CA2446881A1 - Modification of stretched films - Google Patents

Modification of stretched films Download PDF

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Publication number
CA2446881A1
CA2446881A1 CA002446881A CA2446881A CA2446881A1 CA 2446881 A1 CA2446881 A1 CA 2446881A1 CA 002446881 A CA002446881 A CA 002446881A CA 2446881 A CA2446881 A CA 2446881A CA 2446881 A1 CA2446881 A1 CA 2446881A1
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Canada
Prior art keywords
poly
foil
polymer
membrane
weight
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CA002446881A
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French (fr)
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CA2446881C (en
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Thomas Haring
Rima Haring
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
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    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1079—Inducing porosity into non porous precursors membranes, e.g. leaching, pore stretching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1093—After-treatment of the membrane other than by polymerisation mechanical, e.g. pressing, puncturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
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    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08J2300/12—Polymers characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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Abstract

The invention relates to a drawn polymer film, comprising (A) a polymer or polymer blend and at least (B) one additional component with an average particle diameter of between 0.1 and 15 .mu.m, which by means of (C) one or several secondary treatment steps is processed to form a membrane after bein g drawn. The average particle diameter of component (B) ranges between 0.1 and 15 .mu.m, preferably 0.5 - 8.0 .mu.m, with the range between 1.0 and 7.0 .mu .m being particularly preferred. The membranes are used for alkene-alkane separation, electrodialysis, the desalinisation of seawater, in fuel cell applications and other membrane applications.

Claims (5)

1) A process for the production of a membrane, characterised in that a foil containing 20 to 98% by weight of a polymer component (A) and 80 to 2% by weight of a phyllosilicate and/or tectosilicate (B), which is distributed in the matrix of the polymer component (A), is monoaxially or biaxially stretched and after the streching is processed by one or more posttreatment steps (C) to a membrane, in which (A) can be a polymer as defined in the description, in which (B) has a cation-exchange capacity of at least 0.5 meq/g, and in which (C) is characterised in that the cations of the phyllosilicates and/or tectosilicates are completely or partly replaced by organic functionalising hydrophobisation agents having the general formula I and/or II

and wherein the substituents are characterised in that R1, R2, R3, R4 independently of each other represent hydrogen, a straight chain branched, saturated or nonsaturated hydrocarbon radical with 1 to 40, preferably 1 to 20 C atoms, which if necessary carries at least a functional group or 2 of the radicals are linked together, particularly to a heterocyclic rest with 5 to 10 C atoms, preferred particularly with one and more N atoms, and in which, X represents phosphorus, nitrogen or carbon, Y represents oxygen, sulphur or carbon, n is an integer number from 1 to 5, preferably 1 to 3 and Z is an anion, and in which the foil is treated alternating with a multivalent metal salt and the aqueous solution of phosphoric acid, with a concentration of the acid 1 to 85% by weight.
2) A process for the production of a membrane characterised in that a foil comprising 20 to 98% by weight of a polymer component (A) and 2 to 80% per weight of a phyllosilicate and/or tectosilicate (B), which is distributed in the matrix of the polymer component (A), is manoaxially or biaxially stretched and after the streching is processed by one or more posttreatment steps (C) to a membrane, in which (A) can be a polyolefine, such as polyethylene, polypropylene, polyisobutylene, polynorbornene, polymethylpentene, poly (1,4-isoprene), poly (3,4-isoprene), poly (1,4-butadiene), poly (1,2-butadiene) one styrene(co)polymer such as polystyrene, poly (methylstyrene), poly (triflourostyrene), poly (pentaflourostyrene), an N-basic polymer such as polyvinylcarbazole, polyethyleneimine, poly (2-vinylpyridine), poly (3-vinylpyridine), poly (4-vinylpyridine), a (het)aryl main chain polymer, such as polyetherketone PEK Victrex ®, polyetheretherketone PEEK Victrex ®, polyetheretherketoneketone PEEKK, polyetherketoneetherketone ketone PEKEKK Ultrapek ®, one polyethersulfone like polysulfone Udel ®, polyphenylsulfone Radel R ®, polyetherethersulfone Radel A ®, polyethersulfone PES Victrex ®, a poly(Benz) imidazole like PBI Celazol ®.
Polyphenyleneether as poly (2,6-dimethyloxyphenylene), poly (2,6-diphenyloxyphenylene), one polyphenylenesulfide and/or one copolymer of the said, and wherein (B) has a cation-exchange capacity of at least 0.5 meq/g, and in which (C) is characterised in that the cations of the phyllosilicates and/or tectosilicates are completely or partly exchanged by organic functionalising hydrophobisation agents which contain imidazole or pyridine groups, and in which thereafter the foil is inserted into a silver salt solution and thereafter once more the foil is inserted in a solution captaining imidazole or pyridine groups followed by a further post treatment in a silver salt solution, wherein the two last steps can be repeated if necessary several times.
3) Foil available according to the process 1 or 2.
4) Use of a foil according to claim 2 in the alkene alkane separation.
5) Use of foils according to claim 1 into fuel cells, in the alkene alkane separation, electrodialysis, reverse osmosis, dialysis, pervaporation and electrolysis.
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