Zwitterion-functionalized multicomponent copolymers and associated polymer blends and membranes

Patent metadata

Field	Value
Publication number	US-10851241-B2
Application number	US-201815975900-A
Country	US
Kind code	B2
Filing date	May 15, 2018
Priority date	Nov 19, 2014
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

Abstract

Multicomponent copolymers including two or more types of repeat units is presented. In one example, the multicomponent copolymer includes at least one repeat unit AC having a structure (I), at least one repeat unit DC having a structure (II), and at least one repeat unit BC having a structure (III) or (V). The multicomponent copolymer may be cross-linked via a cross-linking agent. A polymer blend including the multicomponent copolymer or a cross-linked copolymer and a second polymer is also provided. The multicomponent copolymer may be a random or a block copolymer. The structural units of the multicomponent copolymers provide improved, tunable properties, such as improved biocompatibility and hydrophilicity, protein fouling, and mechanical properties, to the copolymers and/or the membranes fabricated from the copolymers.

First claim

The invention claimed is:

1. A multicomponent copolymer comprising:
at least one repeat unit AC having a structure (I), at least one repeat unit DC having a structure (II), and at least one repeat unit BC having a structure (III):

wherein “a”, “b” and “c” are independently at each occurrence 1, 2, 3, or 4;
“k” ranges from 0 to 10;
“o”, “p”, “m” and “n” are each, independently, 0 or 1;
R 1 , R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 3 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 3 and Y are each, independently, a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 4 is a bond, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical, and
wherein the copolymer has a formula [(AC) P*S -(DC) Z*S -(BC)R] wherein S is a mole fraction of a total piperazine content, P*S is a mole fraction of a piperazine content of the repeat units AC, Z*S is a mole fraction of a zwitterion content of the repeat units DC, and R is a mole fraction of the repeat units BC in the copolymer, and wherein P+Z=1, S+R=1, wherein P*S ranges from about 0.01 to about 0.4 and Z*S ranges from about 0.10 to about 0.6.

2. The copolymer of claim 1 , wherein the copolymer is a random copolymer comprising randomly distributed sequences of each of the at least one repeat unit AC, BC and DC.

3. The copolymer of claim 1 , wherein Z*S ranges from about 0.3 to about 0.5.

4. The copolymer of claim 1 , wherein P*S ranges from about 0.01 to about 0.15.

5. The copolymer of claim 1 , wherein R ranges from about 0.4 to about 0.75.

6. The copolymer of claim 1 , wherein R ranges from about 0.5 to about 0.6.

7. The copolymer of claim 1 , wherein the weight average molecular weight (M w ) of the copolymer ranges from about 10,000 g/mol to about 90,000 g/mol.

8. The copolymer of claim 1 , wherein the weight average molecular weight (Mw) of the copolymer ranges from about 40,000 g/mol to about 75,000 g/mol.

9. The copolymer of claim 1 , the at least one repeat unit AC having a structure (I) wherein “k” ranges from 1 to 4; “m” and “n” are both 0; R 1 , R 2 , R 3 and R 5 are independently at each occurrence a hydrogen atom or a C 1 -C 4 aliphatic radical.

10. The copolymer of claim 1 , the at least one repeat unit BC having a structure (III) wherein “m” and “n” are both 0; R 2 , R 5 , R 6 and Y′ are independently at each occurrence a hydrogen atom or a C 1 -C 4 aliphatic radical.

11. A membrane comprising:
a multicomponent copolymer comprising at least one repeat unit AC having a structure (I), at least one repeat unit DC comprising a structural unit having a structure (II), and at least one repeat unit BC comprising a structural unit having a structure (III):

wherein “a”, “b” and “c” are independently at each occurrence 1, 2, 3, or 4;
“k” ranges from 0 to 10;
“o”, “p”, “m” and “n” are each, independently, 0 or 1;
R 1 , R 2 and R 5 are independently at each occurrence a hydrogen atom, a halogen atom, a nitro group, a C 3 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;

R 3 and Y are each, independently, a hydrogen atom, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical;
R 4 is a bond, a C 1 -C 12 aliphatic radical, a C 3 -C 12 cycloaliphatic radical, or a C 3 -C 12 aromatic radical, and
wherein the copolymer has a formula [(AC) P*S -(DC) Z*S -(BC)R] wherein S is a mole fraction of a total piperazine content, P*S is a mole fraction of a piperazine content of the repeat units AC, Z*S is a mole fraction of a zwitterion content of the repeat units DC, and R is a mole fraction of the repeat units BC in the copolymer, and wherein P+Z=1, S+R=1 wherein P*S ranges from about 0.01 to about 0.4 and Z*S ranges from about 0.10 to about 0.6.

12. An apparatus comprising a hollow fiber module comprising a plurality of membranes of claim 11 , wherein each membrane is a hollow fiber membrane.

13. A crosslinked polymer, comprising:
the copolymer of claim 11 , wherein the copolymer is crosslinked through one or more piperazine groups of the at least one repeat unit AC with a crosslinking agent.

Assignees

• Gen Electric
• Cytiva Sweden Ab

Inventors

• Moore David
• Misner Matthew Jeremiah
• Zhou Hongyi
• Mccloskey Patrick
• Rainka Matthew

Classifications

• B01D61/243

  Dialysis · CPC title

• B01D67/0009

  by phase separation, sol-gel transition, evaporation or solvent quenching · CPC title

• B01D69/08

  Hollow fibre membranes (manufacture of hollow fibres D01D5/24, D01F1/08) · CPC title

• C08G65/4056

  (I) or (II) containing sulfur (as the sulfone group C08G75/23) · CPC title

• B01D2325/36

  Hydrophilic membranes · CPC title