Method of making single film, high performance bipolar membrane

• US 4,140,815 A
• Filed: 04/26/1977
• Issued: 02/20/1979
• Est. Priority Date: 12/31/1975
• Status: Expired due to Term

• Current Assignee: The Graver Company
• Original Assignee: Allied Chemical Corporation (Honeywell International Inc.)
• Inventors: Dege, Gerald J., Liu, Kang-Jen
• Primary Examiner(s): Newsome, John H.
• Application Number:
  US05/791,088
• Time in Patent Office: 665 Days
• Field of Search: 204/296, 204/180 P, 427/44, 427/337, 427/340, 427/372 R, 427/385 B
• US Class Current: 427/498
• CPC Class Codes: C08J 2353/02 of vinyl aromatic monomers and conjugated dienes
• CPC Class Codes: C08J 5/2243 obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
• CPC Class Codes: C08J 5/2287 After-treatment

Abstract

Novel single film bipolar membranes, of substantially improved efficiency and durability, i.e. having an ion selectivity above 80% in an electrolyte medium of about one mole, are prepared from pre-swollen films containing a relatively high amount, i.e. at least 15% of an insoluble cross-linked aromatic polymer. Under controlled conditions, highly dissociable cationic-exchange groups are chemically bonded to the aromatic nuclei to a desired depth of the film from one side only; subsequently, highly dissociable anion-exchange groups are chemically bonded to the unreacted aromatic nuclei on the other side of the film. The functionalized, densely structured single film ion exchange membrane undergoes negligible degradation, is blister free, and is uniquely suited for electrodialysis particularly water-splitting operations due to its low electrical resistance and low salt leakage. The membrane operates with improved current efficiencies at both high electrolyte concentrations and high current densities, for time periods not previously achievable.

Claims

1. A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polymeric matrix film derived from monomers selected from the group consisting of ##STR6## wherein R₁ to R₇ are substituents selected from the group consisting of hydrogen, chlorine, fluorine, alkyl radicals of 1 to 5 carbon atoms and phenyl radicals and copolymers thereof, and chlorinated and fluorinated polymers and copolymers thereof;

uniformly with an aromatic nuclei containing monomer selected from those having the formula ##STR7## wherein R₈, R₉ and R₁₀ are substituents from the group consisting of hydrogen, alkyl radicals of 1 to 4 carbon atoms, phenyl substituted alkyl radicals of 2-4 carbon atoms, phenyl, phenoxy-, thiophenoxy, and naphthyl radicals and the hydroxyl, alkoxyl, and halo substituted phenyl, phenoxy, thiophenoxy, and naphthyl radicals and wherein at least one substituent is an aromatic radical, and polymerizing and cross-linking said impregnated film to an extent equivalent to that obtained by cross-linking a 2 to 20 percent mixture of a 55 percent divinyl benzene in styrene, to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked aromatic nuclei containing polymer within the film;

removing essentially all excess aromatic polymerizate from the surface of said film;

preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a solvent system supplying cationic functional groups for a period of time sufficient to render the aromatic nuclei readily accessible thereto thereafter chemically bonding highly dissociable cation exchange groups to the aromatic nuclei from one side of said film to a depth of not more than about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both the anionic and cationic functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.

2. The process of claim 1 wherein the matrix film is polyethylene.

3. The process of claim 1 wherein the matrix film is polypropylene.

4. The process of claim 1 wherein the matrix film is a polyethylene-polypropylene copolymer.

5. The process of claim 1 wherein the matrix film is polytrifluorochloroethylene.

6. The process of claim 1 wherein the initial matrix film to be impregnated with the aromatic nuclei containing monomer, has a thickness of from about 0.5 to about 20 mils.

7. The process of claim 1 wherein the concentration of the aromatic nuclei containing polymer comprises from about 15% to about 70% based on the total weight of the membrane.

8. The process of claim 1 wherein the mole ratio of the aromatic nuclei containing monomer to the di- or poly-functional cross-linking compound in the initial monomer mixture is less than 125/1.

9. The process of claim 1 wherein the initial polymeric film is cross-linked by electron beam radiation to a degree equivalent to that obtained from a styrenation mixture comprised of styrene and divinylbenzene in a mole ratio from 14 to 1 to 125 to 1, respectively.

10. The process of claim 1 wherein before polymerization excess liquid polymerizate is wiped from the films surface and after polymerization the last traces of solidified polymerizate are removed from the films surface with a solvent selected from the group consisting of carbon tetrachloride, chloroform, methylene chloride, 1,2-dichloroethane, 1,2-trichloroethane, 1,1,2,2-tetrachloroethane, dimethyl formamide, dimethyl acetamide, decalin, tetralin, and cyclohexane.

11. The process of claim 1 wherein the highly dissociable cationic groups are sulfonic acid groups and prior to sulfonation the polymeric film containing the insoluble, cross-linked aromatic polymer is preswollen in a solvent inert to but miscible with the sulfonating reagent or its mixture for a time period sufficient to render the aromatic nuclei readily accessible to the sulfonating reagent.

12. The process of claim 11 wherein the pre-swelling solvent is selected from the group consisting of carbon tetrachloride, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, dimethyl formamide, dimethyl acetamide, decalin, tetralin, and cyclohexane.

13. The process of claim 1 wherein the highly dissociable cation exchange group is the sulfonic acid group, obtained with sulfonating agents selected from the group comprised of sulfonic acid, SO₃, oleum, chlorosulfonic acid, or mixtures thereof.

14. The process of claim 1 wherein the sulfonic acid cation exchange group is obtained by chlorosulfonating with a solution of chlorosulfonic acid in carbon tetrachloride with at least 53% chlorosulfonic acid by volume and thereafter hydrolyzing the sulfonated reaction produced.

15. The process of claim 1 wherein the cationic functional groups are derived by chlorosulfonation and the chlorosulfonating agent comprises a mixture of chlorosulfonic acid and dichloroethane.

16. The process of claim 1 wherein the cationic functional groups are derived by chlorosulfonation and the chlorosulfonating agent comprises a mixture of chlorosulfonic acid and trichloroethane.

17. The process of claim 1 characterized in that the anionic functional groups are quaternary trimethyl amine anionic exchange groups obtained by chloromethylation of the film with reagents selected from the group consisting of (a) SO₂ Cl₂ with methylal and a Friedel-Crafts catalyst, (b) formaldehyde and hydrochloric acid and (c) chloromethyl methylether and tin tetrachloride;

followed by quaternization with an organic solution of a trialkyl amine.

18. The process of claim 1 wherein chloromethylation is accomplished with chloromethylmethylether containing from about 1-5 weight percent SnCl₄.

19. The process of claim 1 wherein the chloromethylated film is substantially converted to highly dissociated anion exchange groups by quaternization with trimethylamine.

20. A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film;

removng essentially all excess polymerizate from the surface of said film;

preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.

21. A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polypropylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film;

removing essentially all excess polymerizate from the surface of said film;

preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.

22. A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polytrifluoro chloroethylene film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film;

removing essentially all excess polymerizate from the surface of said film;

preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.

23. A process for the manufacture of a durable, high performance, single film bipolar membrane comprising impregnating a polyethylene-polypropylene copolymer film uniformly with a mixture of styrene monomer and a di- or poly-functional cross-linking agent, subsequently polymerizing said impregnated mixture to obtain at least 15 percent by weight based on the total weight of the film, of the cross-linked polystyrene within the film;

removing essentially all excess polymerizate from the surface of said film;

preswelling without substantially dissolving said cross-linked film in a solvent substantially inert to but miscible with a cationic functional group sulfonation reagent, for a period of time sufficient to render the aromatic nuclei of the polystyrene readily accessible to the sulfonating reagent, thereafter chemically bonding highly dissociable sulfonic groups to the aromatic nuclei from one side of said film to a depth of from about 50% to about 98% of the films thickness and thereafter chemically-bonding highly dissociable anionic exchange groups to the remaining aromatic nuclei on the opposite side of said film, and wherein the concentration of both functional groups is at least substantially equal and greater than 1.4 meg/g. of dry resin.