Phosphine-catalyzed, michael addition-curable sulfur-containing polymer compositions

Patent metadata

Field	Value
Publication number	US-9328275-B2
Application number	US-201414200630-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

Compositions comprising Michael acceptor-terminated sulfur-containing prepolymers, thiol-terminated sulfur-containing prepolymers, and e phosphine catalysts useful in aerospace sealant applications are disclosed. The compositions exhibit extended pot life, cure rapidly following activation, and provide cured sealants having improved properties useful in aerospace sealant applications.

First claim

What is claimed is:

1. A composition comprising:
a Michael acceptor-terminated sulfur-containing prepolymer, wherein the Michael acceptor-terminated sulfur-containing prepolymer comprises a Michael acceptor-terminated polythioether prepolymer of Formula (11a), a Michael acceptor-terminated polythioether prepolymer of Formula (11b), 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   (11a)

{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  (11b)

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—, —NH—, and —N(—CH 3 )—;

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;
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 group comprising a terminal group reactive with a thiol group; and

each —V′— is derived from the reaction of —V with a thiol; and
each R 6 independently has the structure of Formula (13a):
—CH 2 —CH 2 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —CH═CH 2   (13a)

wherein each R 10 is independently selected from C 1-3 alkanediyl;

a thiol-terminated sulfur-containing prepolymer, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythioether selected from a thiol-terminated polythioether polymer of Formula (7a), a thiol-terminated polythioether polymer of Formula (7b), or a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (7a)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (7b)

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—, —NH—, and —N(—CH 3 )—;

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;
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 group comprising a terminal group reactive with thiol groups; and
each —V′— is derived from the reaction of —V with a thiol; and

a phosphine catalyst.

2. The composition of claim 1 , wherein the phosphine catalyst comprises a tertiary n-hydroxyl-substituted alkyl phosphine.

3. The composition of claim 1 , wherein the phosphine catalyst comprises trihydroxypropyl phosphine.

4. The composition of claim 1 , wherein the phosphine catalyst comprises from 0.01 wt % to 0.4 wt % of the composition, wherein wt % is based on the total solids weight of the composition.

5. The composition of claim 1 , formulated as a sealant.

6. A cured sealant formed from the composition of claim 5 .

7. A method of using the composition of claim 5 , comprising:
applying the composition of claim 5 to a substrate; and
allowing the composition to cure to provide a cured sealant.

8. A composition comprising:
a Michael acceptor-terminated sulfur-containing prepolymer;
a thiol-terminated sulfur-containing prepolymer, wherein the thiol-terminated sulfur-containing prepolymer comprises a thiol-terminated polythioether selected from a thiol-terminated polythioether polymer of Formula (7a), a thiol-terminated polythioether polymer of Formula (7b), or a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (7a)

{HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (7b)

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—, —NH—, and —N(—CH 3 )—;

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;
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 group comprising a terminal group reactive with thiol groups; and

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

a phosphine catalyst;
wherein the Michael acceptor-terminated sulfur-containing prepolymer comprises the reaction products of reactants comprising:
(a) a sulfur-containing prepolymer; and
(b) a compound comprising a terminal Michael acceptor group and a group that is reactive with a terminal group of the sulfur-containing prepolymer; and
wherein the compound comprising a terminal Michael acceptor group and a group that is reactive with a terminal group of the sulfur-containing prepolymer comprises a bis(sulfonyl)alkanol, a bismaleimide, or a combination thereof.

9. A composition comprising:
a Michael acceptor-terminated sulfur-containing prepolymer, wherein the Michael acceptor-terminated sulfur-containing prepolymer comprises a Michael acceptor-terminated polythioether prepolymer of Formula (11a), a Michael acceptor-terminated polythioether prepolymer of Formula (11b), 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   (11a)

{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  (11b)

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—, —NH—, and —N(—CH 3 )—;

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;
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 group comprising a terminal group reactive with a thiol group; and

each —V′— is derived from the reaction of —V with a thiol; and
each R 6 has the structure of Formula (13a):
—CH 2 —CH 2 —S(O) 2 —R 10 —CH(—OH)—R 10 —S(O) 2 —CH═CH 2   (13a)

wherein each R 10

Assignees

• Prc Desoto Int Inc
• Prc Desoto Int Inc

Inventors

• Anderson Lawrence G
• Cai Juexiao
• Bowman Mark P
• Lin Renhe

Classifications

• C09J181/02 Primary

  Polythioethers; Polythioether-ethers · CPC title

• C09J5/00

  Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers · CPC title

• C08L81/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers · CPC title

• C09J2481/00

  Presence of sulfur containing polymers · CPC title

• C08G75/02 Primary

  Polythioethers · CPC title