was added, the mixture was
kept between 70-80C for one hour, after which time it
was cooled and worked up as follows:
The very viscous reaction mixture was dropped in-to
a large quantity of water and shaken vigorously. ~fter
discarding the water layer, vigorous agitation with
water was repeated three more times. Thc viscous ~um was
then dissolved in methanol, and the solution was transferred
into a round bottom flas]c, provided with stirriny, Dean-
Stark trap and a reflux condenser. 130 ml of benzene was
then added and the solution was then ~oilecl vi~Jorously
while distilling out most of the methanol, which carries
out most of the water. The remaining water, met}lanol and
ben~ene were then distilled off under reduced pressure at a
- 31 -
;'`,)'.

~ ?2135
maximum temperature of 80C. The brown very viscous
product wt. about 95 g of the formula:
Cll2=cllcll~ofll~ o ~ ~C-i~ill_________ 2
Cll3cll2c-cll -OC ~COil
C~l2=cllcll2ocll2 o C~13
~o O '~~ ~~~
,.
-C~/\~,(.'OII
~ , I ll2C112CIi=C'il2
110(` ,C'O-C`II;~-f~ 2C~3 '''`'
Cll2oclf2c~ ll2
will hercinafter l)e rel~err~ o as l'ol~ c?. F

.5
E~AMPLE 7
To a 4-necked, 1 1. round bottom flask equipped wlth
stirrer, addition funnel, thermometer, Dean-Stark trap, and
reflux condenser was charged under a nitrogen blanket 16.0 g of
N,N'-bis~2-carboxyethyl)-dimethylhydantoin, 1.30 g of p-toluene
sulfonic acid as catalyst and 100 ml of benzene. The mixture
was refluxed until the Dean-Stark trap was full of benzene, and
then 3.50 g of allyl alcohol and 12.91 g of trimethylolpropane
diallyl ether in 50 ml of benzene was added during a period of
35 minutes. When no more water was azeotroping into the Dean-
Stark trap, the heat was turned off and the product was worked
up by washing it twice with 150 ml of water, then twice with
100 ml of 5% aq. NaHCO3, and then again twice with 100 ml of
water. The benzene layer containing the product was then dried
with anhydrous MgSO4, treated with decolorizing carbon, and
then distilled under vacuum until all the benzene was taken off.
The product, i. e.,
CH3
,Q
CH3 _ Y
O o fH2ocH2cH=cH2
2 2 OC(CH2)2N~"~N(CH2)2cocH2-c-cH2cH3
CH20CH2CH CH2
had a C=C content of 5.80 mmoles/g and will be re~erred to
hereinafter as Polyene G.
- 33 -

2~13~
The polyenes of the instant invention can be imidized per
se as is shown in the following examples.
EXAMPLE 8
A thin film of Polyene A from Example 1 was placed on a
sodium chloride IR window and heated for 5 minutes at 210C.
The IR spectrum after heating said polyene showed the disappear-
ance of the amide band and a significant increase of the imide
band evidencing imidization. The imidized polyene of the formula:
( ~H3
CH3 ~
HOC~ C\ (C 2) 3~ ~ ~N (CH2)3
,,~ _~ ~,~" . ~ ~
~ll2-1r~ 2 1 2 O O! N~ O
fH3cH2f--cH oc~ ~--o!
CH2=CHCH20CH2
o o
.
/ C ~ COH
N ~ o f 2 2 2
C f
O 2 2 2
will hereinafter be referred to as imidized Polyene H.
EXAMPLE 9
Example 8 was repeated except that Polyene E from Example 5
was substituted for Polyene A. The results were the same. The
imidized polyene of the formula:
- 34 -

2~3~
CH3
o 3 ~ f
CH2=CHcH2olcH2 ~ C (CH2)-3N\ ~ N (CH2)3
CH3CH2C-CH2-OC C .
CH2=CHCH2OCH2
O
&~ o f E~ 2 OCE~ 2 CH--c~ 2
C CO-CH -CCH CH
O 2 1 2 3
CH20CH2C~I=CH2
will hereinafter be referred to as imidized Polyene J.
Example 8 was repeated using Polyenes B, C, D and
F from Examples 2, 3, 4 and 6. The IR spectrum after
heating said polyenes in each case showed the disappearance
of the amlde band and a siynificant increase of the imide
band.
.. . _ . . . .. . .. _ .. .. . _ _. _ . . . . . .. _
EXAMPLE 10
. . _ .
To a four-neck, one-liter, round-bottomed flask
equipped with stirrer, additional unnel, thermometer,
heated (approx. 100-110C) Vigreux column, and a nitrogen
sparge tube was added under nitrogen 226.32 grams of
trimellitic anhydride 248.22 grams of trimethylolpropane-
diallyl ether and 2.5 grams of 1,6-hexamethylene bis(3,5-di-
tert-butyl-4-hydroxyhydrocinnamate). While the reaction
vessel wa`s slowly purged with nltrogen, the reaction mixture
was suddenly heated in an oil bath to ~40C. This tempera-
ture was maintained for about 4.5;hrs. while the slow nitrogen
purge removed the water generated by the reaction. ~very
-35~

~3~ 1L3~i;
40 minutes, the top layer of the distillate was returned to
the pot while the lower layer was discarded. The last two
returns of the top layer were timed such that they were done
about every 15 minutes before the reaction was considered as
finished. The reaction mixture was then rapidly cooled to
170c.
The Vigreux column was removed from the round bottomed
flask. In its place was pla~ed a short inverted U-shaped
tube,
To the product made above was added first 0.2 g of
hydroquinone and 0.1 g of pyrogallol, and then drop-wise
over a 45 minute period 64.32 grams of molten M-phenylene-
diamine while slowly purging the reaction ~essel with
nitrogen.
The reaction mixture was then kept for one h~ur at
175C, and the nitrogen flow was increased to achieve a
rapid removal of the water arising from the imidization
of the amide-acid.
The resultant imidized product of the formula;
O'
CH2=CHCH20CH2 ~ ~ N O
CH CH -fCH20C C ~ ,,C ~
CH2=CHCH20CH2 ~ C ~ 1l Cl 2 2 2
o COCIi2CCH2CH3
CH20CH2CH=CH2
will hereinafter be referred to as Polyene T.
- 36 -

3~
The following examples show various curable compositions
of either the amide-acid polyene or imide polyene in combina-
tion with a polythiol and methods of curing to obtain a
cured polythioether product.
EXAMPLE 11
5.0 g of Polyene E from Example 5 was admixed with
1.57 g of the bis(3-mercaptopropionate) of 1,3-bis
(2-hydroxye-thyl)-5,5-dimethylhydantoin, 0.20 g oE
pentaerythritol tetralcis(~-mercaptopropionate~, 0.10 g
of trime-thylolpropane tris(~-mercaptopropionate) and 0.137 g
of 2,2-dimethoxy-2-phenylacetophenone until homogeneous.
The admixture was exposed to U.V. radia-tion for 15 seconds
from Addalux lamp to form a cured polythioether and,
thereafter, heated for 5 minutes at about 210C to imidize
- the polyene portion. The IR spectrum of the resultant
cured solid product showed disappearance of the thiol
and amide absorption bands and appearance of the imide
absorption bands.
EXAMPLE 12
9.~57 g of Polyene E from Example 5 was heated
at 210C for 5 minutes to imidize the polyene. 'l'he thus
imidized polyene was admixed with 4.14 g of the bis
(3-mercaptopropionate) of 1,3-bis(2-llydroxyethyl)-
5,5-dimethylhydantoin, 0.40 ~ of pcntaerythritol tctrakis
(y-mercaptopropiona-te), 0.20 g of trimethylolpropane
tris(~-mercaptopropionate) and 0.147 y of benzoin iso-
propyl ether. The admixture was exposed to ~.V. radiation
from an ~ddalux lamp for 15 sccon~'s. A cured polythio-
ether produc~ resul-ted.
.
- 37 -

EXAMPLE 13
Using the formula-tion of ~xamplc llf-the proccdure
was reversed and the formulation was heated for 5 minutcs~
at 210C fol.lowed by U.V. curiny for lS seconds under
an Addalux lamp. A cured imidized polythioether product
resulted.
EXAMPLE 14
10 g. of Polyene E from Example 5 was admixed with
4.6 g. of di(2-hydroxyethyl)dimethylhydantoin bis(3-mercapto-
propionate), 2,5 g. of pentaerythritol tetrakis(~-mercapto-
propionate) and 0.166 g. of benzopinacol until homogeneous.
The adr~lixture was heated at 180C for 5 minutes. A cured
solid imidized polythioether product resulted.
The following examples show the'utility of the
polyene of the instant inven-tion with a polythiol in forming
an imidized cured polythioether coating when subjected
to U.V. radiation and heat. When U.V. radiation is
used, a photosensitizer or photocuring rate accelerator
is usually added to the system along with various convèntional
stabilizers to extend shelf life.
The amide-acid polyenes combined with a polythiol'
,will be compared with polyene/polythiol systems in which
the polyene is not imidizable or is not imidized and thus
does not have the improved higher temperature propcrties
such as'are desired,in wire coating.
? EXAMPLE 15,
The following formula'tions were made up from accurately
weighed ingredients and admixed until homogeneous:
- 38 -

213S
Formulation A
5.00 g. Polyene A from Example 1
3.26 g- tris(hydroxyethyl)isocyanurate tris (3-mcrcapto-
- propionate)
0.083 g. benzoin isopropyl ether (photosensitizer)
0.826 g. trimethylolpropane diallyl ether
0.826 g. dimercaptopropionate of N,N'-bis(2-hydroxyetilyl)
dimethylhydan-toin
0.083 g. benzopinacol
0.005 g. stabilizer package
Formulation B
3.78 g. Polyene A from Example 1
1.22 g. -tris(hydroxyethyl)isocya~urate tris (3-mercapto-
propionate)
0.50 g. dimercaptopropiona-te of N,N'-bis(2-hydroxy-
ethyl)dimethylhydantoin
- 0.25 g. trimethylolpropane diallyl ether
0.10 g. benzoin lsopropyl ether
0.005 g. stabilizer package
Formulation C
5.00 g. Polyene D from Example 4
4.28 g. tris(hydroxyethyl)isocyanurate tris (3-mercapto-
propionate)
1.41 g. dimercaptopropionate of N,N'-bis(2-hydroxy-
ethyl)dimethylhydantoin
0.36 g. trimethylolpropanc diallyl ether
0.186 g. benzoin isopropyl e-ther
0.010 g. stabilizer package
- 39 -

Formulation D
10.0 g. Polyene A from ~xample 1
3.25 g. tris(hyclroxyethyl)isocyanurate -tris(3-mercapto-
propionate)
0.66 g. dimercaptopropionate of N,N'-bis(2-hydroxyethyl)
dimethylhydantoin
0.28 g. benzoin isopropyl e-ther
0.014 g. stabilizér package
Formulation E
10.0 g. Polyene F from Example 6
3.02 g. dimethylolpropionic acid bis(3-mercaptopropiollate)
0.33 g. benzoin isopropyl ethcr
0.018 g. stabilizer packagc
Formula-tion F
.... . .
5.0 g Polyene E from Example 5
2.07 g dimerc~ptopropiona-te of N,N'-bis(2-hydroxy-
ethyl)dimethylhydantoin
0.20 g commercia~ly availablc pentaerytilritol tetrakis
- (~-mercaptopropionate)
0.10 g trimethylolpropane tris(~-mercaptopropionate)
0.137 g 2,2-dimethoxy-2-phenylace-tophenon~
0.009 g stabilizer package
Formulation G
45.0 g diallyl maleate
82.7 g tris(hydroxyethyl)isocyanurate tris(3-mercapto-
propionate~
3.83 g benzoin isopropyl ether
1.99 g s-tabilizer package
-- ~0 --

Z~L~3rj
Formulation ~1
-
20.00 g Polyene G from Examplc 7
2.38 g commercially available iso-diallylphthalate
23.66 g tris(hydroxyethyl)isocyanura-te tris(3-mercaPto-
propiona-te)
1.38 g benzoin isopropyl ether
201.41 g stabilizer package
Formula-tion I
.
20~00 g Polyene T of Example 10
3~01 ~ triallyl isocyanurate
15.25 g pen-taerythrito~ tetrak~s (3-mercaptopropionate~
1,34 g dimercaptopropionate o~ N,N'-bis(2-hydroxyethyl)-
d~methylhydantoin
0.792 g 2~2-dimethoxy-2-phenylacetophenone
0~008 g .stabilizer package
EXAMPLE 16
A 24 AWG copper wire was passed -through a degreasing
bath of methylene chloride followed by drying. The wire
was cut intolO sections and each wire section was cooled
.with one of the Formulations A-I from Examp.le15 with
the extra wire section also being coated-with Formulation F,
all at ambient conditions.
Each section of the thus coated wire was thell passed
through a die to insure a homogencous thickness of
1 mil and -through a surrounding barl]; oE U.V. pulscd ~cnon
lamps whose major spectral lines were all above 300 Angstroms

2~
at a speed o~ 20 feet per second for an exposure period
of 2 seconds. The sunlamps were so positioned that the
surface intensity on the radia-tion curable composition was
22,000 microwatts/cm . All the resulting
wire sections had a smooth, cured coating of 1 mil thickness
and showed good flexibility and adhesion on bendiny.
The thus cured coated wire sections coated with Formulations A,
B, C, D and one section coated with Formulation F were then
heated at 210-220C for 5 minutes to affect imidization.
All the wire sections with their cured coating were then
subjected to standard NEMA heat shock and -thermoplastic flow
test. The results are shown in TABL~ I.
TABL~ I
Formulation Properties of Wire-Coated FormulatioJls
Average Cut-Through lleat Shock (20~ S-tretchecl
Temperature (C) Wire at 175C for 30 l~inutes
... .
A 220 passed 1 x mandrel
B 260C passed 3 x mandrel
C - passed 2 x mandrel
D 210 passed 2 x mandrel
E 200 passed 1 x mandrel
F (imidized) 225 passed 3 x mandrel
` F (not imidized)125 passed 2 x mandrel
G 255 failed 5 x mandrel
H 100~ failed 5 x mandrel
I 350 passed 2 x mandrel
.-.
- 42 -
;' ,~,' .

~.Q~2~
Thus, as can be seen from the data in TABLE I, the radi-
ation curable formulations containing an imidized polyene
(Formulations A-F and I~ have improved high temperatures prop-
erties over conventional radiation curable polyene/polythiol
formulations tFormulations G and H) wherein the polyene is not
imidizable and over Formulation F which was not imidized.
The amide-acid polyenes of the instant invention can also
be synthesized in polymeric form as shown by the following
example:
E~AMPLE 17
To a 3-necked, 300 ml round bottom flask equipped with
stirrer, addition funnel, thermometer and nitrogen sparge tube
was charged under a nitrogen blanket 24.37 g. of pyromellitic
dianhydride (PMAn) and 44 ml of freshly distilled N-methyl-2-
pyrrolidone (NMP). The flask was heated to about 90C to
dissolve the PMAn, 13.4 g. of N,N'-bis(3-aminopropyl)dimethyl-
hydantoin and 15 ml NMP were charged to the addition funnel.
The flask was cooled to 75C and the contents of the addition
funnel were added to the flask over a one minute period. The
contents of the flask was stirred at 70C for 30 minutes after
which 6.29 g. of allyl alcohol were added to the flask. The
contents of the flask was then charged into chloroform and
filtered. A light brown polymeric polyene product (molecular
weight 6600 indicating 6-7 repeating units) resulted. The IR
spectrum showed little or no imide present in the product and
a substantial amide band present.
This polymeric polyene will be referred to hereinafter as
Polyene K.
- 43 -

2~
5 g of Polyene K were heated for 10 minutes at
220-C. The resultant product was dark brown, indicative
of imidization.
5 g of Polyene K were admlxed with 1.96 g of
dimethylolpropionic acid bis(3-mercaptopropionate)
and 0.139 g. of 2,2-dimethoxy-2-phenylacetophenone. The
admixture was exposed to U.V. radiation for 3 1/2 minutes
from an Addulux lamp. A cured, solid polythioether resulted.
EXAMPLE 18
The formulation of ExampLe 11 was coated to 1 mil
thlckness on each of the following substrates: paper,
cardboard, aluminum foil, steel plate stock, "Mylar"
polyester film, plywood, ceramic and a concrete block
of the type used in-building construction. The thus
coated substrates were exposed to U.V. radiation for
30 seconds from an Addelux lamp to form a cured polythio-
ether coating and, thereafter, heated for 5 minutes
at 210C to imidize the polyene portion.
- 44 -
, ,
~3 ~ ?

EXAMPLE 19
To a 3-necked, 300 ml round bottom flask equipped
with stirrer, addition funnel and an air sparge tube
(gas disperse system) was added 50 g of glacial acetic
acid, 68.20 g of trimellitic anhydride acid chloride,
0.585 g of 2,6-di-t-butyl-4-methylphenol and 0.0585 g
of methyl hydroquinone. After dissolution of the solids,
the flask was immersed into an ice/water bath. A mixture
of 32.10 g of triethyl amine (TEA) and 45.30 g of hyclroxy-
10 butyl acrylate (HBA) was then added dropwise to the coldsolution while continuously purging the reaction mixture
with air. Once the HBA/TEA mixture was added (addition
took 70 minutes), the cloudy reaction mixture was lef-t
standing for 10 minutes. 17.32 g of solid m-phenylene
diamine was then added slowly while keeping the reaction
mixture at about 35C. The disappearance of -the anhydride
group was followed by lnfrared spectroscopy. Once all the
anhydride reacted with the amine, the reaction mixture
was dropped into a large excess of vigorously agitated
20 water. The viscous gummy product was then dissolved
in acetone and the solution was`dried with anhydrous
magnesium sulfate and treated with decolorizing carbon.
To~the clear slightly yellow solution was added 0.585 g
of 2,6-di-t-butyl-4-methylphenol and 0.0585 g of methyl
hydroquinone. The bulk of the acetone was then evaporated
off slowly at near-room temperature. Residual acetone
was evaporated off at 80C for 0.5 hours.
Interpretation of the IR specti:'um of the final
cloudy brick-red waxy material showed that the material
30 contained primarily the compound of the formula:
-- 45 --

2~
O o~ \NH~ o
CH2=CEiCO ~CH2) 4OC COH NH-C~
o , ~ o o
HOC (C 2) 40CCH CH2
... . . , , ., . .. _ .. , _ . . . . . . . . . . .
hereinafter referred to as Polyene L, and small amounts
of the cyclized imide of the compound above.
EXAMP LE 2 0
A portion of the compound made and described under
Example 19 was heated to 150C for 0.5 hours to effect
imidization of Polyene L.
Interpretation of the IR spectrum of the final
light yellow beige glassy solid showed that the material
contained primarily the compound of the formula:
O
CH2=CHCO(CH2) 40C~'~ ~ ~C~ O O
~C~ CO ( CH 2 ) 4 OCCH=C~ 2
O .. ..
referred to hereinafter as Polyene M, and small amounts
of the uncyclized amide-acid.
, .
-- 46 --

~2~iL3S
EXAMPLE 21
To a 3-neck, 2 liter, round bottomed flask equipped
with stirrer, addition funnel, thermometer, reflux
condenser and a nitrogen sparge tube was added under nitrogen
309.30 g of trimellitic anhydride acid chloride (TMAn.Cl)
and 425 g toluene. The mixture was heated until all
the TMAn.Cl dissolved in the toluene (15-20 minutes).
To this solution was added via a dropping funnel, slowly
over a 2 hour period, 296.40 g of trimethylolpropane
diaIlyl ether (E) while the temperature of the contents
in the reaction flask was kept at about 80C with continuous
N2-purging into the reaction solution.
The N2-effluent, carrying much HCl and some toluene,
was bubbled through a trap, to condense the toluene, and
an aqueous NaOH scrubber, to neutralize the HCl.
Once all the E was added, the reaction mixture was
kept at 80C for another 30 minutes. It was then heated
to its boiling point (118C), and one half of the toluene
was distilled out of the reaction vessel while slowly
purging with nitrogenO The removal of the toluene took
about 20 minutes. The volume of toluene which WdS distilled
out was then replaced with fresh toluene, and the E-ester
of-the trimellitic anhydride (TMAn.E)/toluene solution
- was then subjected to an intermittent stream of steam
while keeping the reaction mixture at a mild reflux.
The water that was distilled ou-t of the vessel was
collected and analyzed for HC1. The total time to remove
the HCl was about 4.75 hours. The;total amount of water
used was about 260 ml.
- 47 -

~ ~,t~
Once the HCl was removed, the TMAn-E/toluene solution
was azeotropically dried and then fil-tered.
To the dry TMAn-E/toluene solution was added batchwise,
while keeping the temperature down to room temperature,
a total of 77.03 g of m-phenylene diamine (PDA). The
PDA was added "tricklewise" in 10% increments and,after
each addition, time was allowed for the PDA to completely
dissolve before the next addition was made. The time
between incremental additions (up to 70% of the total
addition) was about 10 minutes. This time increased to
about 20 minutes for each remaining incremental addition.
Once all the PDA was added and dissolved, the reaction
solution was kep-t at 55C for one hour.
The reaction solution was then refluxed for about
4 1/2 hours while removing azeotropically the water that
is generated during the imidization of the amide-acid.
Once complete imidization was achieved, the toluene
was distilled out at a reduced pressure. When most of
the toluene was removed, the temperature of the kettle
was increased to 130-140C to reduce the viscosity of the
brown product and thus increase the rate of removal of
residual toluene. The resultant imidized polyene of the
formula:
CH2=c~IcH2oclH2 ~ ~ ~ ~
CH CH C-CH -O-C ,CO N ~ O CH2OCH2CH-CH2
CH2=CHCH2OCH2 O C-O-CH -CCH CH
2 2 2
- 30 will hereinafter be referred to as Polyene N.
- 48 -

,2~
EXAMPLE 22
To a 3-neck, 2 li-ter, round bottomed flask equipped
with stirrer, addition funnel, thermometer, reflux
condenser and a nitrogen sparge tube was added under
nitrogen 309.30 g of trimellitic anhydride acid chloride
(TMAn.Cl) and 425 g toluene. The mixture was heated until
all the TMAn.Cl dissolved in the toluene (15-20 minutes).
To this solution was added via a dropping funnel, slowly
over a 2 hour period, 296.40 g of trimethylolpropane
diallyl ether (E) while the temperature of the contents
in the reaction flask was kept at about 80C with continuous
N2-purging into the reaction solution.
The N2-effluent, carrying much HCl and some toluene,
was bubbled through a trap, to condense the toluene,
and an aqueous NaOH scrubber, to neutralize the HCl.
Once all the E was added, the reaction mixture was
kept at 80C for another 30 minutes. It was then heated
to its boiling point (118C), and one half of the toluene
was distilled out of the reaction vessel while slowly
purging with nitrogen. The removal of the toluene took
about 20 minutes. The volume of toluene which was distilled
out was then replaced with fresh toluene.
~ To the hot E-ester of trimellitic anhydride (TMAn.E)/
toluene solution was added batchwi-se a total of 100 ml
of water. The water was added in l0 ml increments and
after each addition the water was azeotroped off again.
Each water increment was added at slightly below 100C,
and it carried over a large amount ~f the residual HCl
left in the TMAn.E/toluene solution. The water increments
which were distilled off were titrated for HCl. The
- 49 -

total time to remove the HCl was abou-t 4.5 hours.
After the bulk of the last wa-ter-increment was removed
(for HCl-content determination), the TMAn.E/toluene
solution was azeotroped further (approximately 3-4 hours)
to achieve complete dryness of the system. The solution
was then filtered.
To the dry TMAn.E/toluene solution was added batchwise,
while keeping the temperature down to room temperature,
a total of 77.03 g of _-phenylene diamine (PDA). The
PDA was added "tricklewise" in 10~ increments and,after
each addition, time was allowed for the PDA to completely
dissolve before the next addition was made. The time
between incremental additions (up to 70~ of the total
addition) was about 10 minutes. This time increased to
about 20 minutes for each remaining incremental addition.
Once all the PDA was added and dissolved, the reaction
solution was kept at 55C for one hour.
The reaction solution was then refluxed for about
4.5 hours while removing azeotropically the water that is
generated during the imidization of the amide-acid.
Once complete imidization was achieved, the toluene
was distilled out at a reduced pressure. When most of
the toluene was removed, the temperature of the kettle
was increased to 130-140C to reduce the viscosity of
the brown product and thus increase the rate of removal
of residual toluene.
.
,?i... ..
-- 50 --

EXAMPLE 23
The following formulations were made up from accurately
weighed ingredients and admixed until homogeneous:~
Formulation I
10.0 g Polyene O (an amide-acid polyene formed from
stoichiometric amounts of trimellitic anhydride
acid chloride, hexamethylene diamine and hydroxy-
butyl acrylate by the procedure in Example 19~
0.44 g dimercaptopropionate of N,N'-bis(2-hydroxyethyl)
dimethylhydantoin
0.029 g 2,2-dimethoxy-2-phenylacetophenone
0.006 g stabilizer package
Formulation J
10.0 g Polyene P (an imidized polyene formed from stoichio-
metric amounts of trimellitic anhydride acid
; chloride, N,N'-bis(3-aminopropyl) dimethylhydantoin
: and hydroxybutyl acrylate by the procedure of
Example 19)
0.2 g 2,2-dimethoxy-2-phenylacetophenone
0.06 g stabilizer package
Formulation ~ .
10.0 g Polyene Q (an amide-acid polyene formed.from
stoichiometric amounts of trimellitic anhydride
acid chloride, N,N'~bis(3-aminopropyl) dimethyl-
hydantoin and hydroxybutyl acrylate by the
procedure of Example 19)
1.5 g trimethylolpropane tris(~-mercaptopropionate)
0.23 g 2,2-dimethoxy-2-phenylacetophenone
0.06 g stabilizer package
- 51 -

il ~''~21~3S
EXAMPLE 24
The formulationsof Example 23 were coated to a
thickness of 2-5 mils onto various substrates and exposed
under atmospheric condi.tions,unless otherwise stated,
to an Addalux U.V. lamp whose major spectral lines
were all above 2400 Angstroms whereby the surface intensity
of the radiation on the coating was 20 milliwatts/cm2.
In some cases the U.V. cure was followed by a heating
step. The results are shown in Table II.

r
~a
.~
~ ~ ~ ~a ~a ~a ~a ~a ~a ~ ~a
.. ~J u,~ I h ~I h
U~ O O O
U~
~ O ~: ~
rl r-l r-l
U~ r~ r~
a) ~a ~a ~a c) ~ ra ~a ~a ra ~a
o o~ o t) ~ o o o o o
~a o o o x x o o o o o
~ . ~ ~ ~ ~ a
~ ~
~; rl ~ O O O O O O O
E~ O O O
,¢ . ~
a) O r~
a h ~ h
H rl ~ ~rl rl rl rl rl -rl rl ~rl
H ~Ll (~1 Z rd 11~
1~ ~
~ C) _
~4~
E~ P Q)-~
~ ~ ~ O O O U~
o o,~ ,~ ~ ~ ~ ~ ~ ,~
X ,~
E~
,~
,~a ~ o ,1:: . rl
rl 1~, 0 ~1 U~
Or~
~ O
5~ ~ rl ~ r~
E~ u~ r~
~ rd ~ ~ Q
,~ ~ O O rl r~ r~
u~ ~ ~ ~ O`U t)
.
H
H 1~1 H 1~ ~ i X .
30 ~
h
-- 53 --

Z:~35
EXAMPLE 25
To a 3-necked, 300 ml round bo-ttomed flask equipped
with stirrer, addition funnel and an air sparge tube
(gas disperse system) was added 59 g of glacial acetic
acid, 71.72 g of trimellitic anhydride acid chloride,
0.596 g of 2,6-di-t-butyl-4-methylphenol and 0.060 g
of methyl hydroquinone. After dissolution of the solids,
the flask was immersed into an ice/water bath. A mixture
of 37.00 g of triethyl amine (TEA) and ~3.27 g of hydroxy-
ethyl methacrylate (HEMA) was then added dropwise to thecold solution while continuously purging the reac-tion
mixture with air. Once the EIEMA/TEA mixture was added
(addition took 70 minutes), the cloudy reaction mixture
was left standing for 10 minutes. 18.15 g of solid
m-phenylene diamine was then added slowly while keeping
the reaction mixture at about 35C. The disappearance
of the anhydride group was followed by infrared spectroscopy.
Once all the anhydride reacted with the amine, the reaction
mixture-was dropped into a large excess of vigorously
agitated water. The viscous gummy product was then
dissolved in acetone and the solution was dried with
anhydrous magnesium sulfate and treated with decolorizing
carbon. To the clear slightly brown solution was added
0.596 g of 2,6-di-t-butyl-4-methylphenol and 0.060 g of
methyl hydroquinone. The bulk of the acetone was then
evaporated off slowly at near-room temperature. Residual
acetone was evaporated off at 80C for 0.5 hours.
Interpretation of the IR spectrum of the final
cloudy tan waxy material showed that the material contained
primarily the compound of the formula:
- 5~ --

21~5i
o
C~12=CCO (CH2) 4OC/~ \NH~
CH 3 ~\ "
.... . .. . IiOC C(Ci~2) 4OCC, CH2
O CH3
hereinafter referred to as Polyene R, and small amounts
of the cyclized imide of the compound above.
EXAMPLE~ 2 6
A portion of the compound made and described under
Example 25 was heated to 150C for 0.5 hours to effect
imidization of Polyene R.
Interpretation of the IR spectrum of the final
tan glassy solid showed that the material contained
primarily the compound of the formula:
' O
o~LC\ _~
...... H.2 C,C(CH2) 4OC " N~ ~
,~ :,. ; CH 3 ~C V--C O ( CH 2 ) 4 OCC~ CH 2
O CH 3
referred to hereinafter as Polyene S, and small amounts
of the uncyclized amide-acid.
Example 2 7
` ~ A 24 AWG copper wire was coated with bullet dies
(two passes, 1.8 mil total build) using Formulation I.
After each pass the coating was cured, for 4 seconds,
with a medium pressure mercury lamp. The resulting
coating was hard, flexible and well adhered to the
copper wire. The coated wire whenisubjected to standard
NEMA tests had a heat shock of 2xpass (20% stretched)
~- 55 -

L3~5
and a cut through of 350C.