Michael acceptor-terminated urethane-containing fuel resistant prepolymers and compositions thereof

Patent metadata

Field	Value
Publication number	US-9328274-B2
Application number	US-201414200569-A
Country	US
Kind code	B2
Filing date	Mar 7, 2014
Priority date	Mar 7, 2014
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

Urethane-containing prepolymers formed from diisocyanates and adapted for Michael addition curing chemistries and compositions thereof for use in sealant applications are disclosed. The prepolymers provide compositions that exhibit room temperature stability and a controlled curing rate following a brief activation.

First claim

What is claimed is:

1. A Michael acceptor-terminated urethane-containing prepolymer comprising the reaction product of reactants comprising:
(a) an isocyanate-terminated urethane-containing adduct; and
(b) a bis(vinylsulfonyl)alkanol.

2. The prepolymer of claim 1 , wherein the bis(vinylsulfonyl)alkanol comprises 1,3-bis(vinylsulfonyl)-2-propanol.

3. A Michael acceptor-terminated urethane-containing prepolymer comprising a prepolymer of Formula (6a), a prepolymer of Formula (6b), or a combination thereof:
R 30 —C(═O)—NH—R 20 —NH—C(═O)—[—R 60 —C(═O)—NH—R 20 —NH—C(═O)—] w —R 60 —C(═O)—NH—R 20 —NH—C(═O)—R 30   (6a)

B {—V′—S—R 50 —S—(CH 2 ) 2 —O—R 13 —O—[—C(═O)—NH—R 20 —NH—C(═O)—R 60 —] w —C(═O)—NH—R 20 —NH—C(═O)—R 30 } z   (6b)

wherein,
w is an integer from 1 to 100;
each R 13 independently comprises C 2-10 alkanediyl;
each R 20 independently comprises a core of a diisocyanate;
each R 30 independently comprises the structure of Formula (9):
—O—CH(—R 10 —S(O) 2 —CH═CH 2 ) 2   (9)

wherein R 10 is C 1-3 alkane-diyl;

each R 50 independently comprises a core of a sulfur-containing prepolymer;
each R 60 independently comprises a moiety having the structure of Formula (7):
—O—R 13 —O—(CH 2 ) 2 —S—R 50 —S—(CH 2 ) 2 —O—R 13 —O—  (7)

B represents a core of a z-valent, polyfunctionalizing agent B(—V) z wherein,
z is an integer from 3to 6; and
each V is a moiety comprising a terminal group reactive with a thiol group; and

each —V′— is derived from the reaction of —V with a thiol.

4. A composition comprising:
the Michael acceptor-terminated urethane-containing prepolymer of claim 3 ; and
an amine catalyst.

5. The composition of claim 4 , comprising a thiol-terminated sulfur-containing adduct.

6. The composition of claim 5 , wherein the thiol-terminated sulfur-containing adduct comprises a thiol-terminated polythioether, a thiol-terminated polysulfide, a thiol-terminated sulfur-containing polyformal, or a combination of any of the foregoing.

7. The composition of claim 4 , wherein the amine catalyst comprises a controlled-release amine catalyst.

8. The composition of claim 4 , formulated as a sealant.

9. A cured sealant, prepared from the composition of claim 4 .

10. The prepolymer of claim 1 , wherein the isocyanate-terminated urethane-containing adduct comprises the reaction product of reactants comprising:
(a) a hydroxy-terminated sulfur-containing adduct; and
(b) a diisocyanate.

11. The prepolymer of claim 10 , wherein the hydroxy-terminated sulfur-containing adduct comprises a hydroxy-terminated polythioether adduct of Formula (12a), a hydroxy-terminated polythioether adduct of Formula (12b), or a combination thereof:
R 6 —S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—R 6   (12a)

{R 6 —S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (12b)

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 for R 1 ;
m is an integer from 0 to 50;
n is an integer from 1 to 60; and
p is an integer from 2 to 6;
each R 6 is independently selected from —CH 2 —CH 2 —O—R 13 —OH, wherein each R 13 is C 2-10 alkanediyl; and
B represents a core of a z-valent, polyfunctionalizing agent B (—V) z wherein, z is an integer from 3 to 6; and
each V is a moiety comprising a terminal group reactive with a thiol group; and

each —V′— is derived from the reaction of —V with a thiol.

12. The prepolymer of claim 10 , wherein the hydroxy-terminated sulfur-containing adduct comprises the reaction product of reactants comprising:
(a) a thiol-terminated sulfur-containing adduct; and
(b) a hydroxy vinyl ether.

13. The prepolymer of claim 12 , wherein the thiol-terminated sulfur-containing adduct comprises a thiol-terminated polythioether adduct of Formula (15a), a thiol-terminated polythioether adduct of Formula (15b), or a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (15a)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 ] n —S—V′—} z B  (15b)

wherein,
each R 1 independently is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 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 as for R 1 ;
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, polyfunctionalizing agent B (—V) z wherein,
z is an integer from 3 to 6; and
each V is a moiety comprising a terminal group reactive with a thiol group; and

each —V′— is derived from the reaction of —V with a thiol.

14. The prepolymer of claim 1 , wherein the isocyanate-terminated urethane-containing adduct comprises an isocyanate-terminated urethane-containing polythioether adduct, an isocyanate-terminated urethane-containing polysulfide adduct, or a combination thereof.

15. The prepolymer of claim 3 , wherein each R 50 comprises the structure of Formula (5):
—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —  (5)

wherein,
each R 1 independently is selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 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 as for R 1 ;
m is an integer from 0 to 50;
n is an integer from 1 to 60; and
p is an integer from 2 to 6.

16. A composition comprising:
the Michael acceptor-terminated urethane-containing prepolymer of claim 1 ; and
an amine catalyst.

17. The composition of claim 16 , comprising a thiol-terminated sulfur-containing adduct.

18. The composition of claim 17 , wherein the thiol-terminated sulfur-containing adduct comprises a thiol-terminated polythioether, a thiol-terminated polysulfide, a thiol-terminated sulfur-containing polyformal, or a combination of any of the foregoing.

19. The composition of claim 16 , wherein the amine catalyst comprises a controlled-release amine catalyst.

20. The composition of cl

Assignees

• Prc Desoto Int Inc

Inventors

• Keledjian Raquel
• Ito Marfi
• Lin Renhe

Classifications

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C09J175/04

  Polyurethanes · CPC title

• C08G18/6715

  Unsaturated monofunctional alcohols or amines · CPC title

• C08G75/02

  Polythioethers · CPC title

• C08G18/758

  containing two or more cycloaliphatic rings · CPC title