Flexible polyamines, flexible amine-terminated adducts, compositions thereof and methods of use

Patent metadata

Field	Value
Publication number	US-9422467-B2
Application number	US-201414307548-A
Country	US
Kind code	B2
Filing date	Jun 18, 2014
Priority date	Mar 18, 2011
Publication date	Aug 23, 2016
Grant date	Aug 23, 2016

Abstract

Disclosed are flexible polyamines, flexible amine-terminated polyformal adducts, flexible-amine-terminated polythioether adducts, compositions comprising flexible polyamines and isocyanate-terminated prepolymers, and compositions comprising flexible amine-terminated adducts and isocyanate-terminated prepolymers. Uses of the compositions as sealants, and particularly as aerospace sealants, are also disclosed.

First claim

What is claimed is:

1. An amine-terminated polythioether adduct selected from an adduct of Formula (13), an adduct of Formula (14), and a combination thereof:
F—CH 2 —CH(OH)—R 16 —S—R 15 —S—R 16 —CH(OH)—CH 2 —F  (13)

{F—CH 2 —CH(OH)—R 16 —S—R 15 —S—R 16 —CH(OH)—CH 2 —V′—} z B  (14)

wherein:
each R 15 is independently selected from C 2-10 alkanediyl, C 2-10 oxyalkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[—(CHR 17 ) s —X—] q —(CHR 17 ) r —; wherein
each R 17 is independently selected from hydrogen and methyl;
each X is independently selected from O, S, —NH—, and —NR— wherein R is selected from hydrogen and methyl;
s is an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;

each R 16 is independently selected from C 3-20 alkanediyl and C 3-20 oxyalkanediyl;
B represents the core of a z-valent polyfunctionalizing agent B(V) z , wherein:
z is an integer from 3 to 6; and
each V comprises a group that is reactive with an epoxy group;

each V′ comprises a moiety resulting from the reaction of V with an epoxy group; and
each F is independently an amine-terminated group of Formula (1′):
A-Y—(CR 2 2 ) p —[—O—(CR 1 2 ) n —] m —O—(CR 2 2 ) p —Y-A′-  (1′)

wherein:
m is an integer from 1 to 4;
each n is independently an integer from 1 to 4;
each p is independently an integer from 1 to 4;
A is amino-substituted phenyl;
-A′- is

each Y is independently selected from O and S;
each R 1 is independently selected from hydrogen and C 1-3 alkyl; and
each R 2 is independently selected from hydrogen and C 1-3 alkyl.

2. The amine-terminated polythioether adduct of claim 1 , wherein each —R 16 —S—R 15 —S—R 16 — has the structure of Formula (18):
—R 21 —X—R 19 —[—S—(CH 2 ) w —O—(R 20 —O) x —(CH 2 ) 2 —S—R 19 —] y —X—R 21 —  (18)

wherein:
each R 19 is independently selected from C 2-10 alkanediyl, C 2-10 oxyalkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[—(CHR 17 ) s —X—] q —(CHR 17 ) r —; wherein
each R 17 is independently selected from hydrogen and methyl;
each X is independently selected from O, S, —NH—, and —NR— wherein R is selected from hydrogen and methyl;
s is an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10;

each w is independently an integer from 2 to 6;
x is an integer from 0 to 50;
y is an integer from 1 to 60;
each R 20 is independently selected from C 3-20 alkanediyl and C 3-20 oxyalkanediyl; and
each R 21 is independently selected from C 3-20 alkanediyl and C 3-20 oxyalkanediyl.

3. The amine-terminated polythioether adduct of claim 1 , wherein each —R 16 —S—R 15 —S—R 16 — has the structure of Formula (19):
—CH 2 —O—(CH 2 ) 3 —[—S—(CH 2 ) 2 —O—(CH 2 ) 2 —O—(CH 2 ) 2 —S—(CH 2 CH 2 O) 3 —(CH 2 ) 2 —] 2 —S—(CH 2 CH 2 O) 2 —(CH 2 ) 2 —S—(CH 2 ) 3 —O—CH 2 —   (19).

4. A composition comprising the amine-terminated polythioether adduct of claim 1 .

5. The composition of claim 4 , comprising an isocyanate-terminated polythioether prepolymer.

6. The composition of claim 5 , wherein the isocyanate-terminated polythioether prepolymer comprises the reaction products of reactants comprising:
(a) an isocyanate-terminated polythioether comprising the reaction product of reactants comprising:
a dithiol of Formula (17):
HS—R 15 —SH  (17)

wherein:
R 15 is selected from C 2-6 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[—(CHR 17 ) s —X—] q —(CHR 17 ) r —; wherein:
each R 17 is independently selected from hydrogen and methyl;
each X is independently selected from O, S, —NH—, and —NR— wherein R is selected from hydrogen and methyl;
s is an integer from 2 to 6;
q is an integer from 1 to 5; and
r is an integer from 2 to 10; and

(ii) a divinyl ether of Formula (26):
CH 2 ═CH—O—[—R 25 —O—] b —CH═CH 2   (26)

wherein:
each R 25 is independently selected from C 2-6 alkanediyl, C 6-8 cycloalkanediyl, C 6-10 alkanecycloalkanediyl, C 5-8 heterocycloalkanediyl, and —[(CH 2 ) s —X—] q —(CH 2 ) r —; wherein:
 each X is independently selected from —O—, —S— and —NR—, wherein R is selected from hydrogen and methyl;
 each s is independently an integer from 2 to 6;
 each q is independently an integer from 0 to 5; and
 each r is independently an integer from 2 to 10; and
each b is independently an integer from 0 to 10;

(iii) an alkyl ω-alkenyl ether of Formula (27):
CH 2 ═CH—(CH 2 ) d —O—R 26   (27)

wherein:
d is an integer from 0 to 10; and
 R 26 is selected from C 1-6 alkyl and substituted C 1-6 alkyl wherein the one or more substituents is selected from —OH and —NHR wherein R is selected from hydrogen and C 1-6 alkyl; and

(iv) a polyfunctionalizing agent B(R 8 ) z , wherein:
B is a core of a z-valent polyfunctionalizing agent B(R 8 ) z ;
each R 8 independently comprises a group selected from a group comprising a terminal group that is reactive with a —SH group and a group comprising a terminal group that is reactive with a —CH═CH 2 group; and
z is independently selected from an integer from 3 to 6; and

(b) a diisocyanate.

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

8. A method of sealing a surface comprising:
applying the composition of claim 7 to a surface; and
curing the composition to seal the surface.

Assignees

• Prc Desoto Int Inc

Inventors

• Hobbs Stephen J
• Ito Marfi
• Cai Juexiao
• Rao Chandra
• Lin Renhe

Classifications

• C08G18/3868

  the sulfur atom belonging to a sulfide group · CPC title

• C08G18/8108

  having only one isocyanate or isothiocyanate group · 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

• C09K2003/1034

  Materials or components characterised by specific properties · CPC title

• C08G2190/00

  Compositions for sealing or packing joints · CPC title