Sulfur-containing polyureas and methods of use

Patent metadata

Field	Value
Publication number	US-9725556-B2
Application number	US-201414532034-A
Country	US
Kind code	B2
Filing date	Nov 4, 2014
Priority date	Sep 22, 2011
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

Sulfur-containing polyurea compositions comprising a polyisocyanate and a polyamine are disclosed. The polyisocyanate comprises the reaction product of reactants comprising a diisocyanate having isocyanate groups with different reactivities toward thiol groups, and a thiol-terminated sulfur-containing polymer such as a thiol-terminated polythioether polymer and/or a thiol-terminated polyformal polymer. The polyamine can be an aromatic polyamine and/or an aromatic amine-terminated polythioether adduct. The sulfur-containing polyurea compositions are useful as aerospace sealants.

First claim

What is claimed is:

1. A composition comprising:
(a) an isocyanate-terminated sulfur-containing polyformal prepolymer comprising the reaction product of reactants comprising:
(i) a diisocyanate having a first isocyanate group and a second isocyanate group, wherein the reactivity of the first isocyanate group with a thiol group is greater than the reactivity of the second isocyanate group with the thiol group; and
(ii) a thiol-terminated sulfur-containing polyformal, wherein the thiol-terminated sulfur-containing polyformal comprises a thiol-terminated sulfur-containing polyformal of Formula (9), a thiol-terminated sulfur-containing polyformal Formula (9′), or a combination thereof:

wherein:
t is an integer selected from 2 to 40;
each u is independently selected from 1 or 2;
each R 4 is independently selected from C 2-6 alkanediyl;
each R 5 is independently selected from hydrogen, C 1-6 alkyl, C 7-12 phenylalkyl, substituted C 7-12 phenylalkyl, C 6-12 cycloalkylalkyl, substituted C 6-12 cycloalkylalkyl, C 3-12 cycloalkyl, substituted C 3-12 cycloalkyl, C 6-12 aryl, or substituted C 6-12 aryl; and
each R 6 is a group comprising a terminal thiol group; and
B represents a core of a z-valent polyol B(OH) z wherein z is an integer from 3 to 6;

wherein the molar ratio of isocyanate groups to thiol groups is from 2.1:1 to 2.5:1; and
(b) a polyamine.

2. The composition of claim 1 , wherein the molar ratio is 2.2:1.

3. The composition of claim 1 , wherein the isocyanate-terminated sulfur-containing polyformal prepolymer is selected from a difunctional isocyanate-terminated sulfur-containing polyformal prepolymer of Formula (3), a multifunctional isocyanate-terminated sulfur-containing polyformal prepolymer of Formula (3′), or a combination thereof:

wherein:
t is an integer selected from 2 to 40;
each u is independently selected from 1 or 2;
each R 4 is independently selected from C 2-6 alkanediyl;
each R 5 is independently selected from hydrogen, C 1-6 alkyl, C 7-12 phenylalkyl, substituted C 7-12 phenylalkyl, C 6-12 cycloalkylalkyl, substituted C 6-12 cycloalkylalkyl, C 3-12 cycloalkyl, substituted C 3-12 cycloalkyl, C 6-12 aryl, or substituted C 6-12 aryl;

each —R 6′ — is selected from a moiety of Formula (a′), Formula (b′), Formula (c′), Formula (d′), Formula (e′), Formula (f′), Formula (g′), or Formula (h′):

wherein:
each R 8 is selected from a moiety derived from a diisocyanate and a moiety derived from an ethylenically unsaturated monoisocyanate;
each R 9 is selected from C 2-14 alkanediyl or C 2-14 heteroalkanediyl; and
each R 10 is selected from C 2-6 alkanediyl, C 2-6 heteroalkanediyl, C 6-12 arenediyl, substituted C 6-12 arenediyl, C 6-12 heteroarenediyl, substituted C 6-12 heteroarenediyl, C 3-12 cycloalkanediyl, substituted C 3-12 cycloalkanediyl, C 3-12 heterocycloalkanediyl, substituted C 3-12 heterocycloalkanediyl, C 7-18 alkanearenediyl, substituted C 7-18 heteroalkanearenediyl, C 4-18 alkanecycloalkanediyl, or substituted C 4-18 alkanecycloalkanediyl;
B represents a core of a z-valent polyol B(OH) z wherein z is an integer from 3 to 6; and
each Y—NH—C(O)— is a moiety derived from the diisocyanate.

4. The composition of claim 3 , wherein:
u is 1;
each R 5 is hydrogen; and
each R 4 is 1,2-ethanediyl.

5. The composition of claim 1 , wherein the diisocyanate is selected from 2,4-toluene diisocyanate, isophorone diisocyanate, or a combination of any of the foregoing.

6. The composition of claim 1 , wherein the composition comprises a metal acetylacetonate catalyst.

7. The composition of claim 1 , wherein the composition comprises a base catalyst.

8. The composition of claim 7 , wherein the base catalyst is selected from triethylamine, trioctylphosphine, or a combination thereof.

9. The composition of claim 1 , wherein the thiol-terminated sulfur-containing polyformal comprises the reaction products of reactants comprising:
the reaction products of reactants comprising a sulfur-containing polyol and a first compound, wherein:
the sulfur-containing polyol is selected from a polyol of Formula (10), a polyol of Formula (10′), or a combination thereof:

wherein:
t is an integer selected from 2 to 40;
each u is independently selected from 1 and 2;
each R 4 is independently selected from C 2-6 alkanediyl;
each R 5 is independently selected from hydrogen, C 1-6 alkyl, C 7-12 phenylalkyl, substituted C 7-12 phenylalkyl, C 6-12 cycloalkylalkyl, substituted C 6-12 cycloalkylalkyl, C 3-12 cycloalkyl, substituted C 3-12 cycloalkyl, C 6-12 aryl, or substituted C 6-12 aryl; and
B represents a core of a z-valent polyol B(OH) z wherein z in an integer from 3 to 6; and

the first compound is selected from a diisocyanate, thiourea, an ethylenically unsaturated monoisocyanate, or a tosylate; and

a mercaptoalkanol when the first compound comprises a diisocyanate;
a metal hydrosulfide when the first compound comprises thiourea;
a dithiol when the first compound comprises an ethylenically unsaturated monoisocyanate; or
a metal hydrosulfide when the first compound comprises a tosylate.

10. The composition of claim 9 , wherein the sulfur-containing polyformal polyol of Formula (10) comprises the reaction product of reactants comprising thiodiglycol and paraformaldehyde.

11. The composition of claim 9 , wherein the sulfur-containing polyformal polyol of Formula (10′) comprises the reaction product of reactants comprising thiodiglycol, paraformaldehyde and 1,3,5-tris(2-hydroxyethyl)isocyanurate.

12. The composition of claim 1 , wherein each R 6 is independently a thiol-terminated group selected from a group of Formula (a), Formula (b), Formula (c), Formula (d), Formula (e), Formula (f), Formula (g), or Formula (h):

wherein:
each R 8 is selected from a moiety derived from a diisocyanate or a moiety derived from an ethylenically unsaturated monoisocyanate;
each R 9 is selected from C 2-14 alkanediyl or and C 2-14 heteroalkanediyl; and
each R 10 is selected from C 2-6 alkanediyl, C 2-6 heteroalkanediyl, C 6-12 arenediyl, substituted C 6-12 arenediyl, C 6-12 heteroarenediyl, substituted C 6-12 heteroarenediyl, C 3-12 cycloalkanediyl, substituted C 3-12 cycloalkanediyl, C 3-12 heterocycloalkanediyl, substituted C 3-12 heterocycloalkanediyl, C 7-18 alkanearenediyl, substituted C 7-18 heteroalkanearenediyl, C 4-18 alkanecycloalkanediyl, or substituted C 4-18 alkanecycloalkanediyl.

13. The composition of claim 1 , wherein the polyamine comprises an aromatic polyamine.

14. The composition of claim 1 , wherein the polyamine is selected from an aromatic polyamine, an aromatic amine-terminated polythioether adduct, or a combination thereof.

15. The composition of claim 14 , wherein the aromatic amine-terminated polythioether adduct is selected from an adduct of Formula (13), an adduct of Formula (13′), or a combination thereof:
Y—NH—CH 2 —CH(OH)-A-CH

Assignees

• Prc Desoto Int Inc

Inventors

• Cai Juexiao
• Hobbs Stephen J
• Ito Marfi
• Moravek Scott
• Lin Renhe

Classifications

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G2190/00

  Compositions for sealing or packing joints · CPC title

• C09J175/02

  Polyureas · 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

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title