Waterborne azido-alkyne click compositions

Patent metadata

Field	Value
Publication number	US-11261344-B2
Application number	US-201916694064-A
Country	US
Kind code	B2
Filing date	Nov 25, 2019
Priority date	Nov 25, 2019
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

A waterborne alternative polyurethane composition is provided which comprises a reaction product of: an azidated polyol; and a waterborne poly(alkynyl carbamate) prepolymer comprising a reaction product of a polyisocyanate and from 1 wt. % to 20 wt. % of an alkynol-polyether having a formula (I),R1—R2—O—R3—OH  (I),wherein,R1=a monovalent group selected from either HC≡C— or HC≡C—CO—,R2=a divalent alkylene group from 1 to 8 carbon atoms, and may be straight chain or branched and may contain cyclic moieties, andR3=a polyethylene glycol with number average molecular weight from 300-1,200 g/mol, wherein the wt. % is based on the weight of the prepolymer, wherein reaction of the azidated polyol and the waterborne poly(alkynyl carbamate) occurs at a temperature of from 20° C. to 200° C. and optionally in the presence of a catalyst. The inclusion of an alkynol-polyether does not materially alter the performance properties and reactivity of the waterborne polyurethane composition relative to a solventborne polyurethane control composition. Inclusion of the alkynol-polyether reduces the need for organic solvents by allowing for the use of water as a carrier. The inventive waterborne alternative polyurethane compositions may find use in or as coatings, adhesives, sealants, films, elastomers, castings, foams, and composites.

First claim

What is claimed is:

1. A waterborne alternative polyurethane composition comprising a reaction product of:
an azidated polyol; and
a waterborne poly(alkynyl carbamate) prepolymer comprising a reaction product of a polyisocyanate and from 1 wt. % to 20 wt. % of an alkynol-polyether having a formula (I),
R 1 —R 2 —O—R 3 —OH  (I),

wherein,
R 1 =a monovalent group selected from either HC≡C— or HC≡C—CO—,
R 2 =a divalent alkylene group from 1 to 8 carbon atoms, and may be straight chain or branched and may contain cyclic moieties, and
R 3 =a polyethylene glycol with number average molecular weight from 300-1,200 g/mol, wherein the wt. % is based on the weight of the prepolymer; wherein reaction of the azidated polyol and the waterborne poly(alkynyl carbamate) occurs at a temperature of from 20° C. to 200° C. and optionally in the presence of a catalyst.

2. The waterborne alternative polyurethane composition according to claim 1 , wherein the alkynol-polyether is a reaction product of an alkynol and a mono-toluenesulfonyl ester of a polyether diol (TsO-POE).

3. The waterborne alternative polyurethane composition according to claim 2 , wherein the mono-toluenesulfonyl ester of a polyether diol (TsO-POE) is a hydrogenation product of a mono-trityl ether of a polyether diol, toluenesulfonyl ester (TrtO-POE-OTs).

4. The waterborne alternative polyurethane composition according to claim 3 , wherein the mono-trityl ether of a polyether diol, toluenesulfonyl ester (TrtO-POE-OTs) is a reaction product of a mono-trityl ether of a polyether diol (TrtO-POE) and tosyl chloride (TOSYL-CL).

5. The waterborne alternative polyurethane composition according to claim 4 , wherein the mono-trityl ether of a polyether diol (TrtO-POE) is a reaction product of a polyether diol (POE) and trityl chloride (TRTCl).

6. The waterborne alternative polyurethane composition according to claim 1 , wherein the alkynol is selected from the group consisting of propargyl alcohol, 2-hydroxyethylpropiolate, and isomers of any of these; or mixtures of any of these.

7. The waterborne alternative polyurethane composition according to claim 1 , wherein the alkynol-polyether comprises 5 wt. % to 15 wt. % of the prepolymer.

8. The waterborne 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.

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

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

11. The waterborne 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 waterborne alternative polyurethane composition according to claim 1 , wherein the catalyst comprises a Cu II catalyst and a reducing agent.

13. The waterborne alternative polyurethane composition according to claim 12 , 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 waterborne alternative polyurethane composition according to claim 12 , 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 waterborne alternative polyurethane composition according to claim 1 .

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 a waterborne alternative polyurethane composition comprising reacting an azidated polyol and a waterborne poly(alkynyl carbamate) prepolymer at a temperature of from 20° C. to 200° C., optionally in the presence of a catalyst, wherein the waterborne poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate component and from 1 wt. % to 20 wt. % of an alkynol-polyether having a formula (I),
R 1 —R 2 —O—R 3 —OH  (I),

wherein,
R 1 =a monovalent group selected from either HC≡C— or HC≡C—CO—,
R 2 =a divalent alkylene group from 1 to 8 carbon atoms, and may be straight chain or branched and may contain cyclic moieties, and
R 3 =a polyethylene glycol with number average molecular weight from 300-1,200 g/mol, and wherein the wt. % is based on the weight of the prepolymer.

18. The process according to claim 17 , wherein the alkynol-ether is a reaction product of an alkynol and a mono-toluenesulfonyl ester of a polyether diol (TsO-POE).

19. The process according to claim 18 , wherein the mono-toluenesulfonyl ester of a polyether diol (TsO-POE) is a hydrogenation product of a mono-trityl ether of a polyether diol, toluenesulfonyl ester (TrtO-POE-OTs).

20. The process according to claim 19 , wherein the mono-trityl ether of a polyether diol, toluenesulfonyl ester (TrtO-POE-OTs) is a reaction product of a mono-trityl ether of a polyether diol (TrtO-POE) and tosyl chloride (TOSYL-CL).

21. The process according to claim 20 , wherein the mono-trityl ether of a polyether diol (TrtO-POE) is a reaction product of a polyether diol (POE) and trityl chloride (TRTCl).

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

23. The process according to claim 17 , wherein the alkynol-polyether comprises 5 wt. % to 15 wt. % of the prepolymer.

24. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, a foam, and a composite comprising the waterborne alternative polyurethane composition produced according to the process of claim 17 .

25. 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 24 .

Assignees

• Covestro Llc
• The Univ Of Southern Mississippi

Inventors

• Storey Robson F
• Ekin Alan
• Wu Jie

Classifications

• C08G18/10

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

• C09D175/16

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

• C08G18/283

  Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds · CPC title

• C08G18/4833

  Polyethers containing oxyethylene units · CPC title

• C08G18/675

  Low-molecular-weight compounds · CPC title