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US4954381A Expired / Lapsed US ⏱️ 0.0 years remaining

Preparation of porous substrates having well defined morphology

Assignee: Research Foundation of the State University of New York
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Filing: 1988-03-21
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Granted: 1990-09-04
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Expires: 2008-03-21
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Abstract

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.

Inventors

  • 👤 Israel Cabasso
  • 👤 Moshe Levy

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-02 23:28
CPC Classifications
B; B01; B01D; B01D67/00; B01D67/0002; B01D67/0006; B01D67/0023; B01D67/003; B01D69/00; B01D69/02; C; C08; C08J; C08J3/00; C08J3/005; C08J9/00; C08J9/28; B01D2323/00; B01D2323/12; B01D2323/40; C08J2201/00; C08J2201/04; C08J2201/05; Y; Y10; Y10S; Y10S260/00; Y10S260/31; Y10S424/00; Y10S424/07; Y10S977/00; Y10S977/70; Y10S977/773; Y10S977/788; Y10S977/84; Y10S977/895; Y10S977/896; Y10T; Y10T428/00; Y10T428/24; Y10T428/24149; Y10T428/29; Y10T428/2982; Y10T428/2984; Y10T428/2985; Y10T428/2987

Claims Analysis

Total Claims: 23
Claim 1
Independent Claim 295 words
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.
Claim 2
Independent Claim 295 words
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.
Claim 3
Dependent Claim 84 words
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.
Claim 4
Dependent Claim 26 words
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.
Claim 5
Dependent Claim 26 words
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.
Claim 6
Dependent Claim 28 words
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.
Claim 7
Dependent Claim 22 words
The process of claim 1 wherein said water-soluble polymer (A) has at least 5% by weight water-soluble groups on its polymer chain.
Claim 8
Dependent Claim 25 words
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.
Claim 9
Dependent Claim 23 words
The process of claim 1 wherein said water-soluble groups are selected from the group consisting of amino, silicone, hydroxy, carboxy and quaternary salts.
Claim 10
Dependent Claim 37 words
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.
Claim 11
Dependent Claim 22 words
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).
Claim 12
Dependent Claim 14 words
The process of claim 10 wherein said organic solvent for polymer (B) is toluene.
Claim 13
Dependent Claim 16 words
The process of claim 1 wherein said organic solvent for polymer (B) is an aromatic compound.
Claim 14
Dependent Claim 21 words
The process of claim 1 wherein said solvent for polymer (A) comprises water, methanol, or an aqueous solution of an alcohol.
Claim 15
Dependent Claim 144 words
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).
Claim 16
Dependent Claim 144 words
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).
Claim 17
Dependent Claim 16 words
The membrane of claim 14 in which said membrane is comprised of polymer (A) and (B).
Claim 18
Dependent Claim 27 words
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).
Claim 19
Dependent Claim 33 words
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%.
Claim 20
Dependent Claim 84 words
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.
Claim 21
Dependent Claim 38 words
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.
Claim 22
Dependent Claim 18 words
The membrane of claim 14 where an organic soluble polymer (A) is dispersed in a water-soluble polymer (B).
Claim 23
Dependent Claim 24 words
The membrane of claim 14 formed from a dispersion where both the dispersed and the continuous phases are in organic solvents of different polarities.

References Cited (Backward Citations)

US3377190A Cited
US3460972A Cited
US3567118A Cited
US4177256A Cited
US4064294A Cited
US4269713A Cited
US4402940A Cited

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