Adhesive compositions and methods

Patent metadata

Field	Value
Publication number	US-9834710-B2
Application number	US-201314394762-A
Country	US
Kind code	B2
Filing date	Apr 16, 2013
Priority date	Apr 16, 2012
Publication date	Dec 5, 2017
Grant date	Dec 5, 2017

Abstract

The present invention encompasses polyurethane adhesive compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane adhesives derived from aliphatic polycarbonate polyols and polyisocyanates wherein the polyol chains contain a primary repeating unit having a structure:. In another aspect, the invention provides articles comprising the inventive polyurethane compositions as well as methods of making such compositions.

First claim

What is claimed is:

1. A reactive polyurethane adhesive formulation comprising segments derived from one or more aliphatic polycarbonate polyols having a structure P1:

wherein
R 1 , R 2 , R 3 , and R 4 are, at each occurrence in the polymer chain, independently selected from the group consisting of —H, fluorine, an optionally substituted C 1-40 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted aryl group;
any two or more of R 1 , R 2 , R 3 , and R 4 may optionally be taken together with intervening atoms to form one or more optionally substituted rings optionally containing one or more heteroatoms;
Y is, at each occurrence, independently —H, a reactive group, or a site of attachment to a chain-extending moiety;

 is a multivalent moiety;
x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6;
n is, at each occurrence independently, an integer from 3 to 1,000; and
wherein the strength of a cured bond formed by the polyurethane adhesive composition between two substrates is at least 30% greater at a temperature of 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C., wherein the strength is measured at each temperature by ASTM D1002 lap sheer test, and the strength is indicated by a measurement selected from the group consisting of: Load at Failure; Tensile Energy to Break; Stress at Yield; and Strain at Yield.

2. The polyurethane adhesive composition of claim 1 , wherein the strength of the cured bond formed by the polyurethane adhesive composition at is at least 40% greater at 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

3. The polyurethane adhesive composition of claim 2 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 50% greater at 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

4. The polyurethane adhesive composition of claim 3 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 75% greater at 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

5. The polyurethane adhesive composition of claim 4 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 100% greater at 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

6. The polyurethane adhesive composition of claim 5 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is between 100% and 200% greater at 70° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

7. The reactive polyurethane adhesive formulation of claim 1 , wherein at least one of Load at Failure, Tensile Energy to Break, or Strain at Yield is higher at 50° C. than at room temperature.

8. The polyurethane adhesive composition of claim 1 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 15% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

9. The polyurethane adhesive composition of claim 8 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 20% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

10. The polyurethane adhesive composition of claim 9 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 30% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

11. The polyurethane adhesive composition of claim 10 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 40% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

12. The polyurethane adhesive composition of claim 11 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 50% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

13. The polyurethane adhesive composition of claim 12 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 75% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

14. The polyurethane adhesive composition of claim 13 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is at least 100% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

15. The polyurethane adhesive composition of claim 14 , wherein the strength of the cured bond formed by the polyurethane adhesive composition is between 100% and 200% greater at 50° C. than the strength of the cured bond formed by the polyurethane adhesive composition at 25° C.

16. The reactive polyurethane adhesive formulation of claim 1 , wherein the cured bond formed by reactive polyurethane adhesive formulation retains at least 50% of its room temperature strength when heated to a temperature of 60° C.

17. The reactive polyurethane adhesive formulation of claim 1 characterized in that a cured sample of the reactive polyurethane adhesive formulation gains less than 5% mass upon immersion in toluene for 1 week at room temperature, or characterized in that a cured sample of the reactive polyurethane adhesive formulation gains less than 1% mass upon immersion in xylene for 1 week room temperature.

18. The reactive polyurethane adhesive formulation of claim 1 , wherein the one or more aliphatic polycarbonate polyols are characterized in that at least 99%, at least 99.5%, at least 99.7%, or at least 99.8% of the end groups are —OH groups.

19. The reactive polyurethane adhesive formulation of claim 1 , wherein the one or more aliphatic polycarbonate polyols comprise a copolymer of carbon dioxide and ethylene oxide.

20. The reactive polyurethane adhesive formulation of claim 1 , wherein the one or more aliphatic polycarbonate polyols comprise a copolymer of carbon dioxide and propylene oxide.

21. The reactive polyurethane adhesive formulation of claim 1 , wherein the one or more aliphatic polycarbonate polyols comprise a terpolymer of carbon dioxide and ethylene oxide along with one or more additional epoxides selected from the group consisting of propylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene oxide, epichlorohydrin, glicydyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.

22. The reactive polyurethane adhesive formulation of claim 1 , wherein the one or more aliphatic polycarbonate polyols comprise a terpolymer of carbon dioxide and propylene oxide along with one or more additional epoxides selected from the group consisting of ethylene oxide, 1,2-butene oxide, 2,3-butene oxide, cyclohexene oxide, 3-vinyl cyclohexene o

Assignees

• Saudi Aramco Tech Co

Inventors

• Allen Scott D
• Sendijarevic Vahid
• O'Connor James

Classifications

• C08G2170/80

  Compositions for aqueous adhesives · CPC title

• C09J175/06

  from polyesters · CPC title

• C08G18/44

  Polycarbonates · CPC title

• C08G2170/20

  Compositions for hot melt adhesives · CPC title

• C08G18/089 Primary

  Reaction retarding agents · CPC title