Polymer compositions and methods

Patent metadata

Field	Value
Publication number	US-10138369-B2
Application number	US-201214116675-A
Country	US
Kind code	B2
Filing date	May 9, 2012
Priority date	May 9, 2011
Publication date	Nov 27, 2018
Grant date	Nov 27, 2018

Abstract

The present invention encompasses polymer compositions comprising aliphatic polycarbonate chains containing functional groups that increase the polymer's ability to wet or adhere to inorganic materials. In certain embodiments, chain ends of the aliphatic polycarbonates are modified to introduce silicon-containing functional groups, boron-containing functional groups, phosphorous-containing functional groups, sulfonic acid groups or carboxylic acid groups.

First claim

What is claimed is:

1. An epoxide CO 2 copolymer composition comprising epoxide CO 2 copolymer chains wherein:
one or more chain ends of at least a portion of the epoxide CO 2 copolymer chains within the epoxide CO 2 copolymer composition have a formula:

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 1-30 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 and/or one or more sites of unsaturation;
—Q— is a bivalent or multivalent moiety;
each Z comprises an adhesion enhancing functional group independently selected from the group consisting of: silicon-containing functional groups, phosphorous-containing functional groups, —SO 3 H, —CO 2 H, and —N(R α ) 3 + where each R α is at each occurrence, independently selected from the group consisting of optionally substituted phenyl, and optionally substituted C 1-12 aliphatic; and
α is an integer from 1 to 4 inclusive;

the epoxide CO 2 copolymer composition is characterized in that, on average in the composition, the percentage of carbonate linkages in epoxide CO 2 copolymer chains is 90% or greater;
the number average molecular weight of the epoxide CO 2 copolymer composition is less than about 20,000 g/mol; and
further, wherein one or more chain ends of at least a portion of the epoxide CO 2 copolymer chains within the epoxide CO 2 copolymer composition have a formula:

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 1-30 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 and/or one or more sites of unsaturation.

2. The epoxide CO 2 copolymer composition of claim 1 , wherein the adhesion enhancing functional group is linked to a chain end via an ester linkage.

3. The epoxide CO 2 copolymer composition of claim 1 , wherein the adhesion enhancing functional group is linked to a chain end via a urethane linkage.

4. The epoxide CO 2 copolymer composition of claim 1 , wherein the adhesion enhancing functional group is linked to a chain end via an ether linkage.

5. The epoxide CO 2 copolymer composition of claim 1 , wherein the adhesion enhancing functional group comprises a silicon-containing functional group and a silicon atom is bonded directly to a terminal oxygen atom of the epoxide CO 2 copolymer.

6. The epoxide CO 2 copolymer composition of claim 1 , wherein the epoxide CO 2 copolymer chains comprise a primary repeat unit having a formula:

7. The epoxide CO 2 copolymer composition of claim 6 , wherein the -Q-(Z) α , moieties are selected from the group consisting of:

where R a and R b are, at each occurrence, independently selected from the group consisting of —H, halogen, an optionally substituted C 1-20 aliphatic group, an optionally substituted C 1-20 heteroaliphatic group, an optionally substituted C 6-14 aryl group, an optionally substituted acyloxy group, an optionally substituted acyl group, an optionally substituted alkoxy group, an optionally substituted 3- to 14-membered carbocyclic group, and an optionally substituted 3- to 12-membered heterocyclic group, where any two or more R a and R b groups may optionally be taken together with intervening atoms to form one or more optionally substituted, optionally unsaturated rings optionally containing one or more heteroatoms, where any two or more R a and R b groups on adjacent carbon atoms may optionally be taken together with intervening atoms to form an optionally substituted aryl ring, where an R a or R b on one carbon atom and an R a or R b , on an adjacent carbon may optionally be taken together with the bond between the adjacent carbons to represent a double bond between the two carbon atoms, and where R a and R b groups attached to the same atom may be taken together to form an optionally substituted moiety selected from the group consisting of: alkene, imine, oxime, and hydrazone;
R d is, at each occurrence, independently selected from the group consisting of: halogen, —NO 2 , —CN, —SR, —S(O)R, —S(O) 2 R, —NRC(O)R, —OC(O)R, —CO 2 R, —NCO, —N 3 , —OR, —OC(O)N(R) 2 , —N(R) 2 , —NRC(O)R, —NRC(O)OR; or an optionally substituted radical selected from the group consisting of C 1-20 aliphatic, C 1-20 heteroaliphatic, a 3- to 14-membered carbocycle, a 3- to 12-membered heterocycle, a 5- to 12-membered heteroaryl, and 6- to 10-membered aryl; where two or more adjacent R d groups can be taken together to form an optionally substituted saturated, partially unsaturated, or aromatic 5- to 12-membered ring containing 0 to 4 heteroatoms; where each occurrence of R is independently —H, or an optionally substituted moiety selected from the group consisting of C 1-6 aliphatic, C 1-6 heteroaliphatic, 3- to 7-membered heterocyclic, 3- to 7-membered carbocyclic 6- to 10-membered aryl, and 5- to 10-membered heteroaryl;
each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;
each R 2s is independently —H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;
each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;
s is an integer from 1 to 8; and
m is 0, 1, 2, or 3.

8. The epoxide CO 2 copolymer composition of claim 6 , wherein each

moiety in the polymer chain is independently selected from the group consisting of:

where each R x is independently an optionally substituted moiety selected from the group consisting of C 2-20 aliphatic, C 2-20 heteroaliphatic, 3- to 14-membered carbocyclic, 6- to 10-membered aryl, 5- to 10-membered heteroaryl, and 3- to 12-membered heterocyclic.

9. The epoxide CO 2 copolymer composition of claim 1 , wherein the epoxide CO 2 polymer chains comprise a copolymer of CO 2 and an epoxide selected from the group consisting of: ethylene oxide, propylene oxide, 1,2 butene oxide, cyclohexene oxide, epichlorohydrin, 3-vinyl cyclohexene oxide, 3-ethyl cyclohexene oxide, a glycidyl ester, a glycidyl ether and any combination of two or more of these.

10. The epoxide CO 2 copolymer composition of claim 1 , wherein the epoxide CO 2 po

Assignees

• Allen Scott D
• Simoneau Christopher A
• Farmer Jay J
• Saudi Aramco Tech Co

Inventors

• Allen Scott D
• Simoneau Christopher A
• Farmer Jay J

Classifications

• C08G64/42 Primary

  Chemical after-treatment · CPC title

• C08G64/0225

  containing atoms other than carbon, hydrogen or oxygen · CPC title

• C08G64/0216

  containing a chain-terminating or -crosslinking agent · CPC title

• C08L69/00 Primary

  Compositions of polycarbonates; Compositions of derivatives of polycarbonates · CPC title

• C08G64/0266

  containing silicon · CPC title