Allophanate carbamate azido-alkyne click compositions

Patent metadata

Field	Value
Publication number	US-11174334-B2
Application number	US-201916694112-A
Country	US
Kind code	B2
Filing date	Nov 25, 2019
Priority date	Nov 25, 2019
Publication date	Nov 16, 2021
Grant date	Nov 16, 2021

Abstract

An alternative polyurethane composition is provided comprising a reaction product of an azidated polyol and a poly(alkynyl carbamate) allophanate prepolymer, wherein the poly(alkynyl carbamate) allophanate prepolymer comprises a reaction product of a first alkynol and a poly(alkynyl carbamate) prepolymer, in the presence of a metallo-organic compound of the formula: M(acac)n, wherein, M=a metal, acac=an acetylacetonate residue, and n=2 or 3, wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of a second alkynol, and wherein the polyisocyanate comprises isocyanate groups and uretdione groups. The inventive alternative polyurethane compositions may be used to provide solventborne or waterborne coatings, adhesives, sealants, films, elastomers, castings, foams, and composites.

First claim

What is claimed is:

1. A poly(alkynyl carbamate) allophanate prepolymer comprising a reaction product of a first alkynol and a poly(alkynyl carbamate) prepolymer, in the presence of a metallo-organic compound of the formula:
M(acac) n ,

wherein,
M=a metal,
acac=an acetylacetonate residue,
n=2 or 3,

wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of a second alkynol, and wherein the polyisocyanate comprises isocyanate groups and uretdione groups.

2. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein the first alkynol and the second alkynol each independently contain from 3 to 10 carbon atoms.

3. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein the first alkynol and the second alkynol are identical or different.

4. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein the first alkynol and the second alkynol are selected from the group consisting of propargyl alcohol, 2-hydroxyethylpropiolate, and isomers of any of these; or mixtures of any of these.

5. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein M is selected from the group consisting of aluminum, calcium, chromium, cobalt, copper, iron, magnesium, manganese, nickel, titanium, vanadium, zinc, and zirconium.

6. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein the metallo-organic compound comprises zinc acetylacetonate.

7. The poly(alkynyl carbamate) allophanate prepolymer 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.

8. The poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , wherein the uretdione groups are selected from the group consisting of aliphatic 1,6-hexamethylene diisocyanate (HDI) uretdiones, aromatic toluene diisocyanate (TDI) uretdiones, and aliphatic isophorone diisocyanate (IPDI) uretdiones.

9. An alternative polyurethane composition comprising a reaction product of an azidated polyol and the poly(alkynyl carbamate) allophanate prepolymer according to claim 1 , optionally in the presence of a catalyst.

10. The alternative polyurethane composition according to claim 9 , wherein the azidated polyol is a reaction product of a polyol and an azide.

11. The alternative polyurethane composition according to claim 10 , 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.

12. The alternative polyurethane composition according claim 10 , wherein the catalyst comprises a Cu II catalyst and a reducing agent.

13. The alternative polyurethane composition according to claim 10 , 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, and copper(II) acetate monohydrate.

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

15. 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 to claim 9 .

16. 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 15 .

17. A process of producing an alternative polyurethane composition, the process comprising reacting:
an azidated polyol; and
a poly(alkynyl carbamate) allophanate prepolymer,
optionally, in the presence of a catalyst,
wherein the poly(alkynyl carbamate) allophanate prepolymer comprises a reaction product of poly(alkynyl carbamate) prepolymer and a first alkynol in the presence of a metallo-organic compound of the formula:
M(acac) n ,

wherein,
M=a metal,
acac=an acetylacetonate residue, and
n=2 or 3,

wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of a second alkynol, and wherein the polyisocyanate comprises isocyanate groups and uretdione groups.

18. The process according to claim 17 , wherein the first alkynol and the second alkynol each independently contain from 3 to 10 carbon atoms.

19. The process according to claim 17 , wherein the first alkynol and the second alkynol are identical or different.

20. The process according to claim 17 , wherein the first alkynol and the second alkynol are selected from the group consisting propargyl alcohol, 2-hydroxyethylpropiolate, and isomers of any of these; or mixtures of any of these.

21. The process according to claim 17 , wherein M is selected from the group consisting of aluminum, calcium, chromium, cobalt, copper, iron, magnesium, manganese, nickel, titanium, vanadium, zinc, and zirconium.

22. The process according to claim 17 , wherein the metallo-organic compound comprises zinc acetylacetonate.

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 17 .

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

• Ekin Alan
• Storey Robson F
• Wu Jie

Classifications

• C08G18/8191

  with acetylenic compounds having active hydrogen · CPC title

• C08G18/6216

  Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof · CPC title

• C09D175/04

  Polyurethanes · CPC title

• C08G2190/00

  Compositions for sealing or packing joints · CPC title

• C08G18/222

  metal compounds not provided for in groups C08G18/225 - C08G18/26 · CPC title