Polyurethane polymers cured via azido-alkyne cycloaddition at ambient or mild curing conditions

Patent metadata

Field	Value
Publication number	US-11312817-B2
Application number	US-201916693837-A
Country	US
Kind code	B2
Filing date	Nov 25, 2019
Priority date	Nov 25, 2019
Publication date	Apr 26, 2022
Grant date	Apr 26, 2022

Abstract

An alternative polyurethane composition is provided which comprises a reaction product of an azidated polyol and a poly(alkynyl carbamate) prepolymer reacted at a temperature of from 20° C. to 120° C., wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of an alkynol of the formula (I),

HC≡C—R 1 R 2 —OH  (I),

and wherein R 1 is an electron-withdrawing group selected from the group consisting of carbonyl, ester, amide, and urethane and R 2 is a linear or branched alkyl chain having from 1 to 15 carbon atoms. The inventive alternative polyurethane composition position may be used to provide adhesives, sealants, films, elastomers, castings, foams, and composites.

First claim

What is claimed is:

1. An alternative polyurethane composition comprising: a reaction product of an azidated polyol and a poly(alkynyl carbamate) prepolymer reacted at a temperature of from 20° C. to 120° C.,
wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of an alkynol of the formula (I),
HC≡C—R 1 R 2 —OH  (I),

and
wherein R 1 is an electron-withdrawing group selected from the group consisting of carbonyl, ester, amide, and urethane and R 2 is a linear or branched alkyl chain having from 1 to 15 carbon atoms.

2. The alternative polyurethane composition according to claim 1 , wherein the alkynol is 2-hydroxyethyl propiolate.

3. The alternative polyurethane composition according to claim 1 , wherein the 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 (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, α,α,α′,α′-tetramethyl-1,3-xylene diisocyanate, α,α,α′,α′-tetramethy-1,4-xylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentane diisocyanate (PDI)—bio-based), and, isomers of any of these; or mixtures of any of these.

4. The alternative polyurethane composition according to claim 1 , wherein the polyisocyanate contains one or more selected from the group consisting of isocyanurate, biuret, allophanate, uretdione, and iminooxadiazine dione groups.

5. The alternative polyurethane composition according to claim 1 , wherein the azidated polyol is a reaction product of a polyol and an azide.

6. The alternative polyurethane composition according to claim 5 , wherein the polyol is selected from the group consisting of polyalkylene ether polyols, polyester polyols, hydroxyl containing polycaprolactones, hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols, polyurethane polyols and combinations thereof.

7. The alternative polyurethane composition according to claim 1 , wherein the azidated polyol and the poly(alkynyl carbamate) prepolymer are reacted in the presence of a Cu I -containing catalyst.

8. The alternative polyurethane composition according to claim 7 , wherein the Cu I containing catalyst comprises a Cu II catalyst and a reducing agent.

9. The alternative polyurethane composition according to claim 8 , wherein the Cu II catalyst is selected from the group consisting of copper(II) chloride, CuCl 2 [PMDETA], copper(II) bromide, copper(II) iodide, copper(II) sulfate, copper(II) 2-ethylhexanoate, and copper(II) acetate monohydrate.

10. The alternative polyurethane composition according to claim 8 , wherein the reducing agent is selected from the group consisting of triphenyl phosphine, sodium ascorbate, tin(II) 2-ethylhexanoate, and hydroquinone.

11. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the alternative polyurethane composition according claim 1 .

12. A substrate having applied thereto the one of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite according to claim 11 .

13. A process of producing an alternative polyurethane composition, the process comprising:
reacting a polyisocyanate with a stoichiometric equivalent of an alkynol of the formula (I),
HC≡C—R 1 R 2 —OH  (I)

to produce a poly(alkynyl carbamate) prepolymer, and
reacting the poly(alkynyl carbamate) prepolymer with an azidated polyol at a temperature of from 20° C. to 120° C. to produce the alternative polyurethane composition,
wherein R 1 is an electron-withdrawing group selected from the group consisting of carbonyl, ester, amide, and urethane and R 2 is a linear or branched alkyl chain having from 1 to 15 carbon atoms.

14. The process according to claim 13 , wherein the alkynol is 2-hydroxyethyl propiolate.

15. The process according to claim 13 , wherein the 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 (isophorone diisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)-cyclohexane, 1,4-bis(isocyanatomethyl)-cyclohexane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane, α,α,α′,α′-tetramethyl-1,3-xylene diisocyanate, α,α,α′,α′-tetramethy-1,4-xylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, 2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentane diisocyanate (PDI)—bio-based), and, isomers of any of these; or mixtures of any of these.

16. The process according to claim 13 , wherein the polyisocyanate contains one or more selected from the group consisting of isocyanurate, biuret, allophanate, uretdione, and iminooxadiazine dione groups.

17. The process according to claim 13 , wherein the azidated polyol is a reaction product of a polyol and an azide.

18. The process according to claim 17 , wherein the polyol is selected from the group consisting of polyalkylene ether polyols, polyester polyols, hydroxyl containing polycaprolactones, hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols, polyurethane polyols and combinations thereof.

19. The process according to claim 13 , wherein the step of reacting the azidated polyol and the poly(alkynyl carbamate) prepolymer occurs in the presence of a Cu I -containing catalyst.

20. The process according to claim 19 , wherein the Cu I -containing catalyst comprises a Cu II catalyst and a reducing agent.

21. The process according to claim 20 , wherein the Cu′ catalyst is selected from the group consisting of copper(II) chloride, CuCl 2 [PMDETA], copper(II) bromide, copper(II) iodide, copper(II) sulfate, copper(II) 2-ethylhexanoate, and copper(II) acetate monohydrate.

22. The process according to claim 20 , wherein the reducing agent is selected from the group consisting of triphenyl phosphine, sodium ascorbate, tin(II) 2-ethylhexanoate, and hydroquinone.

23. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the alternative polyurethane composition made according to the process of claim 13 .

24. A substrate having applied thereto the one of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite according to claim 23 .

Assignees

• Covestro Llc
• The Univ Of Southern Mississippi

Inventors

• Storey Robson F
• Ekin Alan
• Cooke Iii R Hunter
• Wu Jie

Classifications

• C08G18/7837

  containing allophanate groups · CPC title

• C09D175/14 Primary

  Polyurethanes having carbon-to-carbon unsaturated bonds · CPC title

• C08G18/3836

  containing azo groups · CPC title

• C09J175/14

  Polyurethanes having carbon-to-carbon unsaturated bonds · CPC title

• C08G18/7831

  containing biuret groups · CPC title