Preparation of porous substrates having well defined morphology

• US 4,954,381 A
• Filed: 03/21/1988
• Issued: 09/04/1990
• Est. Priority Date: 12/30/1986
• Status: Expired due to Fees

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: Levy, Moshe, Cabasso, Israel
• Primary Examiner(s): Lovering, Richard D.
• Application Number:
  US07/171,497
• Time in Patent Office: 897 Days
• Field of Search: 264/4.6, 264/216, 428/402.21, 428/402.22, 428/116, 424/DIG. 7, 260/DIG. 31, 427/245, 427/246, 210/500.21, 210/500.22
• US Class Current: 428/116
• CPC Class Codes: B01D 2323/12 Specific ratios of components used
• CPC Class Codes: B01D 2323/40 in-situ membrane formation
• CPC Class Codes: B01D 67/0004 by agglomeration of particles
• CPC Class Codes: B01D 67/0006 by chemical reactions in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125
• CPC Class Codes: B01D 67/003 by selective elimination of components, e.g. by leaching
• CPC Class Codes: B01D 69/02 characterised by their properties
• CPC Class Codes: C08J 2201/05 Elimination by evaporation or heat degradation of a liquid phase
• CPC Class Codes: C08J 3/005 Processes for mixing polymers
• CPC Class Codes: C08J 9/28 by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
• CPC Class Codes: Y10S 260/31 Ionic cross-link
• CPC Class Codes: Y10S 424/07 Microporous membranes
• CPC Class Codes: Y10S 977/773 Nanoparticle, i.e. structure having three dimensions of 100 nm or less
• CPC Class Codes: Y10S 977/788 Of specified organic or carbon-based composition
• CPC Class Codes: Y10S 977/896 Chemical synthesis, e.g. chemical bonding or breaking
• CPC Class Codes: Y10T 428/24149 Honeycomb-like
• CPC Class Codes: Y10T 428/2985 Solid-walled microcapsule from synthetic polymer
• CPC Class Codes: Y10T 428/2987 Addition polymer from unsaturated monomers only

Abstract

A membrane of defined pore structure and controlled pore diameter and a method of preparing the membrane which comprises dispersing in a water soluble polymer solution (A) an organic polymer solution (B), the water-soluble polymer solution (A) being a non-solvent for the polymer solution (B), to form micro-spherical droplets of the polymer solution (A) which are enveloped by a solid phase consisting of a coagulated or cross-linked polymer solution (B); evenly casting the dispersion on a flat surface; and evaporating the solvent for the polymer solution (B) to form a microporous membrane comprised of the polymer (B), the porosity, pore size, and void volume of the microporous membrane being a function of the polymer (A) concentration, the microsphere dimensions and the temperature and evaporation rate. The water-soluble polymer (A) is selected from polyethyleneimine, gelatin, polyvinyl-pyrrolidone, polyvinyl pyridinium halide, polyacrylic acid, polyhydroxyethylmethacrylate (HEMA), dextran, or polyvinyl acetate. The continuous phase polymer (B) is selected from a brominated polyphenylene oxide, polyphenylene oxide, polyacetic acid, polystyrene, polyglycol acrylate (PGA), polymethylmethacrylate, cellulose acetate, polyvinyl acetate, polycarbonate and polyvinylidene fluoride.

Claims

1. A method of making a microporous membrane having a preselected pore structure, the diameters of the pores being within a preselected range, the method comprising:

a. providing a solution of polymer (A) in an organic solvent, said polymer (A) having at least about 5% by weight of one or more water-soluble groups on its polymer chain or pendant to the backbone of the polymer (A) and also having one or more functional groups capable of reacting, complexing or polymerizing with polymer (B);

b. providing a solution of a polymer (B) in an aqueous solution which is immiscible in said organic polymer (A) solution, said polymer (B) having at least about 5% by weight of at least one functional group which can react, complex, or polymerize with polymer (A), or, said polymer (B) is capable of coagulating in the presence of polymer (A);

c. uniformly dispersing the organic polymer (B) solution in the water-soluble polymer (A) solution to form a multiplicity of micro-spherical droplets of the polymer (A) solution enveloped by a skin composed of the product of reaction of polymers (A) and (B) or the coagulated polymer (B), said polymer (A) solution droplets being uniformly dispersed within a continuous phase comprised of said organic polymer (B) solution;

d. evaporating the organic solvent to form a honeycomb-like structure comprised of said micro-spherical droplets uniformly dispersed within and held together by a solid continuous phase of said polymer (B); and

e. dehydrating the honeycomb-like structure which cracks the exposed surfaces of the micro-spherical droplets and forms the microporous membrane comprised of a solid continuous phase of polymer (B) having a network of pores uniformly dispersed therein, with no overlapping pores, the pores at the surface having preselected sizes between about submicron and about 10 microns in diameter.

2. The process of claim 1 wherein said polymer (B) comprises a polymer having one or more functional groups in its polymer chain which can react with polymer (A) to form a copolymer of polymer (A) and polymer (B), the functional groups of polymer (B) selected from the group consisting of an isocyanate;

a polyanhydride, and --COX, wherein X is a halide or --OM, wherein M is an alkali metal, alkylammonium of 1 to 4 carbon atoms or alkanolammonium of 1 to 4 carbon atoms.

3. The process of claim 2 wherein polymer (B) is selected from the group consisting of a brominated polyphenylene oxide, polylactic acid, chloromethylated polystyrene and polyglycol acetate.

4. The process of claim 1 where said polymer (B) comprises a polymer which coagulates and forms a precipitate in the presence of the polymer (A) solution.

5. The process of claim 4 wherein said polymer (B) is selected from the group consisting of polyphenylene oxide, polystyrene, polymethylmethacrylate, cellulose acetate, polyvinyl acetate, polycarbonate and polyvinylidene fluoride.

6. The process of claim 1 wherein said water-soluble polymer (A) has at least 5% by weight water-soluble groups on its polymer chain.

7. The process of claim 1 wherein said water-soluble polymer (A) has at least 5% by weight water-soluble groups pendent to the backbone of the polymer.

8. The process of claim 1 wherein said water-soluble groups are selected from the group consisting of amino, silicone, hydroxy, carboxy and quaternary salts.

9. The process of claim 1 wherein said water-soluble polymer (A) is selected from the group consisting of polyoxyisophthaloyl, polyethylenimine, gelatin, polyvinyl-pyrrolidone, polyvinyl pyridinium halide, amino dimethylsiloxane, polyacrylic acid, polyhydroxyethylmethylacrylate (HEMA), dextran, polyvinyl alcohol, and their copolymer derivatives.

10. The process of claim 1 wherein said functional group(s) of polymer (A) is the same as the water-soluble group(s) of polymer (A).

11. The process of claim 10 wherein said organic solvent for polymer (B) is toluene.

12. The process of claim 1 wherein said organic solvent for polymer (B) is an aromatic compound.

13. The process of claim 1 wherein said solvent for polymer (A) comprises water, methanol, or an aqueous solution of an alcohol.

14. A microporous membrane having a preselected pore structure, the diameter of the pores being within a preselected range, said membrane comprised of a solid continuous phase of polymers (A) and (B) configured to have a bee-hive morphology defining a network of pores, with no overlapping pores, the pores at the surface having preselected sizes between submicron and about 10 microns in diameter said polymer (A) having at least about 5% by weight of one or more water-soluble groups on its polymer chain or pendant to its back-bone and also having one or more functional groups capable of reacting, complexing or polymerizing with polymer (B), and said polymer (B) having at least about 5% by weight of at least one functional group which can react, complex or polymerize with polymer (A), or said polymer (B) being capable of coagulating in the presence of polymer (A).

15. The membrane of claim 14 in which said membrane is comprised of polymer (A) and (B).

16. The membrane of claim 14 wherein the composite polymer (A) and (B) becomes insoluble in either a solvent for polymer (A) or a solvent for polymer (B).

17. The membrane of claim 14 wherein the membrane is asymmetric and the skin contains fairly uniform holes that can range from 0.01 micrometer to 10 micrometer in diameter with a deviation of ±

50%.

18. The membrane of claim 14 wherein said polymer (B) comprises a polymer having one or more functional groups in its polymer chain which can react with polymer (A) to form a copolymer of polymer (A) and polymer (B), the functional groups of polymer (B) selected from the group consisting of an isocyanate;

a polyanhydride, and --COX, wherein X is a halide or --OM, wherein M is an alkali metal, alkylammonium of 1 to 4 carbon atoms or alkanolammonium of 1 to 4 carbon atoms.

19. The membrane of claim 14 wherein said water-soluble polymer (A) is selected from the group consisting of polyoxyisophthaloyl, polyethyleneimine, polyamines, gelatin, polyvinyl-pyrrolidine, polyvinyl pyridinium halide, polyamino methylsiloxane, polyacrylic acid, polyhydroxyethylmethylacrylate (HEMA), dextran, polyvinyl alcohol, and their copolymer derivatives.

20. The membrane of claim 14 where an organic soluble polymer (A) is dispersed in a water-soluble polymer (B).

21. The membrane of claim 14 formed from a dispersion where both the dispersed and the continuous phases are in organic solvents of different polarities.