Bipolar membranes and method of making same

• US 4,116,889 A
• Filed: 08/19/1976
• Issued: 09/26/1978
• Est. Priority Date: 08/19/1976
• Status: Expired due to Term

• Current Assignee: The Graver Company
• Original Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Inventors: Chlanda, Frederick P., Liu, Kang-Jen, Lee, Lester T. C.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Tungol, Maria S.
• Application Number:
  US05/715,765
• Time in Patent Office: 768 Days
• Field of Search: 260/2.1 R, 260/2.1 M, 204/180 P, 264/308, 427/385 B, 427/2, 428/520, 428/522, 428/421
• US Class Current: 204/631
• CPC Class Codes: B01J 47/12 characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes electrodialysis or electro-osmosis B01D61/42
• CPC Class Codes: C01B 7/035 Preparation of hydrogen chloride from chlorides
• CPC Class Codes: C01D 1/04 Hydroxides
• CPC Class Codes: C08J 2327/04 containing chlorine atoms
• CPC Class Codes: C08J 2327/12 containing fluorine atoms
• CPC Class Codes: C08J 5/2287 After-treatment
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31928 Ester, halide or nitrile of addition polymer
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

Stable bipolar membranes of high permselectivity and low potential drop are prepared using either an anion or cation preformed first layer upon which a second layer or coating of an ion exchange resin of the opposite charge carried in a matrix polymer is applied. The second layer may be suitably applied such as by casting as a slurry of the ion exchange resin in a solution or by laminating a layer comprising a dispersion of the resin in a solid or fused polymer. Optionally, the surface of the first layer may be treated to increase the resin concentration and/or bonding at the interface, such as by sanding, etching, etc.

Claims

1. A method for preparing bipolar membranes which comprises:

coating on (a) an ion exchange membrane, a fluid mixture of a dispersion of (b) particles of an ion exchange resin in (c) a matrix polymer where (b) has a charge opposite to the charge of (a); and

bonding said membrane and mixture to form a unitary bipolar membrane structure.

2. The method of claim 1 wherein said mixture (b) and (c) of ion exchange resin and matrix polymer is coated on membrane (a) as a slurry of the resin (b) in a solution of the matrix polymer and wherein the bonding thereof is effected by evaporation of the solvent from the slurry.

3. The method of claim 1 wherein the mixture of (b) ion exchange resin and (c) matrix polymer is coated and bonded as a melt on said membrane (a).

4. The method of claim 1 wherein (b) the ion exchange resin bonded to the membrane (a) has a particle size of less than one micron.

15. The product produced by the method of claim 1.

5. A method for preparing bipolar membranes which comprises coating on a membrane which is comprised of an inert polymeric matrix and an anion exchange crosslinked polyelectrolyte, a dispersion of cation exchange resin particles having a particle size of less than one micron diameter in a solution of a matrix polymer, and evaporating the solvent from the cation exchange resin solution to form a unitary bipolar membrane structure.

6. The method of claim 5 in which the polymeric matrix employed with the anion polyelectrolyte and the matrix polymer employed with the cation exchange resin are the same.

7. The method of claim 5 in which the cation exchange resin is crosslinked to at least an equivalent amount as obtained by crosslinking with at least 10% divinylbenzene.

8. The method of claim 5 in which the surface of the anion membrane is coated with a layer of dry crosslinked cation exchange resin before the cation exchange resin dispersion is applied.

9. The method of claim 5 in which the inert matrix is polyvinylidene fluoride.

10. A method for preparing bipolar membranes which comprises mixing a solution of polyvinylidene fluoride with a solution of polyvinylbenzyl chloride, generating quaternary ammonium groups by introducing into said mixture a multifunctional amine, casting the mixture as a film and evaporating the solvent to give an anion membrane, abrading the surface of said membrane, coating said abraded membrane with a dry cation exchange resin, and then with a suspension of cation exchange resin in a solution of polyvinylidene fluoride and evaporating the solvent to provide a unitary bipolar membrane structure.

16. The product produced by the method of claim 10.

11. A method for preparing bipolar membranes which comprises casting a solution of a copolymer which forms quaternary ammonium groups when reacted with a multifunctional amine and an amine or mixture of amines which is capable of forming quaternary ammonium groups by reaction with said copolymer, evaporating the solvent to give an anionic membrane, depositing on said membrane a dispersion of cation exchange resin in a solution of a matrix polymer and evaporating the solvent from the cationic resin solution to provide a unitary bipolar membrane structure.

12. The method of claim 11 in which one of the monomers of the copolymer is vinylbenzyl chloride.

13. The method of claim 11 in which the copolymer is comprised of styrene and vinylbenzyl chloride units.

14. The method of claim 11 in which said anionic membrane is abraded and coated with a dry cation exchange resin having a particle size of less than one micron before depositing said cation exchange resin in a solution of matrix polymer.

17. The product produced by the method of claim 11.