Polymer compositions and methods

1. An epoxide CO 2 copolymer composition comprising aliphatic polycarbonate chains having two or more sites of olefinic unsaturation, wherein

a) the aliphatic polycarbonate chains have a formula:

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, a C 1-30 aliphatic group, a C 1-20 heteroaliphatic group, and a 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 rings optionally containing one or more heteroatoms;

each Y independently comprises an acrylate, acrolein, acrylamide, maleimide, vinyl, or styrene functional group containing olefinic unsaturation;

is a covalent bond, a heteroatom, or a multivalent moiety;

n is, on average in the polymer, an integer from about 5 to about 400; and

x and γ are each independently an integer from 0 to 6, where the sum of x and γ is between 2 and 6;

b) at least two of the sites of olefinic unsaturation comprise carbon-carbon double bonds in a moiety selected from the group consisting of:

R a , R b , and R c are independently selected from the group consisting of —H or a C 1-20 aliphatic group;

R d is, at each occurrence, independently selected from the group consisting of: halogen or C 1-20 aliphatic;

k is from 0 to 4, inclusive;

q is from 1 to 6, inclusive;

R a′ is at each occurrence independently selected from the group consisting of:

halogen and C 1-20 aliphatic;

each occurrence of R is independently —H, or a 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; and

p is an integer from 1 to 6 inclusive; and

c) the number average molecular weight of the aliphatic polycarbonate chains is on average in the range of about 500 g/mol to about 100,000 g/mol.

2. The polymer composition of claim 1 , wherein the sites of olefinic unsaturation disposed at the ends of the aliphatic carbonate chains are independently selected from the group consisting of: acrylate ester, acrolein, acrylamide, maleimide, vinyl ether, and styrene.

3. The polymer composition of claim 1 , wherein the sites of olefinic unsaturation in Y comprise carbon-carbon double bonds in a moiety selected from the group consisting of: acrylate, acrolein, acrylamide, maleimide, vinyl ether, and styrene.

4. The polymer composition of claim 1 , wherein each Y is independently selected from the group consisting of:

5. The polymer composition of claim 1 , wherein each Y is independently selected from the group consisting of:

6. The polymer composition of claim 1 , comprising aliphatic polycarbonate chains having a formula:

wherein x′ is an integer between 1 and 5 inclusive and n is, on average in the polymer, an integer from about 5 to about 400.

7. The polymer composition of claim 6 , wherein

is derived from a dihydric alcohol.

8. The polymer composition of claim 6 , wherein

is derived from a polyhydric alcohol.

9. The polymer composition of claim 1 , wherein

is derived from a polycarboxylic acid.

10. The polymer composition of claim 9 , wherein

is derived from a dicarboxylic acid.

11. The polymer composition of claim 1 , comprising poly(propylene carbonate) chains having a formula:

where

 is selected from the group consisting of: a C 1-40 aliphatic group, a C 1-40 heteroaliphatic group, a aryl moiety, a heteroaryl moiety, a polyether, a polyester, a polyolefin, and a single covalent bond; and

Y is, at each occurrence, independently selected from group consisting of:

12. The polymer composition of claim 11 , wherein

is derived from a polyfunctional chain transfer agent selected from the group consisting of: ethylene glycol; diethylene glycol, trimethylene glycol, 1,3 propane diol; 1,4 butane diol, propylene glycol, hexylene glycol, dipropylene glycol, tripropylene glycol, and alkoxylated derivatives thereof.

13. The polymer composition of claim 1 , wherein sites of olefinic unsaturation are present on at least a portion of the

moieties within the aliphatic polycarbonate chains.

14. A polymer composition comprising aliphatic polycarbonate chains having two or more sites of olefinic unsaturation, wherein

a) each aliphatic polycarbonate chain comprises a repeating unit having a structure:

where R 1 , R 2 , R 3 , and R 4 are, at each occurrence in a polymer chain, independently selected from the group consisting of —H, fluorine, a C 1-20 heteroaliphatic group, a C 1-30 aliphatic group, and a 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 rings optionally containing one or more heteroatoms;

b) each aliphatic polycarbonate chain further comprises a repeating unit having a structure:

where R 1a , R 2a , R 3a , and R 4a are, at each occurrence in a polymer chain, independently selected from the group consisting of —H, fluorine, a C 1-20 aliphatic group, and -T-V, wherein for each unit of B, one or more of R 1a , R 2a , —R 3a , and R 4a is -T-V;

each T is independently a covalent bond or a bivalent C 1-8 saturated or unsaturated, straight or branched, hydrocarbon chain, wherein one or more methylene units are optionally and independently replaced by —NR—, —N(R)C(O)—, —C(O)N(R)—, —N(R)SO 2 —, —SO 2 N(R)—, —O—, —C(O)—, —OC(O)—, —OC(O)O—, —C(O)O—, —N(R)C(O)O—, —OC(O)N(R)—, —S—, —SO—, or —SO 2 —;

each R is independently —H, or a radical selected from the group consisting of C 1-20 aliphatic, heterocyclic, carbocyclic, aryl, and heteroaryl;

each V is an acyl, C 1-12 aliphatic, C 1-12 heteroaliphatic, aryl, heteroaryl, carbocylic, or heterocyclic group containing one or more units of olefinic unsaturation; and

c) the number average molecular weight of the aliphatic polycarbonate chains is on average in the range of about 500 g/mol to about 100,000 g/mol.

15. The polymer composition of claim 8 , wherein the polyhydric alcohol is selected from the group consisting of: glycerol, 1,2,4-butanetriol, 2-(hydroxymethyl)-1,3-propanediol; hexane triols, trimethylol propane, trimethylol ethane, trimethylolhexane, 1,4-cyclohexanetrimethanol, pentaerythritol mono esters, pentaerythritol mono ethers, and alkoxylated analogs thereof.

16. The polymer composition of claim 8 , wherein the polyhydric alcohol comprises a C 2-40 polyhydric alcohol with more than three hydroxyl groups.

17. The polymer composition of claim 1 , characterized in that the aliphatic polycarbonate chains have:

an Mn between about 500 g/mol and about 20,000 g/mol,

greater than 90% carbonate linkages on average, and

at least 90% of the end groups are moieties containing aliphatic unsaturation.

18. A method of combining a polymer composition of claim 1 with a crosslinking initiator under suitable conditions to effect crosslinking between sites of olefinic unsaturation.

19. A composition prepared by the method of claim 18 .

20. A composite comprising a polymer composition or crosslinked composition of claim 1 and further comprising one or more materials suitable for preparing a polymer composite.

21. A composite article comprising a substrate having thereon a coating prepared by at least partially curing a composition of claim 1 .

22. An article of manufacture comprising a crosslinked polymer composition of claim 1 .