Polycarbonate block copolymers
AssigneeNovomer, Inc.
InventorsScott D. Allen, Chris A. Simoneau, John M. Salladay, David M. Hatfield, John W. Stevens
Life of this patent
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Abstract
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.
Claims91
A polymer composition comprising a block copolymer having a formula:
- where X is selected from the group consisting of:
- halogen;
- —OH;
- azide, nitrile, and —ORz;
- each Ra, Rb, Rc, and Rd is independently selected from the group consisting of:
- hydrogen, halogen, —CH2ORz, optionally substituted C1-10 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 Ra, Rb, Rc, and Rd 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;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is an optionally substituted moiety selected from the group consisting of:
- C1-20 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
A polymer composition comprising a block copolymer having a formula:
- wherein
- X′ is selected from the group consisting of —OH and —ORz;
- R100 is optionally present, and if present is selected from the group consisting of —CH3, —CF3, —CH2CH3, —CH2ORz, and —CH2Cl;
- each n is independently an integer between 4 and 100;
- —Z— is an optionally substituted C1-6 aliphatic group;
- m is an integer between 5 and 200;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is at each occurrence an optionally substituted moiety independently selected from the group consisting of:
- C1-12 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
A method of forming an emulsion of supercritical CO2 and an aqueous phase, the method comprising a step of agitating supercritical CO2 and the aqueous phase in the presence of a block copolymer having a formula:
- wherein
- X is selected from the group consisting of halogen;
- —OH;
- azide, nitrile, and —ORz;
- each Ra, Rb, Rc, and Rd is independently selected from the group consisting of:
- hydrogen, halogen, —CH2ORz, optionally substituted C1-10 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 Ra, Rb, Rc, and Rd 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;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is an optionally substituted moiety selected from the group consisting of:
- C1-20 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
A method of modifying the viscosity of a fluid comprising a mixture of supercritical CO2 and water, the method comprising a step of agitating the mixture in the presence of a block copolymer having a formula:
- wherein
- X is selected from the group consisting of:
- halogen, —OH, azide, nitrile, and —ORz;
- each Ra, Rb, Rc, and Rd is independently selected from the group consisting of:
- hydrogen, halogen, —CH2ORz, optionally substituted C1-10 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 Ra, Rb, Rc, and Rd 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;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is an optionally substituted moiety selected from the group consisting of:
- C1-20 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
A method of forming an emulsion of supercritical CO2 and an aqueous phase, the method comprising a step of agitating supercritical CO2 and the aqueous phase in the presence of a block copolymer having a formula:
- wherein
- X′ is selected from the group consisting of —OH and —ORz;
- R100 is optionally present, and if present is selected from the group consisting of —CH3, —CF3, —CH2CH3, —CH2ORz, and —CH2Cl;
- each n is independently an integer between 4 and 100;
- —Z— is an optionally substituted C1-6 aliphatic group;
- m is an integer between 5 and 200;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is at each occurrence an optionally substituted moiety independently selected from the group consisting of:
- C1-12 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
A method of modifying the viscosity of a fluid comprising a mixture of supercritical CO2 and water, the method comprising a step of agitating the mixture in the presence of a block copolymer having a formula:
- wherein
- X′ is selected from the group consisting of —OH and —ORz;
- R100 is optionally present, and if present is selected from the group consisting of —CH3, —CF3, —CH2CH3, —CH2ORz, and —CH2Cl;
- each n is independently an integer between 4 and 100;
- —Z— is an optionally substituted C1-6 aliphatic group;
- m is an integer between 5 and 200;
- Rz is selected from the group consisting of R10, —C(O)R10, —SO2R10, —Si(R10)3, —C(O)N(R10)2;
- and
- R10 is at each occurrence an optionally substituted moiety independently selected from the group consisting of:
- C1-12 aliphatic;
- C1-12 heteroaliphatic;
- 6- to 14-membered aryl;
- and 5- to 14-membered heteroaryl.
Dependencies are inferred from the claim text.