Curable polyisocyanate composition comprising an epoxy

Patent metadata

Field	Value
Publication number	US-9926447-B2
Application number	US-201214355856-A
Country	US
Kind code	B2
Filing date	Nov 7, 2012
Priority date	Nov 22, 2011
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

Curable composition obtained by combining and mixing an epoxy resin composition, comprising an epoxy resin and a carboxamide, and a polyisocyanate composition, comprising a polyisocyanate, a lithium halide and a urea compound, wherein the number of moles of lithium halide per isocyanate equivalent ranges of from 0.0001-0.04 and the number of urea+biuret equivalents per isocyanate equivalent of from 0.0001-0.4.

First claim

The invention claimed is:

1. A curable composition, comprising a mixture of:
(a) a polyisocyanate composition, comprising:
(i) a first polyisocyanate,
(ii) a lithium halide,
(iii) a urea compound, wherein the urea compound is the reaction product of a second polyisocyanate and an amine, and wherein the urea compound has an average molecular weight of 500-15000 Daltons, and, optionally,
containing biuret groups,
wherein the number of moles of lithium halide per isocyanate equivalent ranges from 0.0001-0.04 and the number of urea+biuret equivalents per isocyanate equivalent ranges from 0.0001-0.4, and wherein the first polyisocyanate and the second polyisocyanate may be the same or different; and

(b) an epoxy resin composition comprising (i) an epoxy resin, and (ii) a compound comprising a carboxamide group having the structure —CO—NH 2 ,
wherein the number of epoxy equivalents per isocyanate equivalent in the curable composition ranges from 0.003-1,
wherein the number of carboxamide equivalents per epoxy equivalents is in a range from 0.0005 to 1; and
wherein the number of carboxamide equivalents per lithium halide equivalents is in a range of from 0.054-0.7.

2. The composition according to claim 1 , wherein the compound which comprises a carboxamide group has the structure NH 2 —CO—R wherein R is 1) hydrogen (—H), 2) —NR 1 R 2 , 3) hydrocarbyl having 1-20 carbon atoms and optionally comprising hydroxyl, ether, halogen and/or amine groups, or 4) —R 3 —CO—NH 2 , wherein R 1 and R 2 independently from each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups which hydrocarbyl groups have 1-10 carbon atoms and optionally comprise hydroxy, ether, halogen and/or amine groups and wherein R 3 is a bivalent hydrocarbon radical having up to 8 carbon atoms and mixtures of such compounds.

3. The composition according to claim 1 , wherein the compound which comprises a carboxamide group has the structure NH 2 —CO—R wherein R is 1) —NR 1 R 2 , 2) alkyl having 1-10 carbon atoms and optionally comprising 1-3 hydroxy and/or ether groups, 3) phenyl or 4) tolyl, wherein R 1 and R 2 , independently from each other, are selected from hydrogen, hydroxyl, phenyl, tolyl and alkyl having 1-6 carbon atoms and optionally comprising an hydroxyl and/or an ether group and mixtures of such compounds.

4. The composition according to claim 1 , wherein the epoxy resin composition further comprises at least one of a monool and a polyol, and wherein the number of hydroxy equivalents per epoxy equivalent is at most 0.019.

5. The composition according to claim 1 , wherein the urea compound does not comprise isocyanate-reactive groups other than urea groups, the number of urea+biuret equivalents per isocyanate equivalent is 0.001-0.2 and wherein the urea compound has been prepared by reacting a polyisocyanate selected from the group consisting of methylene diphenyl diisocyanate, a polyisocyanate comprising a methylene diphenyl diisocyanate, and a mixture of such with a polyoxyalkylene monoamine comprising oxypropylene groups in an amount of at least 50% by weight calculated on the total weight of the monoamine molecule, the urea compound having an average molecular weight of 200-3000 Daltons, and wherein the amine is a primary amine and wherein the number of urea+biuret equivalents per mole of lithium halide is 0.5-60.

6. The composition according to claim 1 , wherein the polyisocyanate is selected from the group consisting of methylene diphenyl diisocyanate, a polyisocyanate composition comprising methylene diphenyl diisocyanate, and a mixture thereof.

7. The composition according to claim 1 , wherein the amount of lithium halide is in a range from 0.00015-0.025 moles per isocyanate equivalent.

8. The composition according to claim 1 , wherein the lithium halide is lithium chloride.

9. The composition according to claim 1 , wherein the epoxy resin is liquid at 20° C.

10. A process for making a curable composition, comprising mixing:
a) a polyisocyanate composition, comprising:
(i) a first polyisocyanate,
(ii) a lithium halide,
(iii) a urea compound, wherein the urea compound is the reaction product of a second polyisocyanate and an amine, and wherein the urea compound has an average molecular weight of 500-15000 Daltons, and, optionally,
containing biuret groups,

wherein the number of moles of lithium halide per isocyanate equivalent ranges from 0.0001-0.04 and the number of urea+biuret equivalents per isocyanate equivalent ranges from 0.0001-0.4, and
b) an epoxy resin composition comprising (i) an epoxy resin, and (ii) a compound comprising a carboxamide group having the structure —CO—NH 2 ,
wherein the amount of epoxy resin composition is used in an amount such that the number of epoxy equivalents per isocyanate equivalent ranges from 0.003-1 wherein the number of carboxamide equivalents per epoxy equivalents is in a range from 0.0005 to 1; and
wherein the number of carboxamide equivalents per lithium halide equivalents is in a range of from 0.054-0.7.

11. The process according to claim 10 , further comprising reacting the curable composition at a temperature greater than 50° C. to produce a composition at least partially comprising a polyisocyanurate.

12. The curable composition according to claim 4 , wherein the number of hydroxy equivalents per epoxy equivalent is at most 0.014.

13. The curable composition according to claim 4 , wherein the number of hydroxy equivalents per epoxy equivalent is at most 0.010.

14. The curable composition according to claim 1 , wherein the epoxy resin composition further comprises a solvent which has no isocyanate-reactive groups.

15. The curable composition according to claim 1 , wherein the compound which comprises a carboxamide group has the structure NH 2 —CO—R, wherein R is —NR 1 R 2 , wherein R 1 and R 2 , independently from each other, are selected from hydrogen, hydroxy, halogen and hydrocarbyl groups having 1-10 carbon atoms and, optionally, comprise at least one of hydroxy, ether, halogen, and amine groups.

16. The curable composition according to claim 1 , wherein the compound which comprises a carboxamide group is selected from the group consisting of hydroxyurea, nicotinamide, hydroxypropyl carbamate, lactamide, and combinations thereof.

17. The process according to claim 11 , wherein the curable composition is reacted at a temperature greater than 80° C. to produce a composition at least partially comprising a polyisocyanurate.

18. The composition according to claim 1 , wherein the number of carboxamide equivalents per epoxy equivalents is in a range of from 0.0005 to 0.03.

19. The process according to claim 10 , wherein the number of carboxamide equivalents per epoxy equivalents is in a range of from 0.0005 to 0.03.

Assignees

• Huntsman Int Llc

Inventors

• Esbelin Christian
• Verbeke Hans Godelieve Guido
• Verbeke Hugo

Classifications

• C08G59/066 Primary

  with chain extension or advancing agents · CPC title

• C08L63/00

  Compositions of epoxy resins; Compositions of derivatives of epoxy resins · CPC title

• C08L75/04 Primary

  Polyurethanes · CPC title

• C08G59/44

  Amides · CPC title

• C08G59/4021

  Ureas; Thioureas; Guanidines; Dicyandiamides · CPC title