Sprayable polythioether coatings and sealants

Patent metadata

Field	Value
Publication number	US-11098222-B2
Application number	US-201816026083-A
Country	US
Kind code	B2
Filing date	Jul 3, 2018
Priority date	Jul 3, 2018
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

Isocyanate-terminated chain-extended polythioether prepolymers, compositions thereof, and methods of use thereof are disclosed. The isocyanate-terminated chain-extended polythioether prepolymers are useful in sprayable coatings and sealants and especially sprayable coatings and sealants having a high filler content.

First claim

What is claimed is:

1. An isocyanate-terminated chain-extended polythioether prepolymer comprising reaction products of reactants, wherein the reactants comprise:
a thiol-terminated polythioether, a hydroxyl-terminated polythioether, or a combination thereof;
a diisocyanate;
a diisocyanate trimer; and
a non-linear short chain diol,
wherein the prepolymer:
is characterized by an isocyanate content from 4% to 6%, wherein the isocyanate content is determined according to indirect titration; and
comprises diisocyanates and diisocyanate trimers incorporated into the prepolymer backbone.

2. The prepolymer of claim 1 , wherein the thiol-terminated polythioether, the hydroxyl-terminated polythioether, or both the thiol-terminated polythioether and the hydroxyl-terminated polythioether comprise a moiety having the structure of Formula (2)
—S—R 1 —[S-A-S—R 1 —] n —S—  (2)

wherein,
n is an integer from 1 to 60;
each R 1 is independently selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and [(CHR 3 ) p —X-] q (CHR 3 ) r ;
p 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, S—S, and NR, wherein R is selected from hydrogen and methyl; and
each A is independently a moiety derived from a polyvinyl ether of Formula (3) and a moiety derived from a polyalkenyl polyfunctionalizing agent of Formula (4):
CH 2 ═CH—O—(R 2 —O) m —CH═CH 2   (3)

B 2 (—R 20 —CH═CH 2 ) z   (4)

wherein,
m is an integer from 0 to 50;
each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and —[(CHR 3 ) p —X—] q (CHR 3 ) r —,

wherein p, q, r, R 3 , and X are as defined as for R 1 ; and
B 2 is derived from an atom, a C 2-4 alkane, a C 2-8 heteroalkane, a cycloalkane, a substituted cycloalkane, a heterocycloalkane, a substituted heterocycloalkane, an arene, a substituted arene, a heteroarene, or a substituted heteroarene;
z is an integer from 3 to 6; and
each R 20 is independently selected from C 1-10 alkanediyl, C 1-10 heteroalkanediyl, substituted C 1-10 alkanediyl, and substituted C 1-10 heteroalkanediyl.

3. The prepolymer of claim 2 , wherein each A is independently selected from a moiety of Formula (3a) and a moiety of Formula (4a):
—(CH 2 ) 2 —O—(R 2 —O) m (CH 2 ) 2   (3a)

B 2 {—R 20 —(CH 2 ) 2 —} 2 {—R 20 —(CH 2 ) 2 —S—[—R 1 —S-A-S-] n1 —R 1 —S-} z-2   (4a)

wherein n1 is an integer from 0 to 60.

4. The prepolymer of claim 1 , wherein the thiol-terminated polythioether comprises a thiol-terminated polythioether of Formula (2a):
HS—R 1 —[S-A-S—R 1 —] n —SH  (2a)

wherein,
n is an integer from 1 to 60;
each R 1 is independently selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[(CHR 3 ) p —X—] q (CHR 3 ) r —;
p 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, S—S, and NR, wherein R is selected from hydrogen and methyl; and
each A is independently a moiety derived from a polyvinyl ether of Formula (3) or a moiety derived from a polyalkenyl polyfunctionalizing agent of Formula (4):
CH 2 ═CH—O—(R 2 —O) m —CH═CH 2   (3)

B 2 (—R 20 —CH═CH 2 ) z   (4)

wherein,
each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and —[(CHR 3 ) p —X—] q (CHR 3 ) r —, wherein p, q, r, R 3 , and X are as defined as for R 1 ;
m is an integer from 0 to 50; and
B 2 is derived from an atom, a C 2-4 alkane, a C 2-8 heteroalkane, a cycloalkane, a substituted cycloalkane, a heterocycloalkane, a substituted heterocycloalkane, an arene, a substituted arene, a heteroarene, or a substituted heteroarene;
z is an integer from 3 to 6; and
each R 20 is independently selected from C 1-10 alkanediyl, C 1-10 heteroalkanediyl, substituted C 1-10 alkanediyl, and substituted C 1-10 heteroalkanediyl.

5. The prepolymer of claim 1 , wherein the hydroxyl-terminated polythioether comprises a hydroxyl-terminated polythioether of Formula (2b):
HO—R 10 —S—R 1 —[S-A-S—R 1 —] n —S—R 10 —OH  (2b)

wherein,
n is an integer from 1 to 60;
each R 1 is independently selected from C 2-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[(CHR 3 ) p —X—] q (CHR 3 ) r —;
p 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, S—S, and NR, wherein R is selected from hydrogen and methyl; and
each A is independently a moiety derived from a polyvinyl ether of Formula (3) or a moiety derived from a polyalkenyl polyfunctionalizing agent of Formula (4):
CH 2 ═CH—O—(R 2 —O) m —CH═CH 2   (3)

B 2 (—R 20 —CH═CH 2 ) z   (4)

wherein,
each R 2 is independently selected from C 1-10 alkanediyl, C 6-8 cycloalkanediyl, C 6-14 alkanecycloalkanediyl, and —[(CHR 3 ) p —X—] q (CHR 3 ) r —,

wherein p, q, r, R 3 , and X are as defined as for R 1 ;
m is an integer from 0 to 50;
B 2 is derived from an atom, a C 2-4 alkane, a C 2-8 heteroalkane, a cycloalkane, a substituted cycloalkane, a heterocycloalkane, a substituted heterocycloalkane, an arene, a substituted arene, a heteroarene, or a substituted heteroarene;
z is an integer from 3 to 6; and
each R 20 is independently selected from C 1-10 alkanediyl, C 1-10 heteroalkanediyl, substituted C 1-10 alkanediyl, and substituted C 1-10 heteroalkanediyl; and

R 10 is a moiety derived from the reaction of a compound comprising a hydroxyl group and a group reactive with a thiol group.

6. The prepolymer of claim 5 , wherein each A is independently selected from a moiety of Formula (3a) and a moiety Formula (4a):
—(CH 2 ) 2 —O—(R 2 —O) m —(CH 2 ) 2 —  (3a)

B 2 {—R 20 —(CH 2 ) 2 —} 2 {—R 20 —(CH 2 ) 2 —S—[R 1 S-A-S—] n1 R 1 —S—R 10 —OH} z-2   (4a)

wherein n1 in an integer from 0 to 60.

7. The prepolymer of claim 1 , wherein the diisocyanate comprises a diisocyanate having the structure of Formula (8):
O═C═N—R 4 —N═C═O  (8)

wherein R 4 is selected from C 1-10 alkane-diyl, C 5-8 cycloalkanediyl, C 6-10 arene-diyl, C 6-18 alkanecycloalkane-diyl, C 7-18 alkanearene-diyl, C 1-10 heteroalkane-diyl, C 5-8 heterocycloalkane-diyl, C 6-10 heteroarene-diyl, C 6-18 heteroalkanecycloalkane-diyl, C 7-18 hetero alkanearene-diyl, substituted C 1-10 alkane-diyl, substituted C 5-8 cycloalkane-diyl, substituted C 6-10 arene-diyl, substituted C 6-18 alkanecycloalkane-diyl, substituted C 7-18 alkanearene-diyl, substituted C 1-10 heteroalkane-diyl, substituted C 5-8 heterocycloalkanediyl, and substituted C 6-10 heteroarene-diyl.

8. The prepolymer of claim 1 , wherein the non-linear short chain diol comprises:
a branched short-chain diol;
a cyclic diol; or
a combination thereof.

9. The prepolymer of claim 8 , wherein the branched short-chain diol comprises a branched short-chain diol of Formula (10):
HO—[C(R 5 ) 2 —] s —OH  (10)

wherein,
s is an integer from 1 to 10;
each R 5 is independently selected from hydrogen and C 1-6 alkyl; and
at least one R 5 is C 1-6 alkyl.

10. The prepolymer of claim 1 , wherein the diisocyanate trimer comprises a diisocyanate trimer having the structure of Formula (9):
B 3 {—R 4 —N═C═O} 3   (9)

wherein,
each R 4 is i

Assignees

• Prc Desoto Int Inc

Inventors

• Boghossian Razmik
• Smith James

Classifications

• C08G18/52 Primary

  Polythioethers · CPC title

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C09D175/08

  from polyethers · CPC title

• C08G18/246

  containing also tin-carbon bonds · CPC title

• C08G18/758 Primary

  containing two or more cycloaliphatic rings · CPC title