Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi)

Patent metadata

Field	Value
Publication number	US-9962662-B2
Application number	US-201414320454-A
Country	US
Kind code	B2
Filing date	Jun 30, 2014
Priority date	Jun 30, 2014
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

Disclosed is a fluorinated polymer of the formula: R—S—P, wherein R is a fluorocarbyl group, S is sulfur, and P is: (i) polyglycerol; (ii) poly(allyl glycidyl ether); (iii) a copolymer of glycidol and allyl glycidyl ether, the copolymer having one or more allyl groups; or (iv) poly(allyl glycidyl ether) or copolymer of glycidol and allyl glycidyl ether, wherein one more of the allyl groups have been replaced with a functional group as described herein. Also disclosed is a method of preparing the fluorinated polymer. The fluorinated polymer finds use in improving the hydrophilicity of porous hydrophobic membranes such as PTFE and PVDF.

First claim

The invention claimed is:

1. A fluorinated polymer of the formula: R—S—P, wherein R is a fluorocarbyl group, S is sulfur, and P is: (i) a copolymer of glycidol and allyl glycidyl ether, said copolymer having one or more allyl groups or (ii) poly(allyl glycidyl ether) or copolymer of glycidol and allyl glycidyl ether, wherein one more of the allyl groups have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH 2 ) a —S—(CH 2 ) b —X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula—C(H)(COOH)(NH 2 ), and a group of the formula—C(H)(COOH)(NHAc), or a salt thereof; wherein
the fluorinated polymer is hydrophilic such that when it is coated on a hydrophobic porous support shows a critical wetting surface tension greater than 72 dynes/cm.

2. The fluorinated polymer of claim 1 , where R is a fluorocarbyl group of the formula: C n F 2n+1 (CH 2 ) m− , wherein n and m are independently 1 to 20.

3. The fluorinated polymer of claim 2 , wherein n is 4 to 12 and m is 2 to 6.

4. The fluorinated polymer of claim 2 , wherein n is 8 and m is 2.

5. The fluorinated polymer of claim 1 , wherein the fluorocarbyl group is linear.

6. The fluorinated polymer of claim 1 , wherein P is a copolymer of glycidol and allyl glycidyl ether, said copolymer having one or more allyl groups.

7. The fluorinated polymer of claim 6 , wherein the copolymer comprises the following structure:

8. The fluorinated polymer of claim 1 , wherein P is a copolymer of glycidol and allyl glycidyl ether, said copolymer having one or more allyl groups, and the fluorinated polymer has the following structure:

9. A method of preparing a fluorinated polymer of the formula: R—S—P, wherein R is a fluorocarbyl group, S is sulfur, and P is: (i) a copolymer of glycidol and allyl glycidyl ether, said copolymer having one or more allyl groups or (ii) copolymer of glycidol and allyl glycidyl ether, wherein one more of the allyl groups have been replaced with 1,2-dihydroxypropyl group or a group of the formula: —(CH 2 ) a —S—(CH 2 ) b —X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula—C(H)(COOH)(NH 2 ), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof; the method comprising:
(i) providing a fluorocarbyl thiol; and
(ii) carrying out a ring opening polymerization of a mixture of glycidol and allylglycidyl ether on the fluorocarbyl thiol to obtain the fluorinated polymer where P is a copolymer of glycidol and allyl glycidyl ether, said copolymer having one or more allyl groups, and optionally
(iii) replacing one more of the allyl groups with 1,2-dihydroxypropyl group or a group of the formula: —(CH 2 ) a —S—(CH 2 ) b —X, wherein a is 3 and b is 1 to 3, and X is selected from an acidic group, a basic group, a cation, an anion, a zwitterion, halo, hydroxyl, acyl, acyloxy, alkylthio, alkoxy, aldehydo, amido, carbamoyl, ureido, cyano, nitro, epoxy, a group of the formula —C(H)(COOH)(NH 2 ), and a group of the formula —C(H)(COOH)(NHAc), or a salt thereof; wherein
the fluorinated polymer is hydrophilic such that when it is coated on a hydrophobic porous support shows a critical wetting surface tension greater than 72 dynes/cm.

10. A method of increasing the hydrophilicity of a hydrophobic polymer membrane comprising coating the hydrophobic membrane with a fluorinated polymer according to claim 1 .

11. The method of claim 10 , wherein the hydrophobic polymer membrane comprises a polymer selected from polytetrafluoroethylene, poly(vinylidene fluoride), copolymers of vinylidene fluoride, poly(chlorotrifluoroethylene), poly(fluoroethylene-propylene), poly(ethylene-chlorotrifluorethylene), poly(tetrafluoroethylene-co-hexafluoropropylene), pol(ethylene-tetrafluoroethylene), poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether), perfluoroalkoxy polymer, perfluoropolyether, polyvinylfluoride, and fluorinated ethylene-propylene.

12. The method of claim 10 , wherein hydrophobic polymer membrane comprises polytetrafluoroethylene or poly(vinylidene fluoride).

13. A hydrophilic fluoropolymer membrane comprising a coating of a fluorinated polymer according to claim 1 disposed on a hydrophobic fluoropolymer membrane.

14. The hydrophilic fluoropolymer membrane according to claim 13 , having a critical wetting surface tension greater than 72 dynes/cm.

15. A method of increasing the hydrophilicity of a hydrophobic polymer membrane comprising coating the hydrophobic membrane with a fluorinated polymer according to claim 8 .

16. A hydrophilic fluoropolymer membrane comprising a coating of a fluorinated polymer according to claim 8 disposed on a hydrophobic fluoropolymer membrane.

Assignees

• Pall Corp

Inventors

• Ait-Haddou Hassan
• Onyemauwa Frank

Classifications

• B01D2323/02

  Hydrophilization · CPC title

• C08G75/00

  Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule · CPC title

• B01D71/32

  containing fluorine atoms · CPC title

• C08G2650/54

  Polyglycerols · CPC title

• C08G65/14

  Unsaturated oxiranes · CPC title