Polymer compositions and methods

Patent metadata

Field	Value
Publication number	US-9453100-B2
Application number	US-201214234482-A
Country	US
Kind code	B2
Filing date	Jul 24, 2012
Priority date	Jul 25, 2011
Publication date	Sep 27, 2016
Grant date	Sep 27, 2016

Abstract

The present invention encompasses polyurethane compositions comprising aliphatic polycarbonate chains. In one aspect, the present invention encompasses polyurethane foams, thermoplastics and elastomers 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 foam and elastomer compositions as well as methods of making such compositions.

First claim

What is claimed is:

1. A B-side mixture for the formulation of polyurethane compositions, the mixture comprising an aliphatic polycarbonate polyol having a primary repeating unit with a structure:

where 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, where 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,
wherein the mixture further comprises one or more additional polyols selected from the group consisting of polyether polyols, polyester polyols, and mixtures of these.

2. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that at least 90% of the end groups are —OH groups.

3. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and ethylene oxide.

4. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol comprises a copolymer of carbon dioxide and propylene oxide.

5. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol comprises 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, glycidyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.

6. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol comprises 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 oxide, epichlorohydrin, glycidyl esters, glycidyl ethers, styrene oxides, and epoxides of higher alpha olefins.

7. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol has a number average molecular weight (M n ) in the range of about 500 g/mol to about 10,000 g/mol.

8. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a PDI less than 2.

9. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that, on average in the composition, the percentage of carbonate linkages is 85% or greater.

10. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol has a head-to-tail ratio greater than about 80%.

11. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a viscosity less than about 30,000 cps at 25° C.

12. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is characterized in that it has a Tg less than about 20° C.

13. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol has 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 1-30 aliphatic group, and an optionally substituted C 1-20 heteroaliphatic group, and an optionally substituted C 6-10 aryl group, where 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 or the site of attachment to any of the chain-extending moieties described in the classes and subclasses herein;
n is at each occurrence, independently an integer from about 3 to about 1,000;

is a multivalent moiety; and
x and y are each independently an integer from 0 to 6, where the sum of x and y is between 2 and 6.

14. The B-side mixture of claim 13 , wherein

is derived from a polyfunctional chain transfer agent having two or more sites from which epoxide/CO 2 copolymerization can occur.

15. The B-side mixture of claim 13 , wherein

is derived from a polyfunctional chain transfer agent having a formula:

16. The B-side mixture of claim 13 , wherein

is derived from a dihydric alcohol.

17. The B-side mixture of claim 13 , wherein y is 0 and x is greater than 2.

18. The B-side mixture of claim 1 , wherein the aliphatic polycarbonate polyol is selected from the group consisting of:

wherein, n is at each occurrence, independently an integer from about 3 to about 1,000, t is an integer from 1 to 12 inclusive, and R t is independently at each occurrence —H, or —CH 3 .

19. The B-side mixture of claim 18 , comprising: poly(ethylene carbonate) of formula Q1 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups; or
poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups; or
poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups; or
poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 2,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups; or
poly(ethylene carbonate) of formula Q1 having an average molecular weight number of about 3,000 g/mol, a polydispersity index less than about 1.25, at least 85% carbonate linkages, and at least 98% —OH end groups; or
poly(propylene carbonate) of formula Q2 having an average molecular weight number of between about 500 g/mol and about 3,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups; or
poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 500 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups; or
poly(propylene carbonate) of formula Q2 having an average molecular weight number of about 1,000 g/mol, a polydispersity index less than about 1.25, at least 95% carbonate linkages, and at least 98% —OH end groups; or
poly(propylene carbonate)

Assignees

• Allen Scott D
• Willkomm Wayne R
• Novomer Inc

Inventors

• Allen Scott D
• Willkomm Wayne R

Classifications

• C08G18/7671

  containing only one alkylene bisphenyl group · CPC title

• C08G18/14 Primary

  Manufacture of cellular products · CPC title

• C08G18/1833

  having ether, acetal, or orthoester groups · CPC title

• C08G64/0208

  saturated · CPC title

• C08G64/34 Primary

  and cyclic ethers · CPC title