Polyurea compositions and methods of use

Patent metadata

Field	Value
Publication number	US-9580635-B2
Application number	US-201414319191-A
Country	US
Kind code	B2
Filing date	Jun 30, 2014
Priority date	Mar 18, 2011
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

Disclosed are polyurea compositions comprising the reaction products of a polyformal-isocyanate prepolymer and a curing agent comprising an amine. The compositions are useful as sealants in aerospace applications.

First claim

What is claimed is:

1. A composition comprising:
(a) an isocyanate-terminated polythioether, wherein the isocyanate-terminated polythioether comprises reaction products of reactants comprising:
(i) a polythioether polyol of Formula (20) and a polythioether polyol of Formula (21):
R 13 —S—R 1 —[—S—(CH 2 ) 2 —O—[—R 2 —O—] m —(CH 2 ) 2 —S—R 1 —] n —S—R 13    (20)

{R 13 —S—R 1 —[—S—(CH 2 ) 2 —O—[—R 2 —O—] m —(CH 2 ) 2 —S—R 1 —] n —O—} z —B   (21)

wherein,
each R 1 independently is selected from C 2-6 alkanediyl, —[(—CH 2 —) p —X—] q —(—CH 2 —) r —, and —[(—CH 2 —) p —X—] q —(—CH 2 —) r —, wherein at least one —CH 2 — group is substituted with a methyl group;
each R 2 independently is selected from C 2-6 alkanediyl, and —[(—CH 2 —) p —X—] q —(—CH 2 —) r —; For R 1 and R 2 each X is selected from —O—, and —S—;
Z represents the core of an z-valent polyfunctionalizing agent B(R 8 ) z where each R 8 is a group that is reactive with a terminal —SH and/or a terminal —CH═CH 2 group;
each m is independently selected from a rational number from 1 to 50;
each n is independently selected from an integer from 1 to 60;
each p is independently selected from an integer from 2 to 6;
each q is independently selected from an integer from 0 to 5;
each r is independently selected from an integer from 2 to 10; and
z is selected from an integer from 3 to 6; and
each R 13 is independently —(CH 2 ) 2 —O—R 5 where each R 5 is independently —(CH 2 )—OH where each t is independently selected from an integer from 1 to 6; and

(ii) an alicyclic aliphatic diisocyanate;

(b) a siloxane, wherein the siloxane comprises a condensed hydrolyzed dipodal silane, wherein the dipodal silane comprises bis(triethoxysilylpropyl)amine and bis(triethoxysilylpropyl)tetrasulfide; and
(c) a polyamine, wherein the polyamine comprises diethyltoluenediamine and dimethylthiotoluenediamine.

2. The composition of claim 1 , wherein,
each R 1 is —(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —;
each R 2 is —O—(CH 2 ) 2 —O—(CH 2 ) 2 —O—;
B represents the core of an z-valent polyfunctionalizing agent B(R 8 ) z , wherein B(R 8 ) z is triallyl isocyanurate, each R 8 is a —CH 2 —CH═CH 2 group, and z is 3; and
each R 13 is —(CH 2 ) 2 —O—(CH 2 ) 4 —OH.

3. The composition of claim 1 , wherein an equivalents ratio of the diisocyanate to the polythioether polyol is at least 2 to 1.

4. The composition of claim 1 , further comprising an isocyanate-terminated polyformal.

5. The composition of claim 1 , wherein the alicyclic aliphatic diisocyanate comprises 4,4′-methylene dicyclohexyl diisocyanate.

6. The composition of claim 1 , wherein the polythioether polyol of Formula (20) and Formula (21) comprises reaction products of reactants comprising:
(a) a thiol-terminated polythioether, wherein the thiol-terminated polythioether comprises a thiol-terminated polythioether of Formula (23a), a thiol-terminated polythioether prepolymer of Formula (23b), and a combination thereof:
HS—R 1 —[—S—(CH 2 ) p —O—(R 2 —O) m —(CH 2 ) 2 —S—R 1 —] n —SH  (23a)

{HS—R 1 —[—S—(CH 2 ) p O—(R 2 —O) m (CH 2 ) 2 —S—R 1 —] n —S—V′—} z B  (23b)

wherein,
each R 1 independently is selected from C 2-6 alkanediyl, 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—, and —S—;
each R2 is independently selected from C 2-6 alkanediyl, 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 1 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; and
each —V′— is derived from the reaction of —V with a thiol; and

(b) a C 1-4 hydroxyl functional vinyl ether.

7. The composition of claim 6 , wherein the thiol-terminated polythioether comprises the reaction products of diethylene glycol divinyl ether, dimercaptodioxaoctane, and triallylcyanurate.

8. The composition of claim 6 wherein:
each R 1 is —(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —;
each R 2 is —O—(CH 2 ) 2 —O—(CH 2 ) 2 —O—;
B represents the core of an z-valent polyfunctionalizing agent B(R 8 ) z , wherein B(R 8 ) z is triallylisocyanurate;
each R 8 is a —CH 2 —CH═CH 2 group, and z is 3; and
each R 13 is —(CH 2 ) 2 —O—(CH 2 ) 4 —OH.

9. The composition of claim 6 , wherein the hydroxyl-functional vinyl ether comprises 4-hydroxybutyl vinyl ether.

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

11. A method of sealing a surface, comprising:
applying the composition of claim 10 to a surface; and
curing the applied composition to seal the surface.

Assignees

• Prc Desoto Int Inc

Inventors

• Srivatsan Nagarajan
• Reyes Alfredo
• Manion Sean
• Cai Juexiao
• Ito Marfi
• Lin Renhe

Classifications

• C08G18/758

  containing two or more cycloaliphatic rings · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/52

  Polythioethers · CPC title

• C08G18/281

  Monocarboxylic acid compounds · CPC title

• C08G18/798

  containing urethdione groups · CPC title