Membrane polymer compositions

• US 7,226,541 B2
• Filed: 12/16/2003
• Issued: 06/05/2007
• Est. Priority Date: 06/20/2001
• Status: Expired due to Term

• Current Assignee: Evoqua Water Technologies LLC (Xylem, Inc.)
• Original Assignee: Siemens Building Technologies Incorporated (Siemens AG)
• Inventors: Muller, Heinz-Joachim, Mullette, Daniel
• Primary Examiner(s): Fortuna; Ana
• Application Number:
  US10/738,628
• Publication Number:
  US 20040191894A1
• Time in Patent Office: 1,267 Days
• Field of Search: 210/500.36, 210/500.42, 210/500.23, 210/490, 210/321.89, 210/500.27, 264/41, 264/48, 264/49, 264/176.1, 264/177.1, 264/211.17, 264/177.8, 264/178.12, 264/177.19, 264/209.1, 264/211, 521/64, 521/134, 428/323
• US Class Current: 210/500.36
• CPC Class Codes: B01D 2323/02 Hydrophilization
• CPC Class Codes: B01D 2323/22 Specific non-solvents or non-solvent system
• CPC Class Codes: B01D 2325/0231 Dense layers being placed on the outer side of the cross-section
• CPC Class Codes: B01D 2325/30 Chemical resistance
• CPC Class Codes: B01D 67/0018 Thermally induced processes [TIPS]
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 71/32 containing fluorine atoms
• CPC Class Codes: B01D 71/34 Polyvinylidene fluoride
• CPC Class Codes: B01D 71/36 Polytetrafluoroethene

Abstract

The invention relates to a terpolymer of tetrafluoroethylene (TFE) monomer, polyvinylidene fluoride (PVDF) monomer and hexafluoropropylene (HFP) monomer for forming an ultrafiltration or microfiltration membrane, method of forming said membranes, and to the ultrafiltration or microfiltration membranes themselves. The invention also relates to a method of forming a polymeric ultrafiltration or microfiltration membrane including preparing a leachant resistant membrane dope which incorporates a leachable pore forming agent, casting a membrane from the dope and leaching the pore forming agent from the membrane. The invention also relates to a method of preparing a polymeric ultrafiltration or microfiltration membrane of improved structure including the step of adding a nucleating agent to the membrane dope before casting.

Claims

1. A membrane comprising:

a terpolymer of about 35 wt. % to about 40 wt. % of polyvinylidene fluoride monomer, from about 17 wt. % to about 20 wt. % of hexafluoropropylene monomer, and from about 40 wt. % to about 48 wt. % of tetrafluoroethylene monomer; and

a hydrophobicity modifying agent.

2. The membrane according to claim 1, wherein the terpolymer comprises about 36.5 wt. % of polyvinylidene fluoride monomer, about 18.9 wt. % of hexafluoropropylene monomer, and about 44.6 wt. % of tetrafluoroethylene monomer.

3. The membrane according to claim 1, the filtration membrane having an asymmetric cross section defining a large-pore face and a small-pore face, the membrane having a higher flux at a predetermined pressure from the large-pore face to the small-pore face than from the small-pore face to the large-pore face.

4. The membrane according to claim 1, wherein the filtration membrane comprises a hollow fiber.

5. The membrane according to claim 1, wherein the hydrophobicity modifying agent comprises a polyvinylethylether.

6. The membrane according to claim 1, wherein the membrane comprises about 2 wt. % of the hydrophobicity modifying agent.

7. A method of preparing a polymeric membrane comprising:

preparing a membrane dope resistant to a leachant, the membrane dope comprising a terpolymer derived from about 35 wt. % to about 40 wt. % of polyvinylidene fluoride monomer, about 17 wt. % to about 20 wt. % of hexafluoropropylene monomer, and about 40 wt. % to about 48 wt. % of tetrafluoroethylene monomer, and a leachable pore forming agent;

casting the membrane dope into the polymeric membrane; and

leaching the leachable pore forming agent from the polymeric membrane with the leachant.

8. The method according to claim 7, wherein the terpolymer comprises about 36.5 wt. % of repeating units derived from the polyvinylidene fluoride monomer, about 18.9 wt. % of repeating units derived from the hexafluoropropylene monomer, and about 44.6 wt. % of repeating units derived from the tetrafluoroethylene monomer.

9. The method according to claim 7, further comprising the step of adding a polyvinylethylether to the membrane dope as a hydrophobicity modifying agent.

10. The method according to claim 7, wherein the leachable pore forming agent comprises an inorganic solid having an average particle size of less than about 1 micron.

11. The method of claim 7, wherein the leachable pore forming agent comprises leachable silica, and wherein the leachant comprises a caustic solution.

12. A method of casting a polymeric membrane, the method comprising:

preparing a membrane dope comprising a terpolymer and a catalytic amount of a nucleating agent, wherein said terpolymer is derived from about 35 wt. % to about 40 wt. % of polyvinylidene fluoride monomer, from about 17 wt. % to about 20 wt. % of hexafluoropropylene monomer, and from about 40 wt. % to about 48 wt. % of tetrafluoroethylene monomer; and

casting a filtration membrane from the membrane dope.

13. The method according to claim 12, wherein the nucleating agent comprises an insoluble inorganic solid or an inert inorganic solid.

14. The method according to claim 12, wherein the nucleating agent has an average particle size of less than about 1 micron.

15. The method according to claim 12, wherein the nucleating agent comprises TiO₂.