Metal ligand-containing prepolymers, methods of synthesis, and compositions thereof

Patent metadata

Field	Value
Publication number	US-9062162-B2
Application number	US-201314065554-A
Country	US
Kind code	B2
Filing date	Oct 29, 2013
Priority date	Mar 15, 2013
Publication date	Jun 23, 2015
Grant date	Jun 23, 2015

Abstract

Metal ligand-containing prepolymers, compositions containing metal ligand-containing prepolymers, methods of synthesizing metal ligand-containing prepolymers and the use of metal ligand-containing prepolymers in aerospace sealant applications are disclosed. The metal ligand-containing prepolymers have metal ligands incorporated into the backbone of the prepolymer. Cured sealant compositions comprising the metal ligand-containing prepolymers exhibit enhanced properties suitable for aerospace sealant applications.

First claim

What is claimed is:

1. A metal ligand-containing prepolymer comprising a metal ligand incorporated into a backbone of the prepolymer, wherein the metal ligand comprises a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and a combination of any of the foregoing:
—X—(CH 2 ) n —CH(—OH)—  (25a)

—X—(CH 2 ) n —CH(—OH)—(CH 2 ) n —X—  (25b)

—CH(—OH)—(CH 2 ) n —X—(CH 2 ) n —CH(—OH)—  (25c)

—CH(—OH)—R 5 —CH(—OH)—  (25d)

—C(O)—R 5 —C(O)—  (25e)

wherein,
—X— is independently selected from —C(O)— or —S(O) 2 —;
each n is independently selected from 1, 2, and 3; and
R 5 is a C 1-3 alkane-diyl.

2. The prepolymer of claim 1 , wherein each X is —C(O)— and each n is 1.

3. The prepolymer of claim 1 , wherein each X is —S(O) 2 — and each n is 1.

4. A metal ligand-containing prepolymer comprising a metal ligand incorporated into a backbone of the prepolymer, wherein the prepolymer comprises a moiety of Formula (26):
-A-R 9′ -L-R 9′ -A-  (26)

wherein,
each R 9′ is independently a moiety derived from the reaction of R 9 of a metal chelating agent R 9 -L-R 9 with a thiol group, wherein each R 9 comprises a terminal group reactive with a thiol; and L comprises a metal ligand;
each A is independently a moiety of Formula (12):
—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m (CH 2 ) 2 —S—R 1 —] n —S—  (12)

wherein:
each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—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 independently comprises hydrogen or methyl; and
each X independently comprises —O—, —S—, and —NR 5 —, wherein R 5 is selected from hydrogen and methyl; and

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—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.

5. The prepolymer of claim 4 , wherein the metal chelating agent is selected from a bis(sulfonyl)alkanol, a hydroxypyridinone, an acetylacetonate, and a combination of any of the foregoing.

6. A metal ligand-containing prepolymer comprising a metal ligand incorporated into a backbone of the prepolymer, wherein the prepolymer comprises a metal ligand-containing polythioether of Formula (28a), a metal ligand-containing polythioether of Formula (28b), or a combination thereof:
R 6 -A-[—R 9′ -L-R 9′ -A-] N —R 6   (28a)

{R 6 -A-[—R 9′ -L-R 9′ -A-] N —V′—} z B  (28b)

wherein,
N is an integer from 1 to 10;
each R 9′ is independently a moiety derived from the reaction of R 9 of a metal chelating agent R 9 -L-R 9 with a thiol group, wherein each R 9 comprises a terminal group reactive with a thiol; and L comprises a metal ligand;
each A is independently a moiety of Formula (12):
—S—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m (CH 2 ) 2 —S—R 1 —] n —S—  (12)

wherein:
each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—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 independently comprises hydrogen or methyl; and
each X independently —O—, —S—, or —NR 5 —, wherein R 5 is selected from hydrogen and methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—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;
B represents a core of a z-valent polyfunctionalizing agent B(—V) z wherein:
z is an integer from 3 to 6;
each V is a group comprising a terminal group reactive with terminal thiol groups; and
each —V′— is derived from the reaction of —V with a thiol; and

each R 6 independently is selected from hydrogen and a moiety having a terminal reactive group.

7. The prepolymer of claim 6 , wherein each R 6 is hydrogen.

8. The prepolymer of claim 6 , wherein each R 6 is the same and the terminal reactive group is selected from —SH, —CH═CH 2 , —NH 2 , —OH, an epoxy group, a polyalkoxysilyl group, an isocyanate group, and a Michael acceptor group.

9. A thiol-terminated metal ligand-containing polythioether comprising the reaction product of reactants comprising:
(a) a thiol-terminated polythioether comprising a thiol-terminated polythioether of Formula (18a), a thiol-terminated polythioether of Formula (18b), or a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (18a)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m (CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (18b)

wherein:
each R 1 independently comprises C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, or —[(—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 independently comprises hydrogen or methyl; and
each X independently comprises —O—, —S—, or —NR 5 —, wherein R 5 is selected from hydrogen and methyl;

each R 2 independently comprises C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, or —[(—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;
p is an integer from 2 to 6; and
B represents a core of a z-valent polyfunctionalizing agent B(—V) z wherein:
z is an integer from 3 to 6;
each V is a group comprising a terminal group reactive with terminal thiol groups; and

each —V′— is derived from the reaction of —V with a thiol; and
(b) a metal chelating agent R 9 -L-R 9 , wherein each R 9 independently comprises a terminal group reactive with a thiol; and -L- comprises a metal ligand.

10. The polythioether of claim 9 , wherein the metal ligand comprises a moiety selected from Formula (25a), Formula (25b), Formula (25c), Formula (25d), Formula (25e), and a combination of any of the foregoing:
—X—(CH 2 ) n —CH(—OH)—  (25a)

—X—(CH 2 ) n —CH(—OH)—(CH 2 ) n —X—  (25b)

—CH(—OH)—(CH 2 ) n —X—(CH 2 ) n —CH(—OH)—  (25c)

—CH(—OH)—R 5 —CH(—OH)—  (25d)

—C(O)—R 5 —C(O)—  (25e)

wherein,
—X— is independently selected from —C(O)— or —S(O) 2 —;
each n is independently selected from 1, 2, and 3; and
R 5 is a C 1-3 alkane-diyl.

11. The polythioether of claim 9 , wherein the metal chelating agent comprises a bis(sulfonyl)alkanol, a hydroxypyridinone, an acetylacetonate, or a combination of any of the foregoing.

12. The polythioether of claim 9 , wherein the polythioether of Formula (18a) comprises the reaction product of a dithiol and a divinyl ether.

13. The polythioether of claim 9 , wherein the polythioether of Formula (18a) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane and diethylene glycol divinyl ether.

14. The polythioether of claim 9 , wherein the polythioether of Formula (18b) comprises the reaction product of a dithiol, a divinyl ether, and a polyfunctionalizing agent.

15. The polythioether of claim 9 , wherein the polythioether of Formula (18b) comprises the reaction product of 1,8-dimercapto-3,6-dioxaoctane, diethylene glycol divinyl ether, and triallyl

Assignees

• Prc Desoto Int Inc

Inventors

• Rao Chandra
• Deng Jun
• Lin Renhe

Classifications

• C08G75/12

  Polythioether-ethers (C08G75/0245 takes precedence) · CPC title

• C09J181/02 Primary

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title