Semi-permeable membranes prepared via reaction of cationic groups with nucleophilic groups

• US 4,797,187 A
• Filed: 08/17/1987
• Issued: 01/10/1989
• Est. Priority Date: 10/22/1985
• Status: Expired due to Fees

• Current Assignee: The Dow Chemical Company (Dow, Inc.)
• Original Assignee: The Dow Chemical Company (Dow, Inc.)
• Inventors: Davis, Thomas E., Wessling, Ritchie A., Pickelman, Dale M., Fibiger, Richard F., Schmidt, Donald L., Kau, Jee I., Whipple, Sharon S.
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Gorgos, Kathryn
• Application Number:
  US07/086,123
• Time in Patent Office: 512 Days
• Field of Search: 204/296, 204/180.2, 204/180.9, 204/181.1, 204/181.4, 204/181.6, 204/181.7, 521/28, 521/27, 521/31-33, 427/243, 427/245, 427/301, 427/333, 264/340
• US Class Current: 427/58
• CPC Class Codes: B01D 2323/30 Cross-linking
• CPC Class Codes: B01D 67/0088 Physical treatment with compounds, e.g. swelling, coating or impregnation
• CPC Class Codes: B01D 67/0093 Chemical modification
• CPC Class Codes: B01D 67/00933 by addition of a layer chemically bonded to the membrane
• CPC Class Codes: B01D 69/08 Hollow fibre membranes manufacture of hollow fibres D01D5/24, D01F1/08
• CPC Class Codes: B01D 69/125 In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
• CPC Class Codes: B01D 69/14 Dynamic membranes
• CPC Class Codes: B01D 71/40 Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
• CPC Class Codes: B01D 71/401 Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
• CPC Class Codes: B01D 71/44 Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
• CPC Class Codes: B01D 71/46 Epoxy resins
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5211 Polyethylene glycol or polyethyleneoxide
• CPC Class Codes: B01D 71/68 Polysulfones; Polyethersulfones
• CPC Class Codes: B01D 71/72 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
• CPC Class Codes: B01D 71/80 Block polymers
• CPC Class Codes: B01D 71/82 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• CPC Class Codes: Y10T 428/249953 Composite having voids in a component [e.g., porous, cellular, etc.]
• CPC Class Codes: Y10T 428/249958 Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249965 Cellulosic
• CPC Class Codes: Y10T 428/249972 : Resin or rubber element
• CPC Class Codes: Y10T 428/249978 : Voids specified as micro

Abstract

A novel composite membrane and methods of making the membrane are described. The discriminating layer of the membrane is prepared by reaction of a reactive cationic compound group with a compound bearing a nucleophilic moiety. At least one of the reactants bears an average of two or more reactive groups. The reaction product contains covalent bonds formed via charge eliminating reactions.

In a preferred embodiment of the invention, the nucleophilic group is anionic and a coacervate is formed initially on a microporous substrate. The resulting membrane may be useful for reverse osmosis, gas or ultrafiltration separations.

Claims

1. Method of improving the selectivity of a semi-permeable membrane comprising:

(a) contacting the membrane with a first reactive, ionic compound in an aqueous diluent while maintaining chemical potential gradient so as to deposit the ionic compound on membrane surface; and

(b) maintaining chemical potential gradient while contacting the membrane in an aqueous diluent with a second reactive, ionic compound of a charge opposite to the first compound, so as to form a coacervate.

2. The method as described in claim 1 further comprising subjecting the membrane to reactive conditions so as to convert a plurality of ionic bonds in the coacervate layer to covalent bonds.

3. The method as described in claim 2 wherein the chemical potential gradient is due to a pressure differential applied across the semi-permeable membrane which results in water being transported through the membrane.

4. The method as described in claim 2 wherein the coacervate forming compounds are deposited on the semipermeable membrane by an electrical gradient maintained across the semipermeable membrane in an aqueous solution.

5. The method as described in claim 2 wherein either the first or second reactive compound bears a plurality of ionic groups selected from the group consisting of sulfonium, quaternary ammonium, phosphonium, pyridinium, thiazolinium, imidazolinium and diazonium.

6. The method as described in claim 2 wherein either the first or second reactive compound bears a plurality of ionic groups selected from the group consisting of thioarylates, thioalkylates, arylates, alkylates and carboxylates.

7. The method as described in claim 5 wherein the ionic groups are sulfonium groups.

8. The method as described in claim 7 wherein the reactive compound is a vinyl addition polymer containing at least 10 percent by weight of the reaction product of an ethylenically unsaturated monomer bearing at least one sulfonium group.

9. The method as described in claim 8 wherein the sulfonium-containing monomer corresponds to the formula ##STR57## wherein R¹ at each occurrence is independently a monovalent hydrocarbon radical, a monovalent inertly-substituted hydrocarbon radical or both R¹ groups together with --S⁺ form a 5-, 6- or 7-member ring and A is a compatible anion.

10. The method as described in claim 9 wherein both R¹ groups together form a butylene.

11. The method as described in claim 9 wherein R¹ is methyl at each occurrence.

12. The method as described in claim 9 wherein the remainder of the vinyl addition polymer is derived from monomers selected from the group consisting of monomers corresponding to the formula ##STR58## wherein F is a C₁ to C₂₀ alkyl, C₁ to C₂₀ hydroxyalkyl or corresponds to the formula ##STR59## and m is an integer from 1 to 20.

13. The method as described in claim 9 wherein the remainder of the vinyl addition polymer is derived from monomers selected from the group consisting of acrylamide, methacrylamide, styrene sulfonic acid, butadiene, isoprene, alkyl cyanoacrylate, vinyl benzyl chloride and its derivatives, styrene sulfonamide, vinyl acetate, acrylamide, methacrylamide, vinyl pyrrolidone and 2-sulfoethyl methacrylate, acrylonitrile, (C₁ to C₂₀ alkyl) methacrylates, (C₁ to C₂₀ alkyl) acrylate, (C₂ to C₂₀ hydroxyalkyl) methacrylates, p-tert-butylstyrene, p-tert-butyl-(α

-methyl)styrene, dicyclopentenyl acrylate, isobornyl acrylate, isobornyl methacrylate and dicyclopentenyl methacrylate.

14. The method as described in claim 7 wherein the reactive compound bearing a charge opposite the compound bearing sulfonium groups is a vinyl addition polymer bearing a plurality of carboxylate groups.

15. The method as described in claim 14 wherein the carboxylate polymer is derived from monomers corresponding to the formulae ##STR60## wherein G⁺ is Na⁺, K⁺, NH₄⁺ or other compatible cation and F is a C₁ to C₂₀ alkyl, C₂ to C₂₀ hydroxyalkyl or corresponds to the formula ##STR61## wherein m is an integer from 1 to 20.

16. The method as described in claim 3 wherein the semi-permeable membrane is selected from the group consisting of cellulose acetate, polysulfone and polyamide.

17. The method as described in claim 2 wherein the semi-permeable membrane is cellulose triacetate and further comprising removing essentially all water from the membrane by solvent extraction or freeze drying following Step (b).

18. The method as described in claim 12 wherein the charge density of the second reactive compound is greater than the charge density of the first reactive compound.

19. The method as described in claim 16 wherein either the first or second reactive compound is a vinyl addition polymer containing at least about 1 mole percent of methacrylic acid, acrylic acid or crotonic acid.

20. The method as described in claim 19 wherein the polymer is derived from about 75 to about 99 mole percent vinyl acetate and a remaining amount of crotonic acid.

21. The method as described in claim 19 wherein the polymer contains about 1 to about 50 mole percent methacrylic acid and a remaining amount of ethylenically unsaturated monomers selected from hydroxyethyl methacrylate, C₁ to C₂₀ alkyl methacrylate or a compound corresponding to the formula ##STR62## wherein n is an integer from 2 to 21.

22. The method as described in claim 21 wherein the methacrylic acid polymer is the first reactive compound and the second reactive compound is a vinyl addition polymer derived from:

(a) about 1 to about 50 mole percent of a monomer corresponding to the formula ##STR63## wherein R¹ at each occurrence is a C₁ to C₄ alkyl or both R¹ groups together with --S+<

form a 5-, 6- or 7-membered ring and A^- is a compatible anion and (b) a remaining amount of one or more methacrylate or acrylate esters or monomers of the formula ##STR64## wherein D is a C₈ to C₂₀ or ##STR65##

23. The method as described in claim 22 wherein the methacrylate ester is hydroxyethyl methacrylate.

24. The method as described in claim 23 further comprising contacting the membrane after Step (b) with the first reactive ionic compound in an aqueous diluent while maintaining a chemical potential gradient.

25. The method as described in claim 21 wherein the methacrylic acid polymer is the second reactive compound and the first reactive compound is a vinyl addition polymer derived from:

(a) about 1 to about 50 mole percent of a monomer corresponding to the formula ##STR66## wherein R¹ at each occurrence is a C₁ to C₄ alkyl or both R¹ groups together with --S<

+ form a 5-, 6- or 7-membered ring and A^- is a compatible anion and (b) a remaining amount of one or more methacrylate or acrylate esters or monomers of the formula ##STR67## wherein D is a C₈ to C₂₀ alkyl or ##STR68##

26. The method as described in claim 25 wherein the methacrylate ester is hydroxyethyl methacrylate.