Copolymerizable sulfur-containing adhesion promoters and compositions thereof

Patent metadata

Field	Value
Publication number	US-9365677-B2
Application number	US-201313940813-A
Country	US
Kind code	B2
Filing date	Jul 12, 2013
Priority date	Jun 21, 2012
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

Disclosed are sulfur-containing polymers containing copolymerizable adhesion promoters and compositions including sealant compositions useful in aerospace applications comprising sulfur-containing polymers containing copolymerizable adhesion promoters. In particular, polythioethers and polysulfides incorporating copolymerizable adhesion promoters are disclosed.

First claim

What is claimed is:

1. A copolymerizable sulfur-containing adhesion promoter comprising the reaction product of:
a sulfur-containing compound comprising the reaction product of triallylcyanurate and 1,8-dimercapto-3,6-dioxaoctane; and
a compound having the structure of Formula (3):
CH 2 ═CH—R 7 —P(═O)(OR 8 ) 2   (3)

wherein,
R 7 is selected from a covalent bond and C 1-6 alkanediyl; and
each R 8 is independently selected from hydrogen and C 1-4 alkyl.

2. The copolymerizable sulfur-containing adhesion promoter of claim 1 , wherein the copolymerizable sulfur-containing adhesion promoter comprises an average of one group that promotes adhesion per molecule or an average of two groups that promote adhesion per molecule.

3. The copolymerizable sulfur-containing adhesion promoter of claim 1 , wherein the compound having the structure of Formula (3) comprises vinylphosphonic acid, dimethyl vinylphosphonate, ethyl methyl vinylphosphonate, diethyl vinylphosphonate, vinyl phosphonic methyl ester, or a combination of any of the foregoing.

4. A curable composition comprising:
at least one copolymerizable sulfur-containing adhesion promoter of claim 1 ;
at least one thiol-terminated sulfur-containing polymer; and
at least one curing agent.

5. The curable composition of claim 4 , wherein the at least one thiol-terminated sulfur-containing polymer is selected from a group consisting of a thiol-terminated polythioether and a thiol-terminated polysulfide.

6. The curable composition of claim 4 , wherein the at least one thiol-terminated sulfur-containing polymer is selected from a group consisting of a thiol-terminated polythioether of Formula (13), a thiol-terminated polythioether of Formula (13a), and a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (13)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (13a)

wherein:
each R 1 independently is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein:
s is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R 3 is independently selected from hydrogen and methyl; and
each X is independently selected from O, S, and —NR—, wherein R is selected from hydrogen and methyl;

each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined above;
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6;
B represents a core of a z-valent, vinyl-terminated polyfunctionalizing agent B(—V) z wherein:
z is an integer from 3 to 6; and
—V is a moiety comprising a group that is reactive with a thiol group; and

each —V′— represents a moiety formed by the reaction of —V with a thiol group.

7. The curable composition of claim 4 , wherein the at least one curing agent is selected from an iso-epoxy and an isocyanate.

8. The curable composition of claim 4 , comprising at least one second adhesion promoter.

9. An aperture sealed with a sealant prepared from the curable composition of claim 4 .

10. A copolymerizable sulfur-containing adhesion promoter comprising the reaction product of:
a sulfur-containing compound comprising the reaction product of triallylcyanurate and 1,8-dimercapto-3,6-dioxaoctane; and
a compound comprising 1-(allyloxy)-3-(2-(2-aminoethylamino)ethylamino)propan-2-ol, aminopropylvinylether, or a combination thereof.

11. The copolymerizable sulfur-containing adhesion promoter of claim 10 , wherein the copolymerizable sulfur-containing adhesion promoter comprises an average of one group that promotes adhesion per molecule or an average of two groups that promote adhesion per molecule.

12. A curable composition comprising:
at least one copolymerizable sulfur-containing adhesion promoter of claim 10 ;
at least one thiol-terminated sulfur-containing polymer; and
at least one curing agent.

13. The curable composition of claim 12 , wherein the at least one thiol-terminated sulfur-containing polymer is selected from a group consisting of a thiol-terminated polythioether and a thiol-terminated polysulfide.

14. The curable composition of claim 12 , wherein the at least one thiol-terminated sulfur-containing polymer is selected from a group consisting of a thiol-terminated polythioether of Formula (13), a thiol-terminated polythioether of Formula (13a), and a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (13)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (13a)

wherein:
each R 1 independently is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein:
s is an integer from 2 to 6;
q is an integer from 1 to 5;
r is an integer from 2 to 10;
each R 3 is independently selected from hydrogen and methyl; and
each X is independently selected from O, S, and —NR—, wherein R is selected from hydrogen and methyl;

each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and —[(—CHR 3 —) s —X—] q —(—CHR 3 —) r —, wherein s, q, r, R 3 , and X are as defined above;
m is an integer from 0 to 50;
n is an integer from 1 to 60;
p is an integer from 2 to 6;
B represents a core of a z-valent, vinyl-terminated polyfunctionalizing agent B(—V) z wherein:
z is an integer from 3 to 6; and
—V is a moiety comprising a group that is reactive with a thiol group; and

each —V′— represents a moiety formed by the reaction of —V with a thiol group.

15. The curable composition of claim 12 , wherein the at least one curing agent comprises an iso-epoxy and an isocyanate.

16. The curable composition of claim 12 , comprising at least one second adhesion promoter.

17. An aperture sealed with a sealant prepared from the curable composition of claim 12 .

18. A copolymerizable sulfur-containing adhesion promoter comprising the reaction product of:
a sulfur-containing compound comprising the reaction product of triallylcyanurate and 1,8-dimercapto-3,6-dioxaoctane; and
a compound having the structure of Formula (5):
CH 2 ═CH—R 10 —COOH  (5)

wherein R 10 is C 1-6 alkanediyl.

19. The copolymerizable sulfur-containing adhesion promoter of claim 18 , wherein the compound of Formula (5) comprises but-3-enoic acid, pent-4-enoic acid, hex-5-enoic acid, or a combination of any of the foregoing.

20. The copolymerizable sulfur-containing adhesion promoter of claim 18 , wherein the copolymerizable sulfur-containing adhesion promoter comprises an average of one group that promotes adhesion per molecule or an average of two groups that promote adhesion per molecule.

21. A curable composition comprising:
at least one copolymerizable sulfur-containing adhesion promoter of claim 18 ;
at least one thiol-terminated sulfur-containing polymer; and
at least one curing agent.

22. The curable composition of claim 21 , wherein the at least one thiol-terminated sulfur-containing polymer is selected from a group consisting of a thiol-terminated polythioether and a thiol-terminated polysulfide.

23. The curable composition of claim 21 , wherein the at least one thiol-terminated sul

Assignees

• Prc Desoto Int Inc

Inventors

• Keledjian Raquel
• Lin Renhe
• Virnelson Bruce

Classifications

• C08G2190/00

  Compositions for sealing or packing joints · CPC title

• C08G75/0218 Primary

  containing oxygen · CPC title

• C08K5/378 Primary

  containing heterocyclic rings · CPC title

• Y10T428/24331

  including nonapertured component · CPC title

• C09J181/02

  Polythioethers; Polythioether-ethers · CPC title