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 method for the synthesis of a block copolymer having a formula:
the method comprising the step of reacting an epoxide of formula
with carbon dioxide in the presence of a suitable catalyst and a polyether chain transfer agent having one free OH group;
where X′ is selected from the group consisting of —OH and —OR z ;
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 where 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;
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 , or a hydroxyl protecting group;
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;
—Z— is an optionally substituted C 1-6 aliphatic group;
—Y is selected from the group consisting of —H and R z ;
n is an integer between 4 and 100; and
m is an integer between 5 and 200.
2. The method of claim 1 , wherein the block copolymer has the formula:
wherein L is a bond or a polyfunctional moiety;
and the epoxide has the 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 , and —CH 2 Cl.
3. The method of claim 2 , wherein R 100 is absent.
4. The method of claim 2 , wherein R 100 is present.
5. The method of claim 4 , wherein the block copolymer has the formula:
6. The method of claim 4 , wherein R 100 is a methyl group.
7. The method of claim 4 , wherein R 100 is a random mixture of methyl groups and one or more moieties selected from group consisting of ethyl, trifluoromethyl, chloromethyl, —CH 2 OR z , and a C 6-30 alkyl group.
8. The method of claim 1 , wherein X′ is —OH.
9. The method of claim 1 , wherein X′ is —OR z .
10. The method of claim 9 , wherein a block copolymer formed by the step of reacting the epoxide with carbon dioxide and a polyether chain transfer agent is further modified by a reaction to convert —X′ from an —OH group to an —OR z group.
11. The method of claim 10 , wherein the block copolymer is modified by a reaction chosen from the group consisting of alkylation, acylation, sulfonation, or silylation.
12. The method of claim 1 , wherein —Z— is —CH 2 CH 2 —.
13. The method of claim 1 , wherein —Z— is —CH(CH 3 )CH 2 —.
14. The method of claim 1 , wherein —Z— is —CH 2 —.
15. The method of claim 1 , wherein —Y is —H.
16. The method of claim 1 , wherein —Y is a C 1-6 aliphatic group.
17. The method of claim 1 , wherein —Y is a hydroxyl protecting group.
18. The method of claim 17 , further comprising the step of treating the block copolymer to convert the hydroxyl protecting group to a free hydroxyl group.
19. The method of claim 18 , wherein the hydroxyl protecting group is selected from the group consisting of an allyl ether and benzyl ether.
20. The method of claim 19 , wherein the step of converting the hydroxyl protecting group to a free hydroxyl group comprises hydrogenolysis.
21. The method of claim 18 , wherein the hydroxyl protecting group comprises a silyl ether.
22. A method for the synthesis of a block copolymer having a formula:
the method comprising the step of reacting an epoxide of formula
with carbon dioxide in the presence of a suitable catalyst and a chain transfer agent having a formula:
B-L-OH
where X′ is selected from the group consisting of —OH and —OR z ;
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 where 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;
L is a bond or a polyfunctional moiety;
B is a hydrophilic oligomer having from about 4 to about 100 repeating units;
n is an integer between 4 and 100;
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 , or a hydroxyl protecting group; 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.
23. The method of claim 22 , wherein -B is selected from the group consisting of polyethers, polyolefin bearing hydrophilic functional groups, polypeptides, polysaccharides and polyamines.
24. The method of claim 23 , wherein -B is selected from the group consisting of polyoxymethylene, poly(ethylene oxide), poly(propylene oxide), polyvinyl alcohol, poly(vinyl acetate), partially hydrolyzed poly(vinyl acetate), poly(acrylic acid), polyacrylamide, polyethyleneimine, poly(2-hydroxyethyl methacrylate), poly(N-vinylpyrrolidone), polypeptides, polysaccharides, polyepoxysuccinic acid, poly(methyl vinyl ether), poly(allylamine), poly(2-ethyl-2-oxazoline), and block, tapered or random copolymers of any two or more of the above.
25. The method of claim 23 , wherein -B is a polyether.