Polycarbonate block copolymers
The disclosure pertains to amphiphilic block copolymers comprising an aliphatic polycarbonate chain coupled to a hydrophilic polymer. Such amphiphilic polymers may have the formula A-L-B, where A- is a polycarbonate or polyethercarbonate chain having from about 3 to about 500 repeating units, L is a linker moiety and —B is a hydrophilic oligomer having from about 4 to about 200 repeating units. Provided copolymers are useful as surfactants capable of emulsifying aqueous solutions and supercritical carbon dioxide. Provided copolymers also have utility as additives for use in enhanced oil recovery methods.
1. A polymer composition comprising a triblock copolymer having a formula:
wherein:
—Z— is an optionally substituted C 1-6 aliphatic group,
—Y is an acyl group;
each R a , R b , R c , and R d is independently selected from the group consisting of: hydrogen, halogen, —CH 2 OR z , optionally substituted C 1-10 aliphatic, optionally substituted 6- to 14-membered aromatic, optionally substituted 3- to 14-membered heterocyclic, and optionally substituted 5- to 14-membered heteroaryl, and wherein any two or more of R a , R b , R c , and R d may be taken together to form an optionally substituted 3- to 12-membered ring, optionally containing one or more heteroatoms;
each L is independently a bond or a polyfunctional moiety;
n is an integer between 4 and 100;
m is an integer between about 4 and about 500;
m′ is, on average approximately equal to m;
R z is selected from the group consisting of R 10 , —C(O)R 10 , —SO 2 R 10 , —Si(R 10 ) 3 , —C(O)N(R 10 ) 2 ; and
R 10 is an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic, C 1-12 heteroaliphatic, 6- to 14-membered aryl, and 5- to 14-membered heteroaryl.
2. The polymer composition of claim 1 , wherein —Y is an acyl group of the formula —C(O)R 101 wherein:
R 101 is an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic, C 1-12 heteroaliphatic, 6- to 14-membered aryl, and 5- to 14-membered heteroaryl.
3. The polymer composition of claim 2 , wherein R 101 is optionally substituted C 1-20 aliphatic.
4. The polymer composition of claim 2 , wherein R 101 is optionally substituted C 1-20 alkenyl.
5. The polymer composition of claim 2 , wherein R 101 is optionally substituted C 1-3 alkenyl.
6. The polymer composition of claim 1 , wherein —Y is selected from the group of consisting of formate, acetate, trifluoroacetate, propionate, and optionally substituted benzoate.
7. The polymer composition of claim 1 , wherein the triblock copolymer has a formula:
8. The polymer composition of claim 1 , wherein the copolymer has a formula:
wherein R 100 is optionally present, and if present is selected from the group consisting of —CH 3 , —CF 3 , —CH 2 CH 3 , —CH 2 OR z , —CH 2 Cl, a C 3-30 alkyl group, and mixtures of two or more of these.
9. The polymer composition of claim 8 , wherein R 100 is present, and the head to tail ratio of adjacent
groups is greater than about 80%, greater than about 90%, or greater than about 95%.
10. The polymer composition of claim 8 , wherein R 100 is absent.
11. The polymer composition of claim 8 , wherein R 100 is methyl.
12. The polymer composition of claim 8 , wherein R 100 comprises a random mixture of methyl and one or more C 3-30 alkyl groups.
13. The polymer composition of claim 1 , wherein the value of n is selected from the group consisting of:
between about 4 and about 50;
between about 4 and about 25;
between about 10 and about 20; and
between about 4 and about 10.
14. The polymer composition of claim 1 , wherein the value of m is selected from the group consisting of:
between about 5 and about 200;
between about 5 and about 50;
between about 5 and about 25;
between about 10 and about 20; and
between about 5 and about 10.
15. The polymer composition of claim 1 , wherein the PDI is less than about 2, less than 1.4, less than 1.2, or less than about 1.1.
16. A polymer composition comprising a triblock copolymer having a formula:
wherein:
—Z— is an optionally substituted C 1-6 aliphatic group,
—Y is a silyl group;
each R a , R b , R c , and R d is independently selected from the group consisting of: hydrogen, halogen, —CH 2 OR z , optionally substituted C 1-10 aliphatic, optionally substituted 6- to 14-membered aromatic, optionally substituted 3- to 14-membered heterocyclic, and optionally substituted 5- to 14-membered heteroaryl, and wherein any two or more of R a , R b , R c , and R d may be taken together to form an optionally substituted 3- to 12-membered ring, optionally containing one or more heteroatoms;
each L is independently a bond or a polyfunctional moiety;
n is an integer between 4 and 100;
m is an integer between about 4 and about 500;
m′ is, on average approximately equal to m;
R z is selected from the group consisting of R 10 , —C(O)R 10 , —SO 2 R 10 , —Si(R 10 ) 3 , —C(O)N(R 10 ) 2 ; and
R 10 is an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic, C 1-12 heteroaliphatic, 6- to 14-membered aryl, and 5- to 14-membered heteroaryl.
17. The polymer composition of claim 16 , wherein —Y is a silyl group of the formula —Si(R 101 ) 3 , wherein:
R 101 is an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic, C 1-12 heteroaliphatic, 6- to 14-membered aryl, and 5- to 14-membered heteroaryl.
18. The polymer composition of claim 17 , wherein R 101 is optionally substituted C 1-20 aliphatic.
19. The polymer composition of claim 16 , wherein —Y is a silyl-based oxygen protecting group.
20. The polymer composition of claim 16 , wherein —Y is selected from the group of consisting of: trimethylsilyl, triethylsilyl, triisopropyl silyl, t-butyldimethylsilyl, and t-butyldiphenylsilyl.
21. The polymer composition of claim 16 , wherein the triblock copolymer has a formula:
22. The polymer composition of claim 16 , wherein the copolymer has a formula:
wherein R 100 is optionally present, and if present is selected from the group consisting of —CH 3 , —CF 3 , —CH 2 CH 3 , —CH 2 OR z , —CH 2 Cl, a C 3-30 alkyl group, and mixtures of two or more of these.
23. The polymer composition of claim 22 , wherein R 100 is present, and the head to tail ratio of adjacent
groups is greater than about 80%, greater than about 90%, or greater than about 95%.
24. The polymer composition of claim 22 , wherein R 100 is absent.
25. The polymer composition of claim 22 , wherein R 100 is methyl.
26. The polymer composition of claim 22 , wherein R 100 comprises a random mixture of methyl and one or more C 3-30 alkyl groups.
27. The polymer composition of claim 16 , wherein the value of n is selected from the group consisting of:
between about 4 and about 50;
between about 4 and about 25;
between about 10 and about 20; and
between about 4 and about 10.
28. The polymer composition of claim 16 , wherein the value of m is selected from the group consisting of:
between about 5 and about 200;
between about 5 and about 50;
between about 5 and about 25;
between about 10 and about 20; and
between about 5 and about 10.
29. The polymer composition of claim 16 , wherein the PDI is less than about 2, less than 1.4, less than 1.2, or less than about 1.1.
30. A polymer composition comprising a triblock copolymer having a formula:
wherein:
—Z— is an optionally substituted C 1-6 aliphatic group,
—Y is a sulfonate group;
each R a , R b , R c , and R d is independently selected from the group consisting of: hydrogen, halogen, —CH 2 OR z , optionally substituted C 1-10 aliphatic, optionally substituted 6- to 14-membered aromatic, optionally substituted 3- to 14-membered heterocyclic, and optionally substituted 5- to 14-membered heteroaryl, and wherein any two or more of R a , R b , R c , and R d may be taken together to form an optionally substituted 3- to 12-membered ring, optionally containing one or more heteroatoms;
each L is independently a bond or a polyfunctional moiety;
n is an integer between 4 and 100;
m is an integer between about 4 and about 500;
m′ is, on average approximately equal to m;
R z is selected from the group consisting of R 10 , —C(O)R 10 , —SO 2 R 10 , —Si(R 10 ) 3 , —C(O)N(R 10 ) 2 ; and
R 10 is an optionally substituted moiety selected from the group consisting of: C 1-20 aliphatic, C 1-12 heteroaliphatic, 6- to 14-membered aryl, and 5- to 14-membered heteroaryl.
31. The polymer composition of claim 30 , wherein the triblock copolymer has a formula:
32. The polymer composition of claim 30 , wherein the copolymer has a formula:
wherein R 100 is optionally present, and if present is selected from the group consisting of —CH 3 , —CF 3 , —CH 2 CH 3 , —CH 2 OR z , —CH 2 Cl, a C 3-30 alkyl group, and mixtures of two or more of these.
33. The polymer composition of claim 32 , wherein R 100 is present, and the head to tail ratio of adjacent
groups is greater than about 80%, greater than about 90%, or greater than about 95%.
34. The polymer composition of claim 32 , wherein R 100 is absent.
35. The polymer composition of claim 32 wherein R 100 is methyl.
36. The polymer composition of claim 32 , wherein R 100 comprises a random mixture of methyl and one or more C 3-30 alkyl groups.
37. The polymer composition of claim 30 , wherein the value of n is selected from the group consisting of:
between about 4 and about 50;
between about 4 and about 25;
between about 10 and about 20; and
between about 4 and about 10.
38. The polymer composition of claim 30 , wherein the value of m is selected from the group consisting of:
between about 5 and about 200;
between about 5 and about 50;
between about 5 and about 25;
between about 10 and about 20; and
between about 5 and about 10.
39. The polymer composition of claim 30 , wherein the PDI is less than about 2, less than 1.4, less than 1.2, or less than about 1.1.