Method of producing a membrane

Abstract: A method of producing a membrane comprises providing a solution containing a plurality of polymers in a non-aqueous liquid solvent, at least one of the polymers (hereinafter referred to as the "first polymer") having been prepared by polymerizing at least one vinyl or acrylic monomer, at least one other of the polymers being a membrane-forming hydrophobic polymer (hereinafter referred to as the "second polymer"), the first polymer and the second polymer being mutually incompatible in said solution, and contacting the solution with an aqueous medium thereby to precipitate the polymers from the solution to form the membrane.

Description: The present invention relates to a method of producing a membrane. In particular, but not exclusively, the invention relates to a method of producing a membrane useful for filtration, especially nano-filtration and ultra filtration. Membranes made from hydrophobic polymers, such as aryl sulphones and PVDF, have been used in a variety of industries for many years. Although such membranes tend to be mechanically and chemically more robust that membranes made from hydrophilic polymers, such as cellulose acetate and polyacrylonitrile, their usefulness is often limited by their susceptibility to fouling as a result of ad- and absorption of material from solution being processed. In a first aspect the present invention provides a method of producing a membrane comprising providing a solution containing a plurality of polymers in a non-aqueous liquid solvent, at least one of the polymers (hereinafter referred to as the "first polymer") having been prepared by polymerizing at least one vinyl or acrylic monomer, at least one other of the polymers being a membrane-forming hydrophobic polymer (hereinafter referred to as the "second polymer"), the first polymer and the second polymer being mutually incompatible in said solution, forming the solution into the desired shape of the membrane, and contacting the solution formed into said shape with an aqueous medium thereby to precipitate the polymers from the solution to form the membrane. The first polymer may be formed in situ i.e. by incorporating into the solvent at least one vinyl or acrylic monomer and polymerizing the monomer in the solvent. Instead of the first polymer being produced by in situ polymerisation it may be added to the solution of the second polymer with stirring or agitation to produce the solution comprising the plurality of polymers. The second polymer preferably includes at least one polymer selected from polysulphones, polyethersulphones and PVDFs. The invention enables the fouling resistance of nano- and ultra-filtration membranes made from hydrophobic polymers to be improved without sacrificing their superior chemical and mechanical properties. Polymerisation of the vinyl or acrylic monomer may be achieved by a chemical initiator or by exposure of the solution to light, such as daylight, with or without the incorporation of a photoinitiator into the solution. The solution comprising the polymers may be an emulsion, preferably a stable emulsion, comprising the first polymer evenly dispersed therein and with the second polymer being dissolved in the solvent. The vinyl or acrylic monomer may be 2-hydroxymethylacrylate, which gives a hydrophilic first polymer, or methyl or ethyl methacrylate, both of which give a less hydrophilic first polymer. The aqueous medium may be water. The solution should be in a desired shape as it contacts the aqueous medium in order to ensure that the membrane produced is of the required shape. To this end the solution is generally formed into the desired shape prior to contact with the aqueous medium and maintained in that shape as it contacts the aqueous medium or is formed into the desired shape as it contacts the aqueous medium. The membrane may be required to be in the form of a flat sheet or in the form of a tube. The solution may be coated onto a substrate or support prior to contact with the aqueous medium so that the membrane is formed on the substrate or support. If the substrate or support is pervious or porous the membrane may be left on the substrate or support when used for filtration. Alternatively if the substrate or support is impervious it will be necessary to remove the membrane from the substrate or support before using the membrane for filtration. If the membrane is to be in the form of a hollow fibre or tube the solution may be introduced into the aqueous medium by spinning through a spinneret or by use of a casting bob. Alternatively, for the purpose of producing a tubular membrane, the substrate or support may be in the form of a tube and the membrane may be formed on the inside or outside of the tube. The first polymer is preferably present in the solution in an amount not exceeding 20% by weight based on the weight of the second polymer otherwise the membrane produced tends to compact under pressure. The concentration of the first polymer in solution is preferably 1% to 5% by weight. The concentration of the second polymer in solution is preferably 15 to 30% by weight. The coating is preferably applied to the substrate in a thickness of 0.12 mm to 0.51 mm. The substrate is preferably of a non-woven material. In a second aspect the invention provides a membrane comprising a vinyl or acrylic polymer dispersed in a hydrophobic polymer obtainable by a method according to the invention, and either not carried on a substrate or carried on a pervious or porous substrate. Such a membrane, when not carried on a substrate, may be in the form of a hollow fibre. The hydrophobic polymer may comprise at least one polymer selected from polysulphones, polyethersulphones and PVDFs. Given below are a comparative example and examples illustrating the invention. Comparative example 23 g of Victrex P5200 polyethersulphone were dissolved in a mixture of 55 g of N methyl-pyrrolidone and 22 g of 2-pyrrolidone at ambient temperature. A thin layer (0.025mm (0.010") thick) of the resulting solution was spread on the inside of a porous support tube of non-woven material (polyethylene). The coated tube was then held in air at ambient temperature for 30 seconds prior to immersion in immersion in tap water at 12° C. After 30 minutes the support tube with its membrane was removed from the gelation bath and washed for I hour in running tap water to remove residual solvent prior to testing. Victrex P5200 was a commercial grade of polyethersulphone made by ICI. Tubular membranes were prepared in the same manner from the following solutions:- Example 1 5.0 g of methyl methacrylate, 0.1 g á-azo-iso-butyronitrile and 0.5 g of the surfactant Ethylan HB4 were added to 100 g of a solution prepared in accordance with the comparative example above. The resulting solution was then held at 50 to 55 °C for 24 hours. Example 2 5.0 g of methylmethacrylate and 0.5 g of the surfactant Ethylan HB4 were added to 100 g of a solution prepared in accordance with the comparative example above. The solution was then exposed to daylight for a total of 24 hours at room temperature. Example 3 5.0 g of ethyl methacrylate and 0.5 g of the surfactant Ethylan HB4 were added to 100 g of a solution prepared in accordance with the comparative example above. The solution was then exposed to daylight for a total of 24 hours at room temperature. Example 4 2.0 g of 2-hydroxyethyl methacrylate and 0.1 g á-azo-iso-butyronitrile were added to 100 g of a solution prepared in accordance with the comparative example above. The resulting solution was then held at 50 to 55 °C for 24 hours. Example 5 2.0 g of hydroxypropyl methacrylate and 0.1 g á-azo-iso-butyronitrile were added to 100 g of a solution prepared in accordance with the comparative example above. The resulting solution was then held at 50 to 55 °C for 24 hours. Example 6 5.0 g of 1-vinylimidazole and 0.05 g α-azo-iso-butyronitrile were added to 100 g of a solution prepared in accordance with the comparative example above. The resulting solution was then held at 50 to 55 °C for 24 hours. Example 7 5.0 g of 2-hydroxyethyl methacrylate were added to 100 g of a solution prepared in accordance with the comparative example above. The solution was then exposed to daylight for a total of 24 hours at room temperature. Example 8 5.0 g of 2-hydroxyethyl methacrylate and 0.5 g of the surfactant Ethylan HB4 were added to a pre-prepared solution containing 25.0g of the polysulhpone Udel P1700 and 69.5 g N-methylpyrrolidone. The solution was then exposed to daylight for a total of 24 hours at room temperature. Details of the above monomers and polymers are as follows: CAS Number Formula Monomers 2-hydroxyethyl methacrylate 868-77-9 H 2 C=C(CH 3 )CO 2 CH 2 CH 2 OH hydroxypropyl methacrylate 27813-02-1 H 2 C=C(CH 3 )CO 2 C 3 H 6 OH acrylic acid 79-10-7 H 2 C=CHCO 2 H Polymers Poly(methyl methacrylate) 9011-14-7 [-H 2 C-C(CH 3 )CO 2 CH 3 )-] n Poly(2-hydroxyethyl methacrylate) 25249-16-5 [-H 2 C-C(CH 3 )CO 2 CH 2 CH 2 OH-] n Membrane testing. Table 1 below details the test results obtained for membranes prepared in accordance with Examples 1 to 7. The membranes, left on the support tubes on which they were formed, were run for 0.5 hours at the stated conditions on re-circulated feed solutions prior to measuring their performance. The % solute passages for Examples 4 to 9 are based on conductivity measurements. Example Test solute Test pressure Flux ( 1/m 2 hr, 15°C) % solute passage Comparative 150 ppm Pharmacia 70k dextran 3.0 73.6 64.4 1 150 ppm Pharmacia 70k dextran 3.0 150.0 76.5 2 150 ppm Pharmacia 70k dextran 3.0 110.0 27.4 3 150 ppm Pharmacia 70k dextran 3.0 133.0 70.9 4 5000 ppm MgSO 4 20.0 190.0 85.0 5 5000 ppm MgSO 4 20.0 50.0 60.0 6 Tap water 20.0 355.0 78.9 7 Tap water 20.0 233.0 75.0 8 Tap water 20.0 34.0 69.0

Claims: A method of producing a membrane comprising providing a solution containing a plurality of polymers in a non-aqueous liquid solvent, at least one of the polymers (hereinafter referred to as the "first polymer") having been prepared by polymerizing at least one vinyl or acrylic monomer, at least one other of the polymers being a membrane-forming hydrophobic polymer (hereinafter referred to as the "second polymer"), the first polymer and the second polymer being mutually incompatible in said solution, forming the solution into the desired shape of the membrane, and contacting the solution formed into said shape with an aqueous medium thereby to precipitate the polymers from the solution to form the membrane. A method according to claim 1, wherein the first polymer is formed in situ . A method according to claim 1 or 2, wherein the solution, formed into a flat sheet, is contacted with the aqueous medium to form the membrane. A method according to any of claims 1 to 3, wherein the solution, supported on a support or substrate, is contacted with the aqueous medium to form the membrane. A method according to claim 4, wherein the support or substrate is pervious or porous. A method according to claim 1 or 2, wherein the solution, formed into a tubular shape, is contacted with the aqueous medium to form the membrane as a hollow tube or fibre. A method according to claim 6 wherein the hollow tube or fibre is formed by introducing the solution into the aqueous medium by spinning or with use of a casting bob. A method according to any preceding claim, wherein the second polymer is a polysulphone, a polyethersulphone or a PVDF. A porous membrane comprising a vinyl or acrylic polymer dispersed in a hydrophobic polymer obtainable by the method of any of claims 1 to 8. A membrane according to claim 9, being in the form of a hollow fibre.

Inventors: JANI DIPAK, PEER MARTIN JAMES, JANI, DIPAK, PEER, MARTIN JAMES
Applicants: ITT MFG ENTERPRISES INC, ITT MANUFACTURING ENTERPRISES, INC.
Application year: 1998
Main classification: B01D67
IPC codes: B01D71, B01D69, B01D67