Polymer compositions and methods

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, 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, 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; and

the number average molecular weight of the epoxide CO 2 copolymer composition is less than about 20,000 g/mol;

wherein the epoxide CO 2 copolymer composition further comprises epoxide CO 2 polymer chains of 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, 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 a moiety 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,

α is an integer from 1 to 4 inclusive;

X′ is selected from the group consisting of C 1-20 acyl oxy, halogen, alkoxy, nitrate, azide, optionally substituted phenoxy, nitrophenoxy and sulfonate; and

n is an integer from 5 to about 500.

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 having chains ends of formula:

comprise a primary repeat unit having a formula:

7. The epoxide CO 2 copolymer composition of claim 6 , wherein the —Q-(Z) α moieties of the epoxide CO 2 copolymer chains having chain ends of formula:

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;

where one or more R d groups of the formula

are optionally present, and 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 having chain ends of formula:

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 polymer chains having chain ends of formula:

comprise a copolymer of CO 2 and propylene oxide.

11. The epoxide CO 2 copolymer composition of claim 1 , wherein the number average molecular weight of the epoxide CO 2 copolymer is between about 500 g/mol and 5,000 g/mol.

12. The epoxide CO 2 copolymer composition of claim 6 , wherein the

moieties of the epoxide CO 2 copolymer chains within the epoxide CO 2 copolymer composition having chain ends of formula:

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 and 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;

each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3; and

p is an integer from 1 to 10.

13. The epoxide CO 2 copolymer composition of claim 12 , wherein the

moieties of the epoxide CO 2 copolymer chains within the epoxide CO 2 copolymer composition having chain ends of formula:

are selected from the group consisting of:

14. The epoxide CO 2 copolymer composition of claim 6 , wherein the epoxide CO 2 copolymer chains of formula:

are of formula:

15. The epoxide CO 2 copolymer composition claim 6 , wherein the

moieties of the epoxide CO 2 copolymer chains of formula:

are selected from the group consisting of:

each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3; and

p is an integer from 1 to 10.

16. The epoxide CO 2 copolymer composition of claim 15 , wherein the

moieties of the epoxide CO 2 copolymer chains of formula:

are selected from the group consisting of:

17. A higher polymer comprising the reaction product of an epoxide CO 2 copolymer composition of claim 1 with a polyfunctional reagent selected from the group consisting of: polyisocyanates, melamine, and phenol formaldehyde resins.

18. A higher polymer comprising a reaction product of olefin polymerization between an epoxide CO 2 copolymer composition of claim 1 and a reactive diluent comprising a reactive olefin.

19. A composite comprising a higher polymer composition of claim 17 in combination with one or more inorganic materials.

20. A glass laminate comprising epoxide CO 2 copolymer composition of claim 1 .

21. A method for producing an epoxide CO 2 copolymer composition of claim 1 having improved glass adhesion comprising the step of treating an epoxide CO 2 copolymer comprising —OH end groups with a reagent to convert at least a portion of the free —OH end groups of the epoxide CO 2 copolymer to moieties comprising a functional group selected from the group consisting of: silicon-containing functional groups, —SO 3 H, phosphorus-containing functional groups, —N(R α ) 3 ± , and combinations of two or more of these

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.

22. The epoxide CO 2 copolymer composition of claim 6 , wherein the chain ends of formula:

are of formula:

wherein

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;

each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3;

v is 0 or an integer from 1 to 20;

p is an integer from 1 to 10; and

m′ is 0 or 1.

23. The epoxide CO 2 copolymer composition of claim 6 , wherein the chain ends of formula:

are of formula:

wherein

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;

each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3;

v is 0 or an integer from 1 to 20;

p is an integer from 1 to 10; and

m′ is 0 or 1.

24. The epoxide CO 2 copolymer composition of claim 6 , wherein the chain ends of formula:

are of formula:

25. The epoxide CO 2 copolymer composition of claim 6 , wherein the chain ends of formula:

are of formula:

wherein

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;

each Q′ is a multifunctional organic moiety optionally containing one or more heteroatoms and each Q′ may be the same or different;

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3; and

p is an integer from 1 to 10.

26. The epoxide CO 2 copolymer composition of claim 6 , wherein the chain ends of formula:

are of formula:

wherein

each R 2s is independently H, optionally substituted C 1-6 aliphatic, or optionally substituted phenyl;

each R 1s is independently a C 1-6 aliphatic group or optionally substituted aryl group;

m is 0, 1, 2, or 3; and

v is an integer from 1 to 20.

27. The epoxide CO 2 copolymer composition of claim 1 , wherein 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 95% or greater.

28. The epoxide CO 2 copolymer composition of claim 1 , wherein 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 99% or greater.

29. The epoxide CO 2 copolymer composition of claim 11 , wherein 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 99% or greater.