Azido-alkyne click and oxysilane hybrid compositions

Patent metadata

Field	Value
Publication number	US-11267927-B2
Application number	US-201916693943-A
Country	US
Kind code	B2
Filing date	Nov 25, 2019
Priority date	Nov 25, 2019
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

The present invention provides alternative polyurethane composition comprising the reaction product of an azidated polyol and a poly(alkynyl carbamate) prepolymer, wherein the poly(alkynyl carbamate) prepolymer comprises the reaction product of a polyisocyanate, an alkynol, and an oxysilane. The reaction of the polyol and the prepolymer may occur in the presence of a catalyst or at a temperature of from 20° C. to 120° C. The inventive oxysilane and azido-alkyne hybrid click formulations provide comparable performance, and in some cases better performance, to/than urethane and azido-alkyne control click formulations in terms of pencil hardness, MEK double rubs, and glass transition temperature. The inventive alternative polyurethane compositions may be used to provide coatings, adhesives, sealants, films, elastomers, castings, 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, wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of stoichiometric equivalents of:
(a) a polyisocyanate, and
(b) an active-hydrogen-containing component, wherein the active-hydrogen-containing component comprises 60-99 mol % of an alkynol, and 1-40 mol % of an oxysilane of the formula (I),
H—X—R 1 —Si(OR 2 ) 3 ,  (I)

wherein the alkynol and the oxysilane total 100 mol %, and wherein
X═O, S, or NR 3 ,
R 1 =straight or branched C 1 -C 10 alkyl or a C 1 -C 10 ether,
R 2 =straight or branched C 1 -C 10 alkyl, and
R 3 ═H or straight or branched C 1 -C 10 alkyl.

2. The alternative polyurethane composition according to claim 1 , wherein the alkynol contains from 3 to 10 carbon atoms.

3. The alternative polyurethane composition according to claim 1 , wherein the alkynol is propargyl alcohol or 2-hydroxyethylpropiolate.

4. 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), isomers of any of these and mixtures of any of these.

5. The 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.

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

7. The alternative polyurethane composition according to claim 6 , 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.

8. The alternative polyurethane composition according to claim 1 , wherein the oxysilane is selected from the group consisting of (3-aminopropyl)trimethoxysilane, (3-aminopropyl)triethoxysilane, and N-(2-aminoethyl) 3-aminopropyl trimethoxysilane.

9. The alternative polyurethane composition according to claim 1 further modified with from 5 mol % to 20 mol % (relative to molar amount of the oxysilane component) of a tetrafunctional alkoxysilane of the formula (II)
Si(OR 4 ) 4   (II),

wherein R 4 =straight or branched C 1 -C 10 alkyl.

10. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, and a composite comprising the alternative polyurethane composition according to claim 1 cured at a temperature of from 100° C. to 200° C.

11. One of a coating, an adhesive, a sealant, a film, an elastomer, a casting, and a composite comprising the alternative polyurethane composition according to claim 1 cured at a temperature of from 20° C. to 140° C. in the presence of Cu I -containing catalyst.

12. The coating, adhesive, sealant, film, elastomer, casting, or composite according to claim 11 , wherein the Cu I -containing catalyst comprises a Cu II catalyst and a reducing agent.

13. The coating, adhesive, sealant, film, elastomer, casting, or composite 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, copper(II) 2-ethylhexanoate, and copper(II) acetate monohydrate.

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

16. A process of protecting a substrate comprising contacting at least a portion of the substrate with one of a coating, an adhesive, a sealant, a film, and an elastomer comprising the alternative polyurethane composition according to claim 1 , and curing the coating, adhesive, sealant, film, or elastomer.

17. A process of producing an alternative polyurethane composition comprising:
reacting an azidated polyol and a poly(alkynyl carbamate) prepolymer, wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of stoichiometric equivalents of:
(a) a polyisocyanate, and
(b) an active-hydrogen-containing component, wherein the active-hydrogen-containing component is comprised of 60-99 mol % of an alkynol, and 1-40 mol % of an oxysilane of the formula (I),
H—X—R 1 —Si(OR 2 ) 3   (I)

wherein, the alkynol and the oxysilane total 100 mol %, and wherein
X═O, S, or NR 3 ,
R 1 =straight or branched C 1 -C 10 alkyl or a C 1 -C 10 ether,
R 2 =straight or branched C 1 -C 10 alkyl, and
R 3 ═H or C 1 -C 10 straight or branched alkyl.

18. The process according to claim 17 , wherein the alkynol contains from 3 to 10 carbon atoms.

19. The process according to claim 17 , wherein the alkynol is propargyl alcohol or 2-hydroxyethylpropiolate.

20. The process according to claim 17 , 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), isomers of any of these and mixtures of any of these.

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

22. The process according to claim 21 , 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.

23. The process according to claim 17 , wherein the oxysilane is selected from the group consist

Assignees

• Covestro Llc
• The Univ Of Southern Mississippi

Inventors

• Ekin Alan
• Storey Robson F
• Cooke Iii R Hunter
• Livingston Harrison A

Classifications

• C08G18/3893

  containing silicon · CPC title

• C08G18/246

  containing also tin-carbon bonds · CPC title

• C09J175/14

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

• C08G18/289

  containing silicon · CPC title

• C09D175/04 Primary

  Polyurethanes · CPC title