Use of thermally decomposable acid as inhibitor for preparing polyisocyanurate composites

Patent metadata

Field	Value
Publication number	US-11453739-B2
Application number	US-202016902668-A
Country	US
Kind code	B2
Filing date	Jun 16, 2020
Priority date	Jun 16, 2020
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

Provided is a process for producing a polyisocyanurate comprising: trimerizing an aliphatic polyisocyanate with a trimerization catalyst in the presence of a thermally decomposable acid at a molar ratio of acid to catalyst of from 0.1 to 10, wherein the polyisocyanurate has a greater pot life than the pot life of the polyisocyanurate not containing the thermally decomposable acid. Polyisocyanurates made according to the inventive process lengthen the pot life of pultrusion composite formulations made therefrom without affecting the reactivity of the formulations. The pultrusion composite formulations of the invention may be cured and pultruded to yield a variety of products such as wind turbine blades, yacht shells, window frames, door frames, ladder frames, telegraph pole cross arms, tent poles, solar cell frames, solar cell backsheets, radomes, highway guard rails, floor boards, pipes, telegraph poles, auto trunks, luggage holders, engine covers, golf clubs, tennis poles, badminton poles, bicycle frames, surfboards, and snowboards.

First claim

What is claimed is:

1. A process for producing a polyisocyanurate comprising:
trimerizing an aliphatic polyisocyanate with a trimerization catalyst in the presence of a thermally decomposable acid at a molar ratio of acid to catalyst of from 0.1 to 10, wherein the polyisocyanurate has a greater pot life than the pot life of the polyisocyanurate not containing the thermally decomposable acid, and wherein the thermally decomposable acid has a formula selected from the group consisting of RHNCOOH, RR′NCOOH, and R(HNCOOH) n , wherein R and R′ are organic groups and n is a number from 2-5.

2. The process according to claim 1 , wherein the thermally decomposable acid is present at a molar ratio of acid to catalyst of from 0.2 to 5.

3. The process according to claim 1 , wherein the thermally decomposable acid is an N-substituted (thio)carbamic acid.

4. The process according to claim 1 , wherein the thermally decomposable acid is the reaction product of added water and the polyisocyanate.

5. The process according to claim 1 , wherein the trimerization catalyst is an alkali metal salt or an alkaline earth metal salt.

6. The process according to claim 5 , wherein the metal is selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium, tin, titanium, hafnium, lead, lithium, sodium, potassium, magnesium, calcium, strontium, and barium, and wherein the salt is selected from the group consisting of alkoxides, amides, phenoxides, carbonates, hydrogencarbonates, hydroxides, cyanides, isocyanides, thiocyanides, sulphides, sulphites, sulphinates, phosphites, phosphinates, phosphonates, phosphates, and fluorides.

7. The process according to claim 1 , wherein the aliphatic polyisocyanate is selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, bis-(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, diphenylmethane diisocyanate, dicyclohexylmethane-4,4-diisocyanate, pentane diisocyanate, isomers of any of these, and combinations of any of these.

8. The process according to claim 1 , wherein the aliphatic polyisocyanate is a trimer or prepolymer based on one selected from the group consisting of 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, and dicyclohexylmethane-4,4-diisocyanate.

9. A pultrusion composite formulation comprising:
a fiber; and
a polyisocyanurate formulation,
wherein the polyisocyanate formulation comprises an aliphatic polyisocyanate which is trimerized with a trimerization catalyst in the presence of a thermally decomposable acid at a molar ratio of acid to catalyst of from 0.1 to 10, and wherein the polyisocyanurate has a greater pot life than the pot life of the polyisocyanurate not containing the thermally decomposable acid, and wherein the thermally decomposable acid has a formula selected from the group consisting of RHNCOOH, RR′NCOOH, and R(HNCOOH) n , wherein R and R′ are organic groups and n is a number from 2 to 5.

10. The pultrusion composite formulation according to claim 9 , wherein the thermally decomposable acid is present at a molar ratio of acid to catalyst is from 0.2 to 5.

11. The pultrusion composite formulation according to claim 9 , wherein the thermally decomposable acid is the reaction product of added water and the polyisocyanate.

12. The pultrusion composite formulation according to claim 9 , wherein the trimerization catalyst is an alkali metal salt or an alkaline earth metal salt.

13. The pultrusion composite formulation according to claim 12 , wherein the metal is selected from the group consisting of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium, tin, titanium, hafnium, lead, lithium, sodium, potassium, magnesium, calcium, strontium, and barium, and wherein the salt is selected from the group consisting of alkoxides, amides, phenoxides, carbonates, hydrogencarbonates, hydroxides, cyanides, isocyanides, thiocyanides, sulphides, sulphites, sulphinates, phosphites, phosphinates, phosphonates, phosphates, and fluorides.

14. The pultrusion composite formulation according to claim 9 , wherein the aliphatic polyisocyanate is selected from the group consisting of 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, bis-(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, diphenylmethane diisocyanate, dicyclohexylmethane-4,4-diisocyanate, pentane diisocyanate, isomers of any of these, and combinations of any of these.

15. The pultrusion composite formulation according to claim 9 , wherein the aliphatic polyisocyanate is a trimer or prepolymer based on one selected from the group consisting of 1,6-hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane, and dicyclohexylmethane-4,4-diisocyanate.

16. The pultrusion composite formulation according to claim 9 , wherein the fiber is selected from the group consisting of glass fibers, glass mats, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, basalt fibers, and combinations thereof.

17. A pultrusion composite comprising a reaction product of the pultrusion composite formulation according to claim 9 which is pultruded and cured to form the composite.

18. The pultrusion composite according to claim 17 , wherein the composite is one selected from the group consisting of a wind turbine blade, a yacht shell, a window frame, a door frame, a ladder frame, a telegraph pole cross arm, a tent pole, a solar cell frame, a solar cell backsheet, a radome, a highway guard rail, a floor board, a pipe, a telegraph pole, an auto trunk, a luggage holder, an engine cover, a golf club, a tennis pole, a badminton pole, a bicycle frame, a surfboard, and a snowboard.

Assignees

• Covestro Llc

Inventors

• Chen Liang
• Thompson-Colón James A
• Bushmire Alan D

Classifications

• C08G18/225 Primary

  of alkali or alkaline earth metals · CPC title

• C08K7/14

  Glass · CPC title

• C08G18/73

  acyclic · CPC title

• B29C70/52

  Pultrusion, i.e. forming and compressing by continuously pulling through a die · CPC title

• C08K7/06

  Elements · CPC title