WO2018192368A1 - 一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法 - Google Patents

一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法 Download PDF

Info

Publication number
WO2018192368A1
WO2018192368A1 PCT/CN2018/081864 CN2018081864W WO2018192368A1 WO 2018192368 A1 WO2018192368 A1 WO 2018192368A1 CN 2018081864 W CN2018081864 W CN 2018081864W WO 2018192368 A1 WO2018192368 A1 WO 2018192368A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
conductive polymer
chlorine
polymer resin
containing conductive
Prior art date
Application number
PCT/CN2018/081864
Other languages
English (en)
French (fr)
Inventor
吴慧生
杨颖�
Original Assignee
浙江汉丞科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201710251603.2A external-priority patent/CN106968110B/zh
Priority claimed from CN201710251601.3A external-priority patent/CN106977640B/zh
Priority claimed from CN201710251598.5A external-priority patent/CN106947027B/zh
Application filed by 浙江汉丞科技有限公司 filed Critical 浙江汉丞科技有限公司
Priority to GB1916736.0A priority Critical patent/GB2575951B/en
Priority to DE112018002056.8T priority patent/DE112018002056B4/de
Priority to US16/605,668 priority patent/US11136424B2/en
Publication of WO2018192368A1 publication Critical patent/WO2018192368A1/zh

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/32—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising halogenated hydrocarbons as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1466—Monomers containing sulfur
    • C08F216/1475—Monomers containing sulfur and oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/22—Vinylidene fluoride
    • C08F214/222—Vinylidene fluoride with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/24—Trifluorochloroethene
    • C08F214/242—Trifluorochloroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/26—Tetrafluoroethene
    • C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C08F261/06—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated ethers
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/0023—Electro-spinning characterised by the initial state of the material the material being a polymer melt
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M17/00—Producing multi-layer textile fabrics
    • D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
    • D06M17/10—Polyurethanes polyurea
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/20—All layers being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0223—Vinyl resin fibres
    • B32B2262/0238—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0246—Acrylic resin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0253—Polyolefin fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0276—Polyester fibres
    • B32B2262/0284—Polyethylene terephthalate [PET] or polybutylene terephthalate [PBT]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/105—Metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/107—Ceramic
    • B32B2264/108—Carbon, e.g. graphite particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/548—Creep
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/18—Fuel cells
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/10—Homopolymers or copolymers of unsaturated ethers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles

Definitions

  • the invention relates to a preparation method of a fluorine-containing chlorine-containing conductive polymer resin and a single-sided or double-sided filled composite film prepared by using the fluorine-containing chlorine-containing conductive polymer resin and a preparation method thereof, and belongs to the technical field of polymer materials.
  • Fluorinated polymers especially tetrafluoroethylene homopolymerized, modified, or copolymerized polymer resins have excellent physical and mechanical properties and chemical stability in chemical materials, mechanical and electrical, aerospace, military protection, new materials and New energy and other fields have a wide range of applications; chlorine-containing polymers, such as chlorotrifluoroethylene homopolymerized, modified, or copolymerized polymer resins have excellent physical and mechanical properties and chemical penetration resistance, in chemical protection There are important contributions. Fluorine-containing conductive polymers such as DuPont's Nafion resin have excellent electrical conductivity and chemical stability. They are widely used in fuel cells and chlor-alkali batteries, but there are still many shortcomings, such as low conductivity, and the normal temperature of the single film. Conductivity ⁇ 0.1 (S / cm); high chemical penetration, can not effectively block the penetration of toxic and hazardous chemicals.
  • the expanded polytetrafluoroethylene is prepared by using a high crystallinity polytetrafluoroethylene dispersion resin, which is obtained by biaxial stretching and expansion, and has a microporous structure in which micron or nanofibers are closely combined, and has excellent physical and chemical properties and mechanical properties. Waterproof and chemically stable, it has been used in the manufacture of wire and cable insulation, artificial blood vessels, sealing tapes, environmentally friendly filtration and apparel fabrics since the 1970s.
  • Patent document CN103483748B discloses a special fluorine-containing dispersion resin mixture and a preparation method thereof, which are prepared by blending a tetrafluoroethylene homopolymer dispersion emulsion with a fluorine-containing hot melt processable dispersion emulsion to obtain a special fluorine-containing film. Dispersing the resin mixture, then blending, extruding and stretching the mixture with the lubricating oil to prepare a fluorine-containing microporous film with high mechanical strength and good gas permeability, but its water pressure resistance and penetration resistance against toxic and harmful chemicals Still need to be further improved.
  • micro- or nano-fibers obtained by stretch-expansion have poor puncture resistance, poor creep resistance, and these micro- or nano-fibers continue to be stretched and loosened after being subjected to tension, causing deformation of the film structure. This leads to a decrease in functionality, which seriously affects the overall protective function of the membrane.
  • the present invention provides a method for preparing a fluorine-containing chlorine-containing conductive polymer resin. Further, the present invention also provides a fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film material, which has high mechanical strength and is waterproof, moisture permeable, washable, resistant to poisonous and harmful chemicals, and high in penetration. Excellent physical and chemical properties such as electrical conductivity.
  • the invention provides a preparation method of a fluorine-containing chlorine-containing conductive polymer resin, comprising the following steps:
  • S1 is added to the reaction vessel by free radically polymerized fluorine-containing sulfonyl fluoride liquid monomer 1% to 20%, purified water 79% to 98%, and fluorosurfactant 0.01% to 1% by weight. Stirring to obtain a prepolymer emulsion;
  • S2 is introduced into the reaction vessel by introducing one or two kinds of tetrafluoroethylene and vinylidene fluoride into a gas phase mixed monomer with chlorotrifluoroethylene at a reaction pressure of 5 kg or more; then introducing a radical initiator, the reaction temperature At 20-120 ° C, the reaction pressure is 5-25 kg, the reaction time is 15-180 min, and the reaction product is a fluorine-containing chlorine-containing sulfonyl fluoride-containing polymer emulsion; the fluorine-containing sulfonyl fluoride liquid monomer
  • the ratio of the total weight of the gas phase mixed monomer actually participating in the radical polymerization reaction is 1:3 to 3:1; the total weight of the radical initiator and the weight ratio of the fluorine-containing sulfonyl fluoride liquid monomer 0.01% to 3.0%;
  • S3 hydrolyzes a fluorine-containing chlorine-containing sulfonyl fluoride-containing polymer emulsion, and then agglomerates, washes, and dries to obtain a fluorine-containing chlorine-containing conductive polymer resin.
  • the method for producing a fluorine-containing chlorine-containing conductive polymer resin according to the present invention wherein the fluorine-containing sulfonyl fluoride monomer contains a fluorine-containing sulfonyl fluoride-free reagent, and the fluorine-containing fluorine-free reagent
  • the weight ratio of the fluorine-containing sulfonyl fluoride monomer is less than or equal to 30%.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer resin according to the present invention wherein the fluorine-containing fluorine-free fluorine-containing reagent comprises a fluorine-containing alkyl group, a fluorine-containing alkyl ether, a perfluoromethyl vinyl ether, and a perfluoro group One or more of ethyl vinyl ether, perfluoropropyl vinyl ether, 3,3,3-trifluoropropene or perfluoroalkylethylene.
  • the method for producing a fluorine-containing chlorine-containing conductive polymer resin according to the present invention wherein the gas phase mixed monomer comprises, in a molar ratio, 25% to 90% of tetrafluoroethylene, 0% to 70% of vinylidene fluoride, 5% to 50% chlorotrifluoroethylene.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer resin according to the present invention wherein the fluorosurfactant comprises an organic substance having 6 to 16 carbons and having at least one functional group of a carboxylic acid or a sulfonic acid.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer resin according to the present invention wherein the radical initiator comprises one or more of a persulfate, hydrogen peroxide, and an organic peroxy compound.
  • the present invention provides a fluorine-containing chlorine-containing conductive polymer single-sided filled composite film comprising a microporous film skeleton and the fluorine-containing chlorine-containing conductive polymer resin of the present invention, the microporous film skeleton More than 85% of the pore volume of one side is filled with the fluorine-containing chlorine-containing conductive polymer resin.
  • a method for fabricating a fluorine-containing chlorine-containing conductive polymer single-sided filled composite film according to the present invention comprises the following steps:
  • microporous film skeleton is coated or immersed, and the fluorine-containing chlorine-containing conductive polymer resin is filled into the pores of one side of the microporous film skeleton to obtain a composite material; the composite material is dried to obtain fluorine-containing chlorine.
  • Conductive polymer single-sided filled composite film is obtained.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer single-sided filled composite film wherein the weight ratio of the microporous film skeleton to the fluorine-containing chlorine-containing conductive polymer resin is (25:75) ⁇ 75:25).
  • One kind is subjected to spinning, and is uniformly collected into a random network microporous structure by hot melt spinning or wet spinning, and is obtained by heat setting to obtain a microporous film skeleton.
  • a method for preparing a fluorine-containing chlorine-containing conductive polymer single-sided filled composite film according to the present invention wherein the microporous film skeleton is coated or immersed, and the activated carbon powder, graphite powder, graphene, and rare metal powder are used.
  • the activated carbon powder, graphite powder, graphene, and rare metal powder are used.
  • One or more of them are mixed with a fluorine-containing chlorine-containing conductive polymer resin and filled into pores of one side of the microporous film thereof, preferably, the activated carbon powder, graphite powder, graphene, and rare metal powder.
  • the total weight of one or more of the ones does not exceed 25% by weight of the fluorine-containing chlorine-containing conductive polymer resin.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer single-sidedly filled composite film according to the present invention wherein the rare metal powder is silver, platinum or palladium.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer single-sidedly filled composite film according to the present invention wherein the hot meltable fluorine-containing resin or the chlorine-containing fluorine-containing resin comprises a hot meltable polytetrafluoroethylene copolymer Or one or more of polychlorotrifluoroethylene or a copolymer thereof, polyvinylidene fluoride or a copolymer thereof.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer single-sidedly filled composite film according to the present invention wherein the number of acid equivalents of the sulfonic acid or carboxylic acid of the fluorine-containing chlorine-containing conductive polymer resin (meq/g ) at 400 to 1600.
  • a method for preparing a fluorine-containing chlorine-containing conductive polymer single-sided filled composite film according to the present invention wherein a wet phase change method, a temperature difference phase change method, a dry solvent method, an electrospinning method or an ultra-high speed centrifugation Spinning is carried out by a spinning method.
  • the present invention provides a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film comprising a microporous film skeleton and the fluorine-containing chlorine-containing conductive polymer resin of the present invention, the microporous film skeleton double More than 60% of the pore volume of the surface is filled with a fluorine-containing chlorine-containing conductive polymer resin.
  • a method for fabricating a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention comprises the following steps:
  • the microporous film skeleton is coated or immersed, and the fluorine-containing chlorine-containing conductive polymer resin is filled into the pores of both sides of the microporous film skeleton to obtain a composite material; the composite material is dried to obtain a fluorine-containing content. Chlorine conductive polymer double-sided filled composite film.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film wherein the weight ratio of the microporous film skeleton to the fluorine-containing chlorine-containing conductive polymer resin is (5:95) ⁇ 40:60).
  • One kind is subjected to spinning, and is uniformly collected into a random network microporous structure by hot melt spinning or wet spinning, and is obtained by heat setting to obtain a microporous film skeleton.
  • a method for preparing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention wherein the microporous film skeleton is coated or immersed, and the activated carbon powder, the graphite powder, the graphene, the rare metal powder
  • the activated carbon powder, the graphite powder, the graphene, the rare metal powder is mixed into the pores of both sides of the microporous film; preferably, the activated carbon powder, graphite powder, graphene, rare metal
  • the total weight of one or more of the powders does not exceed 25% by weight of the fluorine-containing chlorine-containing conductive polymer resin.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention wherein the rare metal powder is silver, platinum or palladium.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention wherein the hot meltable fluorine-containing resin or the chlorine-containing fluorine-containing resin comprises a hot meltable polytetrafluoroethylene copolymer Or one or more of polychlorotrifluoroethylene or a copolymer thereof, polyvinylidene fluoride or a copolymer thereof.
  • a method for producing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention wherein the fluorine-containing chlorine-containing conductive polymer resin has an acid equivalent number (meq/g) of 400 to 1,500.
  • a method for preparing a fluorine-containing chlorine-containing conductive polymer double-sided filled composite film according to the present invention wherein a wet phase change method, a temperature difference phase change method, a dry solvent method, an electrospinning method or an ultra-high speed centrifugation is used. Spinning is carried out by a spinning method.
  • the fluorine-containing chlorine-containing conductive polymer resin can be prepared by the preparation method of the fluorine-containing chlorine-containing conductive polymer resin of the invention, and the fluorine-containing chlorine-containing polymer has higher mechanical strength than the perfluoropolymer, and is on the polymer main chain.
  • the inclusion of a small amount of chlorine atoms can increase the intermolecular attraction, and the mechanical strength of the polymer is enhanced to make the creep resistance better and less deformable.
  • its anti-toxic and harmful chemical substances are also better penetrating, suitable for protective clothing film, and its anti-alcohol permeability is also good, suitable for alcohol fuel cell membrane applications.
  • the fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film material provided by the invention has high physical and mechanical strength and high water repellency, and the film can meet the resistance to water and prevent intrusion of toxic and harmful chemicals. Higher, more moisture permeable; when applied to biochemical protective clothing, it has high protection against water and toxic and harmful chemicals, comfort, warmth, and can greatly enhance the combat effectiveness of soldiers; for fuel cell applications Because of its high conductivity, the obtained electrical properties are better, and fuels such as hydrogen or alcohol can be more completely burned and utilized.
  • fluorine-containing sulfonyl fluoride liquid phase monomer means a monomer which is added to a liquid phase containing both a sulfonyl fluoride group and an additional fluorine-containing group.
  • fluorine-containing sulfonyl fluoride-containing polymer means that the polymer contains both a sulfonyl fluoride group and an additional fluorine-containing group and a chlorine-containing group.
  • molecular weight means number average molecular weight (M n), M n is defined as the number of (optionally in combination with size exclusion chromatography SEC) was measured by a light scattering average molecular weight.
  • the invention provides a preparation method of a fluorine-containing chlorine-containing conductive polymer resin, which comprises the following steps:
  • S1 is added to the reaction vessel by free radically polymerized fluorine-containing sulfonyl fluoride liquid monomer 1% to 20%, purified water 79% to 98%, and fluorosurfactant 0.01% to 1% by weight.
  • Stirring gives a prepolymer emulsion; the agitation time is between 20 and 50 min, and without limitation, in one embodiment of the invention, the agitation time is 30 min.
  • S2 is introduced into the reaction vessel by introducing one or two kinds of tetrafluoroethylene and vinylidene fluoride into a gas phase mixed monomer with chlorotrifluoroethylene at a reaction pressure of 5 kg or more; then introducing a radical initiator, the reaction temperature At 20 to 120 ° C, the reaction pressure is 5 to 25 kg, and the reaction time is 15 to 180 min, and the reaction product is a fluorine-containing chlorine-containing sulfonyl fluoride-containing polymer emulsion, which is not limited, in a specific embodiment of the present invention.
  • the reaction temperature was 70 ° C and the reaction time was 1 hour.
  • the ratio of the fluorine-containing sulfonyl fluoride liquid phase monomer to the total weight of the gas phase mixed monomer actually participating in the radical polymerization reaction is 1:3 to 3:1, and preferably, the weight ratio is 1:2.5. ⁇ 3:1; the weight ratio of the total weight of the radical initiator to the fluorine-containing sulfonyl fluoride liquid monomer is 0.01% to 3.0%, preferably, the weight ratio is 0.05%;
  • S3 hydrolyzes a fluorine-containing chlorine-containing sulfonyl fluoride-containing polymer emulsion, and then agglomerates, washes, and dries to obtain a fluorine-containing chlorine-containing conductive polymer resin.
  • the conductivity can be improved, and on the other hand, the polymer can be A small amount of chlorine atoms are introduced into the chain to increase the intermolecular attraction, enhance mechanical strength, improve creep resistance, and improve penetration resistance to toxic and harmful chemicals.
  • the above monomers help to increase the ionic conductivity of the polymer.
  • the fluorine-containing sulfonyl fluoride monomer may contain a fluorine-containing sulfonyl fluoride-free reagent having a weight ratio of less than or less than a fluorine-containing sulfonyl fluoride monomer. Equal to 30%, can be 0%.
  • the addition of a fluorine-containing sulfonyl fluoride-free reagent is mainly for the purpose of adjusting its stability and dielectric properties.
  • the fluorine-containing non-sulfonyl fluoride reagent includes a fluorine-containing alkyl group, a fluorine-containing alkyl ether, a perfluoroalkyl vinyl ether (such as perfluoromethyl vinyl ether, perfluoroethyl vinyl ether) One or more of perfluoropropyl vinyl ether), 3,3,3-trifluoropropene or perfluoroalkylethylene.
  • the gas phase mixed monomer does not contain vinylidene fluoride.
  • the amount of chlorotrifluoroethylene added is from 5% to 30%, and a small amount of chlorine atoms contributes to enhancing mechanical strength while maintaining chemical resistance.
  • a fluorosurfactant can be used as an emulsifier in the present invention.
  • the fluorosurfactant is ammonium perfluorooctanoate.
  • the fluorosurfactant refers to a compound exhibiting surface activity in a fluorine-containing compound having at least one fluorine atom in its molecular structure.
  • the fluorinated surfactant include a hydrocarbon having 6 to 16 carbon atoms substituted with at least one hydrogen atom and a fluorine atom, and a carboxylic acid, a carboxylate, a sulfonic acid, and a sulfonic acid group.
  • the surfactant composed of a hydrophilic group may, for example, be ammonium perfluorooctanoate or perfluorooctanoate or the like.
  • the radical initiator in the present invention includes one or more of a persulfate, hydrogen peroxide, and an organic peroxy compound.
  • a persulfate include ammonium persulfate (APS) and potassium persulfate (KPS).
  • KPS potassium persulfate
  • organic peroxide include peroxydisuccinic acid (DSP) and dipentane peroxide.
  • APS is more preferable in view of an appropriate decomposition temperature of the initiator, ease of handling, cost, and polymer terminal structure.
  • the fluorine-containing chlorine-containing conductive polymer resin prepared by the above method of the present invention has a primary particle having an average particle diameter of about 40 to 200 nm and an emulsion solid content of about 18 to 25%, and the obtained fluorine-containing chlorine-containing conductive polymer emulsion is subjected to a sulfonyl group.
  • a conductive polymer containing fluorine-containing sulfonic acid (-SO 3 H) is obtained.
  • the specific gravity is about 1.7 to 2.1, and the number of acid equivalents (meq/g) is 300 to 1700. Preferably, it is 400 to 1600.
  • the invention also provides a fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film and a preparation method thereof.
  • the fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film is a microporous film skeleton and a filled composite film prepared by the above method of the invention to obtain a fluorine-containing chlorine-containing conductive polymer resin.
  • the fluorine-containing chlorine-containing conductive polymer single-sided composite film of the present invention most of the pores on one side of the microporous film skeleton (>85%, preferably >95%, optimally >99%) are fluorine-containing Filled with a chlorine-containing conductive polymer resin.
  • the pore volume of both sides of the microporous film skeleton exceeds 60% (preferably >75%, optimally >90%) by fluorine-containing chlorine The conductive polymer resin is filled.
  • the preparation method of the fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film of the invention comprises the following steps:
  • Step 1 Making a microporous film skeleton: firstly spinning the raw materials by wet phase change method, temperature difference phase change method, dry solvent method, electrospinning method or ultra high speed centrifugal spinning method, by hot melt spinning or wet method (with solvent or water) spinning, the diameter of the sprayed wire is about 50 ⁇ 1000 nm, which can be uniformly collected into a random network microporous structure.
  • the mesh microporous structure can be formed into a nanoporous film after heat setting.
  • the microporous film skeleton has a weight of about 1 to 50 g/m 2 , preferably 3 to 25 g/m 2 , and an open porosity of about 50% to 95%, preferably 70% to 90%;
  • the material of the microporous film skeleton is selected from the group consisting of: (I) a hot meltable fluorine-containing (chlorine-containing) resin selected from the group consisting of a hot meltable polytetrafluoroethylene copolymer, polychlorotrifluoroethylene or a copolymer thereof, and a poly (V) fluorine-containing chlorine-containing conductive polymer resin (the number of equivalents of sulfonic acid or carboxylic acid (meq/g) is from 1,000 to 2,000, preferably from 1200 to 1600); (III) The carbon fiber precursor such as polyacrylonitrile and its copolymer or other resin which can be derivatized into carbon fiber, preferably, the microporous film prepared by the carbon fiber precursor can be subjected to high temperature pre-oxidation, graphitization, carbonization and the like to become nano carbon fiber micro Orifice film; (IV) other advanced engineering materials selected from: polyimide, polyamide (nylon), polyester (PET), aramid
  • Step 2 preparing the fluorine-containing chlorine-containing conductive polymer single-sided or double-sided composite film by filling the fluorine-containing chlorine-containing conductive polymer resin according to the present invention into the pores of one or both sides of the microporous film skeleton:
  • the microporous film skeleton obtained in the first step coated or immersed in a (single or double sided) manner, the fluorine-containing chlorine-containing conductive polymer of the present invention and optionally a small amount of activated carbon powder, graphite powder, graphene or rare
  • the metal powder is filled into the pores of the microporous film skeleton on one side or both sides to dry the composite material, and the composite material is dried to obtain a fluorine-containing chlorine-containing polymer single-sided or double-sided filled composite film;
  • the total weight of the added small amount of activated carbon powder, graphite powder, graphene or rare metal powder does not exceed 25% by weight of the fluorine-containing chlorine-containing conductive polymer resin,
  • the acid equivalent number (meq/g) of the sulfonic acid or carboxylic acid of the fluorine-containing chlorine-containing conductive polymer resin is preferably from 400 to 1600, more preferably 600. Between 1200 and 1200, more preferably from 800 to 1100, the single film has a conductivity of >0.05 (S/cm), preferably >0.1 (S/cm), more preferably >0.15 (S/cm).
  • the weight ratio of the microporous film skeleton to the fluorine-containing chlorine-containing conductive polymer resin is (25:75) to (75:25), preferably at (35:65) to (65:35).
  • the pores on one side of the microporous membrane skeleton are mostly (>85%, preferably >95%, optimally >99%) are fluorine-containing chlorine-containing conductive polymer resins or a small amount of activated carbon powder, graphite powder, graphene Or a rare metal powder filled, the fluorine-containing chlorine-containing conductive polymer resin single-sided filled composite film has a low air permeability, and the time required for 100 ml of air to pass through the composite film by a Gurley gas permeability meter is >3 minutes, preferably >10. minute.
  • the total weight of the fluorine-containing chlorine-containing polymer single-sided filled composite film is 10 to 200 g/m 2 , preferably 20 to 100 g.
  • the thickness of which is from 1 ⁇ m to 100 ⁇ m, preferably from 3 ⁇ m to 50 ⁇ m, optimally from 5 ⁇ m to 30 ⁇ m; as in step two, a small amount is added
  • the total weight of the fluorine-containing chlorine-containing polymer single-sided filled composite film is 10 to 250 g/m 2 , preferably 20 to 150 g/m 2 .
  • the optimum is 25 to 100 g/m 2 and the thickness is 2 to 100 ⁇ m, preferably 3 to 50 ⁇ m, and most preferably 5 to 30 ⁇ m.
  • the acid equivalent number (meq/g) of the sulfonic acid or carboxylic acid containing the chlorine-containing conductive polymer resin is preferably from 400 to 1,500, more preferably from 500 to 1,100. More preferably in the 600 ⁇ 950.
  • the weight ratio of the microporous film skeleton to the fluorine-containing chlorine-containing conductive polymer resin is from (5:95) to (40:60), preferably from (10:90) to (30:70).
  • the pores on both sides of the microporous membrane skeleton are fluorine-containing chlorine-containing conductive polymer resins or a small amount of activated carbon powder, graphite powder, graphene Or a rare metal powder filled, the fluorine-containing chlorine-containing conductive polymer double-sided filled composite film has a low air permeability, and the time required for 100 ml of air to pass through the composite film by a Gurley gas permeability meter is >3 minutes, preferably >10. minute.
  • the total weight of the fluorine-containing chlorine-containing conductive polymer double-sided filled composite film is 5 to 200 g/m 2 , preferably 10 to 100. ⁇ /square meter, optimally 20-90 g/m2, thickness from 3 ⁇ m to 100 ⁇ m, preferably from 5 ⁇ m to 50 ⁇ m, optimally from 10 ⁇ m to 45 ⁇ m, fluorine-containing chlorine-containing conductive polymer
  • the double-sided filled composite film has a conductivity of >0.10 (S/cm), preferably >0.15 (S/cm), more preferably >0.20 (S/cm); as in step two, a small amount of activated carbon is added.
  • the total weight of the obtained fluorine-containing chlorine-containing conductive polymer double-sided filled composite film is 5 to 250 g/m 2 , preferably 10 to 150 g/m 2 , optimal It is 20-100 g/m2, and its thickness is 3 micrometers to 100 micrometers, preferably 5 micrometers to 50 micrometers, optimally 10 micrometers to 30 micrometers, and its normal temperature conductivity is 0.1 (S/cm). ), preferably > 0.15 (S/cm), more preferably > 0.20 (S/cm).
  • the mechanical strength of the fluorine-containing chlorine-containing conductive polymer single-sided or double-sided filled composite film of the invention is much better than that of the fluorine-containing chlorine-containing conductive polymer alone, and the high tensile strength can ensure that it can be applied to Proton exchange membrane fuel cell field.
  • the obtained composite fabric has a water pressure resistance (JIS L1092 method) initially greater than 200 kPa, and after water washing for 10 times, the water pressure resistance is still greater than 100 kPa; the moisture permeability rate >4000g/m 2 /day, according to the US military regulations MIL-DTL-32102 3April 2002 to test the erosive gas: chloroethyl ether (ClCH 2 CH 2 OCH 2 CH 2 Cl) penetration rate qualified ⁇ 4 ⁇ g / cm 2 / day, enough It is proved that the composite membrane of the invention has strong anti-biochemical penetration ability and is suitable for preparing nuclear biochemical protective clothing.
  • the porosity test method is tested according to ASTM standard D6093;
  • Tensile strength is measured by a tensile strength machine (Instron); test method: ASTM-D882
  • the water pressure resistance test method is tested according to the JIS L1092 method
  • the moisture vapor transmission rate also known as MVTR, is a measure of the amount of water vapor passing through the sheet material, expressed in grams per square meter per day; the outer layer is directed upwards according to the JIS L1099A1 method;
  • Gas permeability is measured by Gurley method, measuring the time when 100 ml of air passes through the sample, and the outer layer is facing downward;
  • chloroethyl ether (ClCH 2 CH 2 OCH 2 CH 2 Cl) penetration rate
  • Conductivity test method at room temperature The conductivity at 25 ° C was measured using a Crison 525 conductivity meter.
  • Test method for the amount of sizing the unit membrane weight of the skeleton is subtracted from the unit film after sizing.
  • a pre-emulsified reactor A of about 100 liters of internal volume, 39000 g of purified water, 100 g of ammonium perfluorooctanoate was added at room temperature, and the mixture was stirred at a high speed, and then slowly added to the kettle at a weight ratio of 5000 g of 70%
  • the kettle is first depleted of oxygen until the oxygen content in the kettle is less than 20 ppm, then all the prepolymer emulsion from the reactor A is added, and the gas phase mixed monomer is introduced into the kettle.
  • the molar ratio is 90% tetrafluoroethylene and 10% chlorotrifluoroethylene, the temperature is raised to 70 degrees, the pressure in the kettle is maintained at 11 kg, and 2.5 g of ammonium persulfate is added to pre-dissolve in 1 liter of deionized water to start free radicals. polymerization.
  • the ratio of the total weight of the fluorine-containing sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer actually participating in the radical polymerization reaction is about 4:5; the total weight of the radical initiator and the fluorine-containing sulfonate The weight ratio of the acyl fluoride liquid monomer is 0.05%;
  • the reaction temperature is controlled at 70 to 75 degrees, and the reaction time is one hour.
  • the stirring is stopped, and the reactant is discharged to obtain a fluorine-containing chlorine-containing conductive polymer emulsion, and the average particle diameter of the primary particles is about 100.
  • the emulsion solid content is about 19%, and the obtained fluorine-containing chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride (-SO 2 F) to obtain a fluorine-containing chlorine-containing sulfonic acid (-SO 3 H) conductive polymer, and dried.
  • the specific gravity is about 1.99
  • the acid equivalent number (meq/g) is about 900
  • the single-film normal temperature conductivity (Conductivity) is >0.15 (S/cm).
  • CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -SO 2 F and 20% CF 2 CF-O-CF 2 CF 2 -SO 2 F mixture, continuous high-speed shear mixing After 30 minutes, a prepolymer emulsion was prepared; in another reactor of about 100 liters of internal volume, the kettle was first evacuated until the oxygen content in the kettle was less than 20 ppm, and then all prepolymerization from reactor A was added.
  • the body emulsion the kettle is mixed with mixed gas phase mixed monomer, the molar ratio is 75% tetrafluoroethylene, 20% vinylidene fluoride and 5% chlorotrifluoroethylene, the temperature is raised to 70 degrees, the pressure in the kettle is maintained at 9 kg, added 2.5 grams of ammonium persulfate was pre-dissolved in 1 liter of deionized water to initiate free radical polymerization.
  • the ratio of the total weight of the fluorine-containing sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer actually participating in the radical polymerization reaction is about 5:4; the total weight of the radical initiator and the fluorine-containing sulfonate The weight ratio of the acyl fluoride liquid monomer is 0.05%;
  • the reaction temperature is controlled at 70 to 75 degrees, and the reaction time is about one hour.
  • the stirring is stopped, and the reactant is discharged to obtain a fluorine-containing chlorine-containing conductive polymer emulsion, and the average particle diameter of the primary particles is about 120 nm, the emulsion solid content is about 21%, and the obtained fluorine-containing chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride (-SO 2 F) to obtain a fluorine-containing chlorine-containing sulfonic acid (-SO 3 H) conductive polymer.
  • the specific gravity is about 1.91
  • the number of acid equivalents (meq/g) is about 800
  • the normal temperature conductivity of the single film is >0.20 (S/cm).
  • the polymer emulsion is fed into the gas phase mixed monomer, the molar ratio is 50% tetrafluoroethylene and 50% chlorotrifluoroethylene, the temperature is raised to 70 degrees, the pressure in the kettle is maintained at 14 kg, and 1.5 g of ammonium persulfate is added. Dissolved in 1 liter of deionized water to initiate free radical polymerization.
  • the ratio of the total weight of the fluorine-containing sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer actually participating in the radical polymerization reaction is about 1:3; the total weight of the radical initiator and the fluorine-containing sulfonate The weight ratio of the acyl fluoride liquid monomer is 0.05%;
  • the reaction temperature is controlled at 70 to 75 degrees, and the reaction time is about one hour.
  • the stirring is stopped, and the reactant is discharged to obtain a fluorine-containing chlorine-containing conductive polymer emulsion, and the average particle diameter of the primary particles is about 150 nm, the emulsion solid content is about 22%, and the obtained fluorine-containing chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride (-SO 2 F) to obtain a fluorine-containing chlorine-containing sulfonic acid (-SO 3 H) conductive polymer.
  • the specific gravity is about 2.02
  • the acid equivalent number (meq/g) is about 1,500
  • the normal temperature conductivity of the single film is >0.02 (S/cm).
  • CF-O-CF 2 CF(CF 3 )-O-CF 2 CF 2 -SO 2 F and 80% CF 2 CF-CF 2 -O-CF 2 CF 2 -SO 2 F mixture, continuous high speed shear After stirring for about 30 minutes, a prepolymer emulsion is prepared; in another reactor of about 100 liters of internal volume, the kettle is first evacuated until the oxygen content in the kettle is less than 20 ppm, and then added from the reactor A.
  • the ratio of the total weight of the fluorine-containing sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer actually participating in the radical polymerization reaction is about 3:1; the total weight of the free radical initiator and the fluorine-containing sulfonate The weight ratio of the acyl fluoride liquid monomer is 0.05%;
  • the reaction temperature is controlled at 70 to 75 degrees, and the reaction time is about one hour.
  • the stirring is stopped, and the reactant is discharged to obtain a fluorine-containing chlorine-containing conductive polymer emulsion, and the average particle diameter of the primary particles is about 70 nm, the emulsion solid content is about 19.5%, and the obtained fluorine-containing chlorine-containing conductive polymer emulsion is hydrolyzed by sulfonyl fluoride (-SO 2 F) to obtain a fluorine-containing chlorine-containing sulfonic acid (-SO 3 H) conductive polymer.
  • the specific gravity is about 1.97
  • the number of acid equivalents (meq/g) is about 500
  • the normal temperature conductivity of the single film is >0.35 (S/cm).
  • CF-CF 2 -O-SO 2 F and 40% CF 2 CF-CF 2 -O-CF 2 CF 2 -SO 2 F mixture, continuous high-speed shear stirring for about 30 minutes, to prepare prepolymer Emulsion; in another reactor B of about 100 liters of internal volume, the tank is first evacuated until the oxygen content in the kettle is less than 20 ppm, then all the prepolymer emulsion from the reactor A is added, and the kettle is mixed into the gas phase.
  • the molar ratio is 25% tetrafluoroethylene, 70% vinylidene fluoride, 5% chlorotrifluoroethylene, the temperature is raised to 80 degrees, the pressure in the kettle is maintained at 17 kg, and 1.5 g of ammonium persulfate is added to pre-dissolve 1 liter. Deionized water starts the free radical polymerization.
  • the ratio of the total weight of the fluorine-containing sulfonyl fluoride liquid phase monomer to the gas phase mixed monomer actually participating in the radical polymerization reaction is about 1:2.5; the total weight of the radical initiator and the fluorine-containing sulfonate The weight ratio of the acyl fluoride liquid monomer is 0.05%;
  • the reaction temperature is controlled at 80 to 85 degrees, and the reaction time is about 45 minutes.
  • the stirring is stopped, and the reactant is discharged to obtain a fluorine-containing conductive polymer emulsion, and the average particle diameter of the primary particles is about 50 nm.
  • the emulsion solid content is about 20%, and the obtained fluorine-containing conductive polymer emulsion is hydrolyzed by sulfuryl fluoride (-SO 2 F) to sulfonic acid (-SO 3 H), and (-CF 2 -O-SO 2 F) is hydrolyzed to carboxylate.
  • Acid-(COOH) fluorine-containing sulfonic acid/carboxylic acid conductive polymer after drying, has a specific gravity of about 1.72, an acid equivalent number (meq/g) of about 950, and a single film having a normal temperature conductivity of >0.10 (S/cm). ).
  • the fluorine-containing chlorine-containing conductive polymer resin produced in Preparation Example 3 and dimethylacetamide were mixed at a weight ratio of about 1:4, stirred at a temperature, and after the resin was dissolved, the nanofiber filaments were sprayed by electrospinning.
  • the minute production capacity is about 5 grams, and the nanofiber filaments produced are collected by release paper.
  • the nanofiber filaments are deposited on the release paper, and the release paper is advanced at a speed of 0.1 meters per minute.
  • a nanofiber silk film having a width of about 1 m, the silk film is gradually dried under a hot air treatment at about 90 ° C, and finally a nanofiber film having a thickness of about 20 ⁇ m and a width of about 100 cm is formed.
  • the average diameter is about 170 nm.
  • the film weighs about 10 g/m2, the porosity is about 78-82%, the specific gravity is 0.39, and the gas permeability Gurley test 100 ml air permeation speed is about 7-12 seconds.
  • Polyacrylonitrile PAN resin (copolymerized from acrylonitrile and a small amount of methyl ketone and methylidene diacrylate to form a copolymerized polyacrylonitrile resin with a molecular weight of more than 60,000 to 80,000) and dimethyl sulfoxide at a weight of about 1:4
  • the nanofiber filaments are sprayed by ultra-high speed centrifugal spinning, and the capacity per minute is about 20 g.
  • the produced nanofiber filaments are collected by the release paper, and the obtained nanofiber filaments are piled up.
  • the release paper advances at a speed of 0.1 m per minute, and a nanofiber silk film having a width of about 1 m is collected, and the silk film is gradually dried under a hot air treatment at about 160 ° C.
  • the silk film finally forms a nanofiber film having a thickness of about 70 ⁇ m and a width of about 100 cm, and the fiber has an average diameter of about 350 nm; after testing, the film has a weight of about 39 g/m 2 , a porosity of about 82 to 86%, and a specific gravity of 0.28.
  • the gas permeable Gurley test has a 100 ml air transmission rate of about 13 to 17 seconds.
  • the polyacrylonitrile nanoporous film prepared in Preparation Example 7 was heated to about 270 ° C under air for 2 h, and the color of the polyacrylonitrile PAN resin nanoporous film gradually changed from white to yellow and brown, and finally formed.
  • the black pre-oxidized microporous film is a result of a series of chemical reactions such as oxidation, pyrolysis, crosslinking, and cyclization to form a heat-resistant ladder type polymer after thermal oxidation of a polyacrylonitrile linear polymer, and then pre-oxidation
  • the porous film is subjected to high temperature treatment in nitrogen at 1600 ° C for carbonization treatment, and the nanofiber further generates cross-linking cyclization, aromatization and polycondensation, and removes hydrogen, nitrogen and oxygen atoms, and finally forms a two-dimensional carbon ring planar network.
  • the PAN-based nano carbon fiber film with a layered structure and a layer of coarse and parallel layered graphite structure finally forms a nanofiber film having a thickness of about 15 ⁇ m and a width of about 100 cm.
  • the average diameter of the fiber is about 160 nm, and the film is about 7 g / square meter, porosity of about 89 ⁇ 93%, specific gravity of 0.27, gas permeability Gurley test 100 ml air transmission speed of about 7 ⁇ 9 seconds.
  • ECTFE resin ethylene and chlorotrifluoroethylene copolymer, from Solvay
  • ECTFE fiber nanowires by melt spinning, and about 20 grams per minute was sprayed.
  • the resulting nanofiber filaments were collected with release paper.
  • the prepared nanofiber filaments were deposited on a release paper, and the release paper was advanced at a speed of 1 meter per minute.
  • a ECTFE nanofiber silk film having a width of about 1 meter was collected, and finally formed to a thickness of about 45 micrometers.
  • the speed is about 12 to 15 seconds.
  • the PET polyester resin and the ethylene carbonate are mixed at a weight ratio of about 1:4, stirred at a temperature, and after the resin is dissolved, the resin film is completely coated on the release paper at a solution temperature slightly exceeding 200 ° C, and the formed PET film is passed through.
  • the film was rapidly cooled to room temperature, the release paper was peeled off, and the PET film was gradually dried under a hot air treatment at about 170 ° C to form a nanoporous film having a thickness of about 50 ⁇ m and a width of about 160 cm.
  • the microporous film has a film weight of about 15 g/m 2 , a porosity of about 68 to 72%, a specific gravity of 0.29, and a gas permeability Gurley measurement of 100 ml of air permeation speed of about 17 to 23 seconds.
  • the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) produced in Preparation Example 5 was first dissolved in a dimethylformamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution was about 20%. Then, adding about 5% of the activated carbon powder in the solution, the ECTFE microporous film skeleton prepared in Preparation Example 9 was immersed in the solution at room temperature for about one minute, and the single-sided soaked film was taken out and gently scraped off.
  • the surface of the surface is immersed in excess liquid and slowly dried at 90 ° C to obtain a composite film; after testing, the resulting composite film has a final thickness of about 47 ⁇ m and a transparent film having a width of about 100 cm, and the film weighs about 39 g/m 2 .
  • the amount of glue is about 19 g/m2, and the gas permeability Gurley test has a 100 ml air transmission speed of more than 3 minutes.
  • the mechanical strength (tensile strength of more than 50 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) obtained in Preparation Example 5 alone (tensile strength is less than 20 MPa).
  • the composite film and nylon 6 plain woven fabric (90 g / square meter), the film is combined with the cloth through the point-like polyurethane bonding glue point, the composite fabric, the water pressure resistance is initially greater than 200 kPa, after washing 10 times, the water pressure resistance is still It is greater than 100 kPa; the moisture vapor transmission rate is >4000 g/m 2 /day, and the penetration rate of chloroethyl ether is ⁇ 4 ⁇ g/cm 2 /day, which proves that the composite membrane has strong penetration resistance against toxic and harmful chemicals.
  • the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) produced in Preparation Example 5 was first dissolved in a dimethylformamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution was about 20%.
  • the PET polyester microporous film skeleton obtained in Example 10 was immersed in a 20% fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) solution at room temperature for about one minute, and the single-sided immersion was taken out. Soak the film, gently scrape off the excess liquid on the surface of the single-sided immersion film, and slowly dry at 90 ° C to obtain a composite film; after testing, the obtained fluorine-containing chlorine polymer single-sided filled composite film has a final thickness of about 53 ⁇ m.
  • the mechanical strength (tensile strength of more than 30 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) obtained in Preparation Example 5 alone (tensile strength is less than 20 MPa).
  • the composite film and nylon 6 plain woven fabric (90 g / square meter), the film is combined with the cloth through the point-like polyurethane bonding glue point, the composite fabric, water pressure resistance (JIS L1092 method) is initially greater than 200 kPa, washed 10 times by water After that, the water pressure resistance is still greater than 100 kPa; the moisture vapor transmission rate is >4000 g/m 2 /day, and the penetration rate of chloroethyl ether (ClCH 2 CH 2 OCH 2 CH 2 Cl) is ⁇ 4 ⁇ g/cm 2 /day, which proves that the composite membrane is resistant. Strong resistance to poisonous and harmful chemicals.
  • the fluorine-containing chlorine-containing conductive polymer resin produced in Preparation Example 1 is first dissolved in a dimethylacetamide/ethanol (1:1) solution, and the concentration of the fluorine-containing chlorine-containing conductive polymer resin in the solution is about 20%.
  • the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 1500) microporous film skeleton prepared in Preparation Example 6 was immersed in a 20% fluorine-containing chlorine-containing conductive polymer (acid equivalent number 900) at room temperature on both sides.
  • the soaked film was taken out, and the excess liquid on the surface of the film was gently scraped off, and slowly dried at 90 ° C to obtain a composite film; after testing, the final thickness of the composite film was about 25 ⁇ m and the width was about 100 cm.
  • the mechanical strength (tensile strength of more than 30 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number of 900) obtained in Preparation Example 1 alone (tensile strength is less than 20 MPa), and is suitable. Do fuel cell applications.
  • the fluorine-containing chlorine-containing conductive polymer resin produced in Preparation Example 4 is first dissolved in a dimethylacetamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution is about 20%, and then the solution weight is added. About 5% of graphite powder and 1 ppm of metal platinum nanoparticles, the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 1500) microporous film skeleton prepared in Preparation Example 6 was immersed in the prepared solution at room temperature on both sides.
  • the resulting composite film has a final thickness of about 25 ⁇ m and a width of about 100 cm.
  • the film has a film weight of about 47 g/m 2 , a gluing amount of about 37 g/m 2 , a specific gravity of 1.83, a gas permeability Gurley test method of 100 ml air permeation speed of more than 3 minutes, and a composite film conductivity of about 0.23 (S/cm).
  • the mechanical strength (tensile strength of more than 30 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number of 500) obtained in Preparation Example 4 alone (tensile strength is less than 10 MPa, no Strength), suitable for fuel cell applications.
  • the fluorine-containing chlorine-containing conductive polymer resin (acid number: 900) obtained in Preparation Example 1 was first dissolved in a dimethylacetamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution was about 20 %, adding 10 ppm of graphene, the carbon fiber microporous film skeleton prepared in Preparation Example 8 was immersed in the prepared solution for about one minute at room temperature, and the soaked film was taken out, and the excess liquid on the surface of the film was gently scraped off. After drying slowly at 90 ° C, a composite film is obtained; after testing, the resulting composite film has a final thickness of about 19 ⁇ m and a transparent film having a width of about 100 cm.
  • the film has a weight of about 37 g/m 2 and a gluing amount of about 12 g/m 2 .
  • the specific gravity is about 1.93
  • the gas permeability Gurley test 100 ml air transmission speed is more than 3 minutes
  • the composite film conductivity is about 0.19 (S/cm).
  • the mechanical strength (tensile strength of more than 60 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number of 900) obtained in Preparation Example 1 alone (tensile strength is less than 20 MPa), and is suitable. Do fuel cell applications.
  • the fluorine-containing chlorine-containing conductive polymer resin (acid number: 500) obtained in Preparation Example 4 is first dissolved in a dimethylacetamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution is about 20 %, the ECTFE microporous film skeleton obtained in Example 9 was immersed in a 20% fluorine-containing chlorine-containing conductive polymer (acid equivalent number 500) solution at room temperature for about one minute, and the soaked film was taken out. Gently scrape off excess liquid on the surface of the film and slowly dry at 90 ° C to obtain a composite film. After testing, the resulting composite film has a final thickness of about 50 ⁇ m and a transparent film with a width of about 100 cm.
  • the film weighs about 98 g/m 2 .
  • the glue amount is about 78 g/m2, the specific gravity is 1.96, the gas permeability Gurley test 100 ml air permeation speed is more than 3 minutes, and the composite film conductivity is about 0.17 (S/cm).
  • the mechanical strength (tensile strength greater than 50 MPa) of the composite film is much better than that of the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 500) obtained in Preparation Example 4 alone (tensile strength is less than 10 MPa, no Strength), suitable for fuel cell applications.
  • the fluorine-containing chlorine-containing conductive polymer resin (acid equivalent number 950) produced in Preparation Example 5 was first dissolved in a dimethylformamide/ethanol (1:1) solution, and the concentration of the conductive polymer in the solution was about 20 %, the carbon fiber microporous film skeleton prepared in Preparation Example 8 was immersed in a 20% fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) solution at room temperature for about one minute, and the soaked film was taken out. Gently scrape off excess liquid on the surface of the film and slowly dry at 90 ° C to obtain a composite film. After testing, the resulting composite film has a final thickness of about 21 ⁇ m and a transparent film with a width of about 100 cm.
  • the film weighs about 39 g/m 2 .
  • the amount of glue is about 32 g / square meter
  • the specific gravity is about 1.86
  • the gas permeability Gurley test 100 ml air transmission speed is more than 3 minutes
  • the composite film conductivity is about 0.13 (S / cm)
  • the mechanical strength of the composite film is more than 1000 MPa), which is far superior to the film prepared by using the fluorine-containing chlorine-containing conductive polymer (acid equivalent number 950) obtained in Preparation Example 5 alone.
  • the composite film and nylon 6 plain woven fabric (90 g / square meter), the film and the cloth are composited by a point-like polyurethane bonding glue point, the composite fabric, water pressure resistance (JIS L1092 method) is initially greater than 200 kPa, after washing 10 times The water pressure resistance is still greater than 100 kPa; the moisture vapor transmission rate is >4000 g/m 2 /day, and the toxic gas: chloroethyl ether (ClCH 2 CH 2 OCH 2 CH 2 Cl) is penetrated according to the US military regulations MIL-DTL-32102 3April 2002. The rate is ⁇ 4 ⁇ g/cm 2 /day, which proves that the composite film has strong penetration resistance against toxic and harmful chemicals.
  • DuPont's perfluoro-conductive polymer film (Nafion NR-211, film thickness 25 microns) and nylon 6 plain woven fabric (90 g / square meter), the film is laminated with the cloth through the point-like polyurethane bonding glue point, the composite fabric Water pressure resistance (JIS L1092 method) is initially greater than 200 kPa. After washing 10 times, the film is completely separated from the cloth and cannot withstand water pressure; the moisture permeability rate is >4000 g/m 2 /day, and the penetration rate of chloroethyl ether is >60 ⁇ g/cm. 2 /day, which proves that this composite membrane has poor penetration resistance to toxic and harmful chemicals.
  • DuPont's perfluoro-conductive polymer film (Nafion NR-212, film thickness 50 microns) and nylon 6 plain woven fabric (90 g / square meter), the film is laminated with the cloth through the point-like polyurethane bonding point, the composite fabric Water pressure resistance (JIS L1092 method) is initially greater than 200 kPa. After washing 10 times, the film is completely separated from the cloth and cannot withstand water pressure; the moisture permeability rate is >4000 g/m 2 /day, and the penetration rate of chloroethyl ether is >40 ⁇ g/cm. 2 /day, which proves that this composite membrane has poor penetration resistance to toxic and harmful chemicals.
  • DuPont Nafion's D520 perfluorosulfonic acid resin solution was vacuum-concentrated until the concentration of the perfluorosulfonic acid conductive polymer Nafion in the solution was about 20%, and the expanded polytetrafluoroethylene film purchased from the net was used as a microporous film skeleton at room temperature.
  • Double-sided immersion in the prepared 20% perfluoroconductive polymer solution for about one minute take out the soaked film, gently scrape off the excess liquid on the surface of the film, and slowly dry at 90 ° C to obtain a composite film;
  • the obtained special fluorine-containing chlorine-containing double-sided filled composite film has a final thickness of about 25 ⁇ m and a transparent film having a width of about 100 cm.
  • the film has a weight of about 50 g/m 2 and a specific gravity of 1.98.
  • the gas permeability of the gas permeability Gurley test is greater than 100 ml.
  • the composite film has a normal temperature conductivity of about 0.08 (S/cm), and the composite film has a normal temperature conductivity of less than 0.1 (S/cm), which cannot be accepted by the fuel cell membrane market.
  • the D520 Nafion D520 perfluorosulfonic acid resin solution was concentrated under vacuum until the concentration of the perfluorosulfonic acid conductive polymer in the solution was about 20%, and the carbon fiber microporous film skeleton prepared in Preparation Example 8 was immersed at room temperature on both sides.
  • the prepared 20% perfluoroconductive polymer solution for about one minute, take out the soaked film, gently scrape off the excess liquid on the surface of the film, and slowly dry at 90 ° C to obtain a composite film;
  • the fluorine-containing chlorine-containing conductive polymer double-sided filled composite film has a final thickness of about 21 ⁇ m and a transparent film having a width of about 100 cm.
  • the film has a weight of about 40 g/m 2 and a specific gravity of about 1.89.
  • the gas permeability Gurley method has a 100 ml air transmission speed.
  • the fluorine-containing conductive polymer double-sided filled composite film has a room temperature electrical conductivity of about 0.09 (S/cm) for more than 3 minutes.
  • the composite film and nylon 6 plain woven fabric (90 g / square meter), the film and the cloth are composited by a point-like polyurethane bonding glue point, the composite fabric, water pressure resistance (JIS L1092 method) is initially greater than 200 kPa, after washing 10 times
  • the film is separated from the cloth and cannot be accepted by the market; the moisture permeability rate is >4000g/m 2 /day, and the penetration rate of the chloroethyl ether is >40 ⁇ g/cm 2 /day, indicating that the composite film has poor penetration resistance to toxic and harmful chemicals. .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Conductive Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Fuel Cell (AREA)

Abstract

本发明提供一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法。本发明的含氟含氯导电高分子单面或双面填充复合薄膜材料包括微孔薄膜骨架与含氟含氯导电高分子，其物理机械强度高，防水性较高，此薄膜能满足对抵抗水及阻止有毒有害化学品侵入性能更高、透湿性更高；当将其应用于生化防护服时，具有轻便和对水及有毒有害化学品的高防护性能、舒适、保暖、可大大提升战士的战斗力；用于燃料电池的应用，因其导电度高，获得的电性能较好，且燃料如氢气或酒精较能较完全燃烧利用。

Description

一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法
交叉引用
本申请主张2017年4月18日提交的中国专利申请号为201710251598.5、201710251601.3、201710251603.2的优先权，其全部内容通过引用包含于此。
技术领域
本发明涉及一种含氟含氯导电高分子树脂的制备方法及使用该含氟含氯导电高分子树脂所制备的单面或双面填充复合薄膜及制备方法，属于高分子材料技术领域。
背景技术
含氟高分子，尤其是四氟乙烯的均聚、改性、或共聚高分子树脂都具有优异的物理机械性能和化学稳定性，在化工材料、机械电子、航空航天、军工防护、新型材料和新能源等各领域都有着广泛的应用；含氯高分子，如三氟氯乙烯的均聚、改性、或共聚高分子树脂均具有优异的物理机械性能和抗化学穿透性，在化学防护上有重要贡献。含氟导电高分子如杜邦的Nafion树脂，有优异的导电性及化学稳定性，在燃料电池及氯碱电池的应用广泛，但仍存在不少缺点，如导电性能还不够高，其单膜的常温电导率(Conductivity)<0.1(S/cm)；化学穿透性高，无法有效阻隔有毒有害化学品穿透。
膨体聚四氟乙烯制备是采用高结晶度的聚四氟乙烯分散树脂，经双向拉伸膨化获得，具有高度微米或纳米纤维紧密结合的微孔结构，有优良的物理化学性能，机械性能，防水透气性和化学稳定性，从七十年代以来就被用于制造电线电缆绝缘材料、人造血管、密封带、环保过滤以及服装面料等。专利文件CN103483748B公开了一种特种含氟分散树脂混合料及其微孔薄膜的制备方法，其通过将四氟乙烯均聚物分散乳液与含氟可热熔加工性分散乳液共混制备得到特种含氟分散树脂混合料，然后将该混合料与润滑油共混、挤压、拉伸制备机械强度高、透气性好的含氟微孔薄膜，但其耐水压性和抗有毒有害化学物质穿透性仍需进一步提高。此外，这类经拉伸膨化得到的微米或纳米纤维耐穿刺性不好，抗蠕变性能不佳，且在受张力后这些微米或纳米纤维会继续被拉长拉松，造成膜组织变形，导致功能性下降，严重影响膜整体防护性功能。
发明内容
发明要解决的问题
为了解决以上现有技术的缺点和不足之处，本发明提供一种含氟含氯导电高分子树脂的制备方法。进一步地，本发明还提供含氟含氯导电高分子单面或双面填充复合薄膜材料，其具有较高的机械强度及防水、透湿、耐水洗、抗有毒有害化学物质穿透性及高导电性等优秀的物化性能。
用于解决问题的方案
本发明提供一种含氟含氯导电高分子树脂的制备方法，包括如下步骤：
S1按重量百分比将可自由基聚合的含氟带磺酰氟液相单体1％～20％、纯净水79％～98％、含氟表面活性剂0.01％～1％加入反应釜中进行高速搅拌，得到预聚体乳液；
S2往反应釜内通入四氟乙烯、偏氟乙烯中的一种或两种与三氟氯乙烯的气相混合单体，反应压力为5公斤或以上；然后通入自由基引发剂，反应温度在20～120℃，反应压力在5～25公斤，反应时间为15～180min，得到反应产物为含氟含氯带磺酰氟的高分子乳液；所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比为1：3～3：1；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.01％～3.0％；
S3对含氟含氯带磺酰氟的高分子乳液进行水解，再经凝聚、水洗、干燥后得到含氟含氯导电高分子树脂。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，步骤S1中，所述含氟带磺酰氟液相单体包括CF 2＝CF-O-R f-SO 2F、CF 2＝CF-O-R f1-O-R f2-SO 2F、CF 2＝CF-CF 2-O-R f3-SO 2F中一种或几种，其中R f、R f1、R f2是1～6个碳的含氟烷基，R f3是0～5个碳的含氟烷基，优选地，所述含氟带磺酰氟液相单体包括CF 2＝CF-O-CF 2CF 2-SO 2F、CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F、CF 2＝CF-CF 2-O-SO 2F、CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F中的一种或几种。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，当所述含氟含氯导电高分子树脂应用于电池领域时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0～80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F 20％～99％，CF 2＝CF-CF 2-O-SO 2F 0％～20％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，以上物质重量百分比之和为100％。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，当所述含氟含氯导电高 分子树脂应用于核生化防护膜材时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0～80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F 0％～20％，CF 2＝CF-CF 2-O-SO 2F 20％～100％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，以上物质重量百分比之和为100％。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，所述含氟带磺酰氟单体里含有含氟不带磺酰氟试剂，所述含氟不带磺酰氟试剂与含氟带磺酰氟单体的重量比小于或等于30％。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，所述含氟不带磺酰氟试剂包括含氟烷基、含氟烷基醚、全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚、3，3，3-三氟丙烯或全氟烷基乙烯中的一种或多种。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，所述气相混合单体以摩尔比计含：25％～90％的四氟乙烯、0％～70％的偏氟乙烯、5％～50％的三氟氯乙烯。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，所述含氟表面活性剂包括含6～16个碳的有机物，并至少含一个羧酸或者磺酸的官能团。
根据本发明的含氟含氯导电高分子树脂的制备方法，其中，所述自由基引发剂包括过硫酸盐、双氧水、有机过氧化合物中的一种或多种。
进一步地，本发明还提供一种含氟含氯导电高分子单面填充复合薄膜，其中，包括微孔薄膜骨架与本发明所述的含氟含氯导电高分子树脂，所述微孔薄膜骨架的单面的孔隙体积超过85％被所述含氟含氯导电高分子树脂所填充。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，包括如下步骤：
将微孔薄膜骨架以涂布或浸泡方法，把所述含氟含氯导电高分子树脂填充入微孔薄膜骨架单面的孔隙里得到复合材料；将复合材料烘干，制得含氟含氯导电高分子单面填充复合薄膜。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(25:75)～(75:25)。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，微孔薄膜骨架通过如下方法制备：
先将可热熔性含氟树脂或含氯含氟树脂、所述含氟含氯导电高分子树脂、碳纤维前体、聚酰亚胺、聚酰胺、聚酯、芳纶、聚醚酮中的一种进行纺丝，经热熔喷丝或湿法喷 丝，均匀地收集成无规则网状微孔结构，经热定形后得到微孔薄膜骨架。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，微孔薄膜骨架以涂布或浸泡方法，将活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种，与含氟含氯导电高分子树脂混合一并填充入其微孔薄膜单面的孔隙里，优选地，所述活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种的总重量不超过含氟含氯导电高分子树脂的重量的25％。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，所述稀有金属粉为银、铂或钯。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，可热熔性含氟树脂或含氯含氟树脂包括可热熔性聚四氟乙烯共聚物、聚三氟氯乙烯或其共聚物、聚偏氟乙烯或其共聚物中的一种或几种。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，所述含氟含氯导电高分子树脂的磺酸或羧酸的酸当量数(meq/g)在400～1600。
根据本发明所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其中，采用湿式相变化法、温差相变化法、干式溶剂法、静电纺丝法或超高速离心纺丝法进行纺丝。
进一步地，本发明还提供一种含氟含氯导电高分子双面填充复合薄膜，其中，包括微孔薄膜骨架与本发明的含氟含氯导电高分子树脂，所述微孔薄膜骨架的双面的孔隙体积超过60％被含氟含氯导电高分子树脂所填充。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，包括如下步骤：
将微孔薄膜骨架以涂布或浸泡的方式，把所述含氟含氯导电高分子树脂填充入微孔薄膜骨架双面的孔隙里得到复合材料；将复合材料烘干，制得含氟含氯导电高分子双面填充复合薄膜。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(5:95)～(40:60)。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，微孔薄膜骨架通过如下方法制备：
先将可热熔性含氟树脂或含氯含氟树脂、所述含氟含氯导电高分子树脂、碳纤维前体、聚酰亚胺、聚酰胺、聚酯、芳纶、聚醚酮中的一种进行纺丝，经热熔喷丝或湿法喷 丝，均匀地收集成无规则网状微孔结构，经热定形后得到微孔薄膜骨架。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，微孔薄膜骨架以涂布或浸泡方法，将活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种，与所述含氟含氯导电高分子树脂混合一并填充入其微孔薄膜双面的孔隙里；优选地，所述活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种的总重量不超过含氟含氯导电高分子树脂的重量的25％。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，所述稀有金属粉为银、铂或钯。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，可热熔性含氟树脂或含氯含氟树脂包括可热熔性聚四氟乙烯共聚物、聚三氟氯乙烯或其共聚物、聚偏氟乙烯或其共聚物中的一种或几种。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，所述含氟含氯导电高分子树脂的酸当量数(meq/g)在400～1500。
根据本发明所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其中，采用湿式相变化法、温差相变化法、干式溶剂法、静电纺丝法或超高速离心纺丝法进行纺丝。
发明的效果
通过本发明的含氟含氯导电高分子树脂的制备方法可以制备得到一种含氟含氯导电高分子树脂，含氟含氯高分子比全氟的高分子机械强度高，高分子主链上含少量氯原子可增加分子间吸引力，使高分子机械强度增强，使其抗蠕变性较好，不易变形。另外，其抗有毒有害化学物质穿透性也较好，适合做防护性服装膜，而且其抗酒精穿透性也较好，适合做酒精燃料电池膜等应用。
进一步地，本发明提供的含氟含氯导电高分子单面或双面填充复合薄膜材料，其物理机械强度高，防水性较高，此薄膜能满足对抵抗水及阻止有毒有害化学品侵入性能更高、透湿性更高；当将其应用于生化防护服时，具有轻便和对水及有毒有害化学品的高防护性能、舒适、保暖、可大大提升战士的战斗力；用于燃料电池的应用，因其导电度高，获得的电性能较好，且燃料如氢气或酒精较能较完全燃烧利用。
具体实施方式
以下将对本发明作进一步的描述，需要说明的是，本实施例以本技术方案为前提， 给出了详细的实施方式和具体的操作过程，但本发明的保护范围并不限于本实施例。
定义
本发明的“含氟带磺酰氟液相单体”是指既含磺酰氟基团又含额外含氟基团的加入到液相中的单体。本发明的“含氟含氯带磺酰氟的高分子”是指该高分子既含有磺酰氟基团又含额外含氟基团以及含氯基团。
本发明的反应压力以公斤计，严格意义上是指“公斤力/平方厘米”，1公斤压力＝1kg/cm 2。
在本发明中术语“分子量”是指数均分子量(M n)，M n被定义为通过光散射(可选与尺寸排斥色谱SEC组合)测定的数均分子量。
<含氟含氯导电高分子树脂的制备方法>
本发明提供一种含氟含氯导电高分子树脂的制备方法，其包括如下步骤：
S1按重量百分比将可自由基聚合的含氟带磺酰氟液相单体1％～20％、纯净水79％～98％、含氟表面活性剂0.01％～1％加入反应釜中进行高速搅拌，得到预聚体乳液；搅拌时间在20～50min，非限制性地，在本发明的一个具体实施方案中，搅拌时间为30min。
S2往反应釜内通入四氟乙烯、偏氟乙烯中的一种或两种与三氟氯乙烯的气相混合单体，反应压力为5公斤或以上；然后通入自由基引发剂，反应温度在20～120℃，反应压力在5～25公斤，反应时间为15～180min，得到反应产物为含氟含氯带磺酰氟的高分子乳液，非限制性地，在本发明的一个具体实施方案中，反应温度为70℃，反应时间为1小时。所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比为1：3～3：1，优选地，该重量之比为1:2.5～3：1；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.01％～3.0％，优选地，该重量比为0.05％；
S3对含氟含氯带磺酰氟的高分子乳液进行水解，再经凝聚、水洗、干燥后得到含氟含氯导电高分子树脂。
通过采用上述特定的制备工艺同时引入含氟带磺酰氟液相单体和三氟氯乙烯单体对含氟聚合物进行改性，一方面可以改善导电性，另一方面可以在高分子主链上引入少量氯原子以增加分子间吸引力，增强机械强度，改善抗蠕变性，提高抗有毒有害化学物质穿透性。
进一步地，步骤S1中，所述含氟带磺酰氟液相单体包括CF 2＝CF-O-R f-SO 2F、CF 2＝CF-O-R f1-O-R f2-SO 2F、CF 2＝CF-CF 2-O-R f3-SO 2F中一种或几种，其中R f、R f1、R f2是1～6个碳的含氟烷基，R f3是0～5个碳的含氟烷基。更进一步地，所述含氟带磺酰氟液相 单体包括CF 2＝CF-O-CF 2CF 2-SO 2F、CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F、CF 2＝CF-CF 2-O-SO 2F、CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F中的一种或几种。上述单体有助于提高聚合物的离子电导性。非限制性地，在本发明的一个具体实施方案中，含氟带磺酰氟液相单体包括CF 2＝CF-O-CF 2CF 2-SO 2F和CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F；在本发明的另一个具体实施方案中，含氟带磺酰氟液相单体包括CF 2＝CF-O-CF 2-SO 2F和CF 2＝CF-O-CF 2CF 2-SO 2F。
当所述含氟含氯导电高分子树脂应用于电池领域时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0-80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F20％～99％，CF 2＝CF-CF 2-O-SO 2F 0％～20％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，上述组分重量百分比加和为100％。当所述含氟含氯导电高分子树脂应用于核生化防护膜材时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0-80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F 0％～20％，CF 2＝CF-CF 2-O-SO 2F 20％～100％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，上述组分重量百分比加和为100％。任选地，所述含氟带磺酰氟单体里可含有含氟不带磺酰氟试剂，所述含氟不带磺酰氟试剂与含氟带磺酰氟单体的重量比小于或等于30％，可以为0％。含氟不带磺酰氟试剂的加入主要是为了调整其稳定性和介电性。更进一步地，所述含氟不带磺酰氟试剂包括含氟烷基、含氟烷基醚、全氟烷基乙烯基醚(如全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚)、3，3，3-三氟丙烯或全氟烷基乙烯中的一种或多种。
在本发明中气相混合单体以摩尔比计含：25％～90％的四氟乙烯(TFE；CF 2＝CF 2)、0％～70％的偏氟乙烯(VdF；CH 2＝CF 2)、5％～50％的三氟氯乙烯(CTFE；CF 2＝CFCl)，上述组分摩尔百分比加和为100％。非限制性地，在本发明的一个具体实施方案中，气相混合单体不含有偏氟乙烯。在本发明的另一个具体实施方案中，三氟氯乙烯的添加量在5％～30％，少量氯原子有助于在保持耐化学性的同时增强机械强度。
在本发明中可以使用含氟表面活性剂起乳化剂作用。非限制性地，在本发明的一个具体实施方案中，含氟表面活性剂为全氟辛酸铵。在本说明书中，上述含氟表面活性剂是指，分子结构中含有至少1个氟原子的含氟化合物中的显示出表面活性的化合物。作为所述含氟表面活性剂，在实用方面可以举出由至少1个氢原子被氟原子所取代的碳原子数为6～16的烃与羧酸、羧酸盐、磺酸、磺酸基等亲水基团构成的表面活性剂，在工业上可以举出全氟辛酸铵、全氟辛酸锍盐等。
在本发明中所述自由基引发剂包括过硫酸盐、双氧水、有机过氧化合物中的一种或 多种。作为上述过硫酸盐，可以举出例如过硫酸铵(APS)、过硫酸钾(KPS)。作为上述有机过氧化物，可以举出例如过氧化二琥珀酸(DSP)、过氧化二戊二酸。如果考虑到引发剂适宜分解温度、处理的简便性、成本、聚合物末端结构，更优选为APS。
通过本发明上述方法制备得到的含氟含氯导电高分子树脂其初级粒子的平均粒径约40～200纳米，乳液固含量约18～25％，所得含氟含氯导电高分子乳液经磺酰氟(-SO 2F)水解后得到含氟含氯带磺酸(-SO 3H)的导电高分子，干燥后，其比重约1.7～2.1，酸当量数(meq/g)为300～1700，优选400～1600。
<含氟含氯导电高分子单面或双面填充复合薄膜及其制备方法>
本发明还提供一种含氟含氯导电高分子单面或双面填充复合薄膜及其制备方法。
所述含氟含氯导电高分子单面或双面填充复合薄膜是微孔薄膜骨架与经本发明上述方法制备得到含氟含氯导电高分子树脂的填充复合薄膜。
对于本发明的含氟含氯导电高分子单面复合薄膜而言，其中微孔薄膜骨架单面的孔隙大部分(>85％，优选的>95％，最优的>99％)被含氟含氯导电高分子树脂所填充。对于本发明的含氟含氯导电高分子双面复合薄膜而言，所述微孔薄膜骨架的双面的孔隙体积超过60％(优选>75％，最优>90％)被含氟含氯导电高分子树脂所填充。
本发明的含氟含氯导电高分子单面或双面填充复合薄膜的制备方法包括以下工序：
步骤一、制作微孔薄膜骨架：先将原料以湿式相变化法、温差相变化法、干式溶剂法、静电纺丝法或超高速离心纺丝法纺丝，经热熔喷丝或湿法(含溶剂或水)喷丝，喷出来的丝其直径约50～1000纳米，可均匀的收集成无规则网状微孔结构，此网状微孔结构经热定形后可行成纳米微孔薄膜，此微孔薄膜骨架重约1～50克/平米，优选的3～25克/平米，其开孔隙率约50％～95％，优选的70％～90％；
所述微孔薄膜骨架的材料选自：(I)可热熔性含氟(含氯)树脂，选自可热熔性聚四氟乙烯共聚物，聚三氟氯乙烯或其共聚物，聚偏氟乙烯或其共聚物；(II)含氟含氯导电高分子树脂(其磺酸或羧酸的当量数(meq/g)在1000～2000，优选的在1200～1600)；(III)碳纤维前体如聚丙烯腈及其共聚物或其它可衍生成碳纤维的树脂，优选的，碳纤维前体所制出的微孔薄膜可经高温预氧化、石墨化、碳化等制程，成为纳米碳纤维微孔薄膜；(IV)其它高级工程材料选自：聚酰亚胺，聚酰胺(尼龙)，聚酯(PET)，芳纶，聚醚酮(PEEK)等；
步骤二、把本发明所述的含氟含氯导电高分子树脂填充入微孔薄膜骨架单面或双面 的孔隙里分别制备到含氟含氯导电高分子单面或双面复合薄膜：将步骤一所得的微孔薄膜骨架，以(单面或双面)涂布或浸泡方法，把本发明的含氟含氯导电高分子和任选的少量的活性炭粉、石墨粉、石墨烯或稀有金属粉，填充入微孔薄膜骨架单面或双面的孔隙里将复合材料烘干，将复合材料烘干，制得含氟含氯高分子单面或双面填充复合薄膜；其中，任选添加的少量的活性炭粉、石墨粉、石墨烯或稀有金属粉的总重量不超过含氟含氯导电高分子树脂25％的重量，优选的不超过含氟含氯导电高分子树脂11％的重量；较佳地，所述稀有金属粉选自银(Ag)、铂(Pt)、钯(Pd)。
制备本发明的含氟含氯导电高分子单面复合薄膜时，所述含氟含氯导电高分子树脂的磺酸或羧酸的酸当量数(meq/g)优选400～1600，更优选600～1200，更佳的在800～1100，其单膜的常温电导率(Conductivity)>0.05(S/cm)，优选的>0.1(S/cm)，更佳的>0.15(S/cm)。微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(25:75)～(75:25)，优选的在(35:65)～(65:35)。微孔薄膜骨架单面的孔隙大部分(>85％，优选的>95％，最优的>99％)被含氟含氯导电高分子树脂或其与少量的活性炭粉、石墨粉、石墨烯或稀有金属粉所填充，含氟含氯导电高分子树脂单面填充复合薄膜透空气率低，用Gurley透气仪测量让100毫升空气透过复合薄膜所需的时间>3分钟，优选的>10分钟。如在步骤二中不添加少量的活性炭粉、石墨粉、石墨烯或稀有金属粉时，含氟含氯高分子单面填充复合薄膜总重在10～200克/平米，优选的20～100克/平米，最优的在25～90克/平米，其厚度在1微米～100微米，优选的在3微米～50微米，最优的在5微米～30微米；如在步骤二中添加少量的活性炭粉、石墨粉、石墨烯或稀有金属粉时，此时含氟含氯高分子单面填充复合薄膜的总重在10～250克/平方米，优选的在20～150克/平方米，最优的在25～100克/平方米，其厚度在2微米～100微米，优选的在3微米～50微米，最优的在5微米～30微米。
制备本发明的含氟含氯导电高分子双面复合薄膜时含氟含氯导电高分子树脂的磺酸或羧酸的酸当量数(meq/g)优选400～1500，更优选在500～1100，更佳的在600～950。微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(5:95)～(40:60)，优选的在(10:90)～(30:70)。微孔薄膜骨架双面的孔隙大部分(>60％，优选的>75％，最优的>90％)被含氟含氯导电高分子树脂或其与少量的活性炭粉、石墨粉、石墨烯或稀有金属粉所填充，含氟含氯导电高分子双面填充复合薄膜透空气率低，用Gurley透气仪测量让100毫升空气透过此复合薄膜所需的时间>3分钟，优选的>10分钟。如在步骤二中不添加少量的活性炭粉、石墨粉、石墨烯或稀有金属粉时，含氟含氯导电高分子双面填充复合薄 膜总重在5～200克/平米，优选的10～100克/平米，最优的在20～90克/平米，其厚度在3微米～100微米，优选的在5微米～50微米，最优的在10微米～45微米，含氟含氯导电高分子双面填充复合薄膜的常温电导率(Conductivity)>0.10(S/cm)，优选的>0.15(S/cm)，更佳的>0.20(S/cm)；如在步骤二中添加少量的活性炭粉、石墨粉、石墨烯或稀有金属粉时，所得的含氟含氯导电高分子双面填充复合薄膜的总重在5～250克/平米，优选的在10～150克/平米，最优的在20～100克/平米，其厚度在3微米～100微米，优选的在5微米～50微米，最优的在10微米～30微米，其常温电导率(Conductivity)>0.1(S/cm)，优选的>0.15(S/cm)，更佳的>0.20(S/cm)。
本发明的含氟含氯导电高分子单面或双面填充复合薄膜的机械强度远优于单独用含氟含氯导电高分子所制得的膜，高的拉伸强度可以保证其能适用于质子交换膜燃料电池领域。此外，若将本发明的复合薄膜与尼龙6平织布进行复合，所得到的复合面料耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，耐水压仍大于100kPa；透湿气率>4000g/m 2/day，根据美国军规MIL-DTL-32102 3April 2002测仿糜烂毒气：氯乙醚(ClCH 2CH 2OCH 2CH 2Cl)穿透率合格<4μg/cm 2/day，足以证明本发明的复合膜抗生化穿透能力强，适用于制备核生化防护服。
实施例
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
以上实施例中所采用的测试方法和仪器分别为：
孔隙率的测试方法是根据ASTM标准D6093法检测；
拉伸强度利用拉力强度机(Instron)检测；测试方法：ASTM-D882
耐水压的测试方法依据JIS L1092法检测；
透湿气率，也称为MVTR，为水蒸汽通过片材材料的度量，用克/平方米/天表示；依据JIS L1099A1法测试，外层面布朝上；
透气性采用Gurley测法，测量100毫升空气透过样品的时间，外层布朝下；
根据美国军规MIL-DTL-32102 3April 2002测仿糜烂毒气：氯乙醚(ClCH 2CH 2OCH 2CH 2Cl)穿透率；
常温电导率(Conductivity)测试方法：在25℃温度下的电导率采用Crison 525电导计 测定。
上胶量的测试方法：将上胶后的单位膜重减去骨架的单位膜重。
(1)含氟含氯导电高分子树脂的制备
制备例1
在一个约100升内容积密闭的预乳化反应釜A内，常温下加入39000g纯净水，100g的全氟辛酸铵，开高速剪切搅拌，然后往釜里慢慢加入5000g的重量比70％CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F及30％CF 2＝CF-O-CF 2CF 2-SO 2F混合组成的含氟带磺酰氟液相单体，连续高速剪切搅拌约30分后，制得预聚体乳液；
在另一个约100升内容积的反应釜B内，釜里先排氧，直到釜里氧含量小于20ppm，然后加入从反应釜A来的全部预聚体乳液，釜里通入气相混合单体，其摩尔比为90％四氟乙烯及10％三氟氯乙烯，升温至70度，釜内压力维持在11公斤，加入2.5克过硫酸铵预溶于1升的去离子水，开始自由基聚合。
所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比约为4：5；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.05％；
反应温度控制在70～75度，反应时间一小时，将釜内温度降至室温后，停止搅拌，反应物放料，获得含氟含氯导电高分子乳液，其初级粒子的平均粒径约100纳米，乳液固含量约19％，所得含氟含氯导电高分子乳液经磺酰氟(-SO 2F)水解后得到含氟含氯带磺酸(-SO 3H)的导电高分子，干燥后，其比重约1.99，酸当量数(meq/g)约900，其单膜的常温电导率(Conductivity)>0.15(S/cm)。
制备例2
在一个约100升内容积密闭的预乳化反应釜A内，常温下加入39000g去离子水，100g的全氟辛酸铵，开高速剪切搅拌，然后往釜里慢慢加入5000g的重量比80％CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F及20％CF 2＝CF-O-CF 2CF 2-SO 2F的混合物，连续高速剪切搅拌约30分后，制得预聚体乳液；在另一个约100升内容积的反应釜B内，釜里先排氧，直到釜里氧含量小于20ppm，然后加入从反应釜A来的全部预聚体乳液，釜里通入混合气相混合单体，其摩尔比为75％四氟乙烯、20％偏氟乙烯及5％三氟氯乙烯，升温至70度，釜内压力维持在9公斤，加入2.5克过硫酸铵预溶于1升的去离子水，开始自由基聚合。
所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比约为5：4；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.05％；
反应温度控制在70～75度，反应时间约一小时，将釜内温度降至室温后，停止搅拌，反应物放料，获得含氟含氯导电高分子乳液，其初级粒子的平均粒径约120纳米，乳液固含量约21％，所得含氟含氯导电高分子乳液经磺酰氟(-SO 2F)水解后得到含氟含氯带磺酸(-SO 3H)的导电高分子，干燥后，其比重约1.91，酸当量数(meq/g)约800，其单膜的常温电导率>0.20(S/cm)。
制备例3：
在一个约100升内容积密闭的预乳化釜A内，常温下加入39000g纯净水，100g的全氟辛酸铵，开高速剪切搅拌，然后往釜里慢慢加入3000g的重量比50％CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F及50％CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F的混合物，连续高速剪切搅拌约30分后，制得预聚体乳液；在另一个约100升内容积的反应釜B内，釜里先排氧，直到釜里氧含量小于20ppm，然后加入从反应釜A来的全部预聚体乳液，釜里通入气相混合单体，其摩尔比为50％四氟乙烯及50％三氟氯乙烯，升温至70度，釜内压力维持在14公斤，加入1.5克过硫酸铵预溶于1升的去离子水，开始自由基聚合。
所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比约为1：3；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.05％；
反应温度控制在70～75度，反应时间约一小时，将釜内温度降至室温后，停止搅拌，反应物放料，获得含氟含氯导电高分子乳液，其初级粒子的平均粒径约150纳米，乳液固含量约22％，所得含氟含氯导电高分子乳液经磺酰氟(-SO 2F)水解后得到含氟含氯带磺酸(-SO 3H)的导电高分子，干燥后，其比重约2.02，酸当量数(meq/g)约1500，其单膜的常温电导率>0.02(S/cm)。
制备例4：
在一个约100升内容积密闭的预乳化反应釜A内，常温下加入39000g去离子水，300g的全氟辛酸铵，开高速剪切搅拌，然后往釜里慢慢加入6000g的重量比20％CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F及80％CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F的混合物，连续高速剪切搅拌约30分后，制得预聚体乳液；在另一个约100升内容积的反应釜B内，釜里先排氧，直到釜里氧含量小于20ppm，然后加入从反应釜A来的全部预聚体乳液，釜里通入气相混合单体，其摩尔比为70％四氟乙烯及30％三氟氯乙烯，升温至70度，釜内压力维持在10公斤，加入3克过硫酸铵预溶于1升的去离子水，开始自由基聚合。
所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比约为3:1；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.05％；
反应温度控制在70～75度，反应时间约一小时，将釜内温度降至室温后，停止搅拌，反应物放料，获得含氟含氯导电高分子乳液，其初级粒子的平均粒径约70纳米，乳液固含量约19.5％，所得含氟含氯导电高分子乳液经磺酰氟(-SO 2F)水解后得到含氟含氯带磺酸(-SO 3H)的导电高分子，干燥后，其比重约1.97，酸当量数(meq/g)约500，其单膜的常温电导率>0.35(S/cm)。
制备例5
在一个约100升内容积密闭的预乳化釜A内，常温下加入39000g去离子水，300g的全氟辛酸铵，开高速剪切搅拌，然后往釜里慢慢加入3公斤的重量比60％CF 2＝CF-CF 2-O-SO 2F及40％CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F的混合物，连续高速剪切搅拌约30分后，制得预聚体乳液；在另一个约100升内容积的反应釜B内，釜里先排氧，直到釜里氧含量小于20ppm，然后加入从反应釜A来的全部预聚体乳液，釜里通入气相混合单体，其摩尔比为25％四氟乙烯、70％偏氟乙烯、5％三氟氯乙烯，升温至80度，釜内压力维持在17公斤，加入1.5克过硫酸铵预溶于1升的去离子水，开始自由基聚合。
所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比约为1:2.5；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.05％；
反应温度控制在80～85度，反应时间约45分钟，将釜内温度降至室温后，停止搅拌，反应物放料，获得含氟导电高分子乳液，其初级粒子的平均粒径约50纳米，乳液固含量约20％，所得含氟导电高分子乳液经磺酰氟(-SO 2F)水解成磺酸(-SO 3H)，(-CF 2-O-SO 2F)水解成羧酸(-COOH)的含氟含磺酸/羧酸导电高分子，干燥后，其比重约1.72，酸当量数(meq/g)约950，其单膜的常温电导率>0.10(S/cm)。
(2)微孔薄膜骨架的制备
制备例6：
将制备例3中制造得的含氟含氯导电高分子树脂与二甲基乙酰胺以约1：4的重量比混合，升温搅拌，树脂溶解后，用静电纺丝法喷纳米纤维丝，每分钟产能约5克，所产生纳米纤维丝用离型形纸收集，所制得的纳米纤维丝堆积在离形纸上，离形纸以每分钟0.1米的速度前进，所收集到的是一幅宽约1米的纳米纤维丝膜，将此丝膜在约90℃热风处理下渐烘干纳米纤维丝薄膜，最终行成厚度约20微米，宽度约100厘米的纳米纤维丝薄膜，纤维的平均直径约170纳米，经检测，膜重约10克/平米，孔隙率约78～82％， 比重为0.39，透气性Gurley测法100毫升空气透过速度约7～12秒。
制备例7：
将聚丙烯腈PAN树脂(由丙烯腈和少量丙烯酸甲醋、甲叉丁二脂共聚生成共聚聚丙烯腈树脂，分子量高于6到8万)与二甲基亚矾以约1：4的重量比混合，升温搅拌，树脂溶解后，用超高速离心纺丝法喷纳米纤维丝，每分钟产能约20克，所产生纳米纤维丝用离型形纸收集，所制得的纳米纤维丝堆积在离形纸上，离形纸以每分钟0.1米得速度前进，所收集到的是一幅宽约1米的纳米纤维丝膜，将此丝膜在约160℃热风处理下渐烘干纳米纤维丝薄膜，最终形成厚度约70微米，宽度约100厘米的纳米纤维丝薄膜，纤维的平均直径约350纳米；经检测，膜重约39克/平米，孔隙率约82～86％，比重为0.28，透气性Gurley测法100毫升空气透过速度约13～17秒。
制备例8：
将制备例7中制造得到的聚丙烯腈纳米微孔薄膜，在空气下加热至约270℃，保温2h，聚丙烯腈PAN树脂纳米微孔薄膜的颜色由白色逐渐变成黄色、棕色，最后形成黑色的预氧化微孔薄膜，是聚丙烯腈线性高分子受热氧化后，发生氧化、热解、交联、环化等一系列化学反应形成耐热梯型高分子的结果，然后将预氧化微孔薄膜在氮气中进行高温处理1600℃的碳化处理，则纳米纤维进一步产生交联环化、芳构化及缩聚等反应，并脱除氢、氮、氧原子，最后形成二维碳环平面网状结构和层片粗糙平行的乱层石墨结构的PAN基纳米碳纤维薄膜，最终形成厚度约15微米，宽度约100厘米的纳米纤维丝薄膜，纤维的平均直径约160纳米，经检测，膜重约7克/平米，孔隙率约89～93％，比重为0.27，透气性Gurley测法100毫升空气透过速度约7～9秒。
制备例9：
将ECTFE树脂(乙烯与三氟氯乙烯共聚物，来自苏威公司)用熔融纺丝法喷ECTFE纤维纳米丝，每分钟喷丝约20克，所产生纳米纤维丝用离型形纸收集，所制得的纳米纤维丝堆积在离形纸上，离形纸以每分钟1米的速度前进，所收集到的是一幅宽约1米的ECTFE纳米纤维丝膜，最终形成厚度约45微米，宽度约100厘米的纳米纤维丝薄膜，纤维的平均直径约450纳米，经检测，膜重约20克/平米，孔隙率约75～80％，比重为0.42，透气性Gurley测法100毫升空气透过速度约12～15秒。
制备例10
将PET聚酯树脂与碳酸乙烯酯以约1：4的重量比混合，升温搅拌，树脂溶解后，在略超过200℃的溶液温度下全面涂布在离形纸上，所生成的PET膜经急速冷却至室温， 撕去离形纸，将此PET膜在约170℃热风处理下渐烘干PET薄膜，最终形成厚度约50微米，宽度约160厘米的纳米微孔薄膜，经检测，所得纳米微孔薄膜的膜重约15克/平米，孔隙率约68～72％，比重为0.29，透气性Gurley测法100毫升空气透过速度约17～23秒。
(3)含氟含氯导电高分子单面复合薄膜
实施例1
将制备例5中制造得到的含氟含氯导电高分子(酸当量数950)先溶解在二甲基甲酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，再加入溶液重量约5％的活性碳粉，将制备例9中制得到的ECTFE微孔薄膜骨架，常温单面浸泡在溶液里约一分钟，取出单面浸泡的薄膜，轻轻刮去单面浸泡膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得复合薄膜最终厚度约47微米，宽度约100厘米的透明薄膜，膜重约39克/平米，上胶量约19克/平米，透气性Gurley测法100毫升空气透过速度大于3分钟。
此复合薄膜的机械强度(拉伸强度大于50MPa)远优于单独用制备例5所得的含氟含氯导电高分子(酸当量数950)所制得的膜(拉伸强度小于20MPa)。
将此复合薄膜与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复合，此复合面料，耐水压初始大于200kPa，经水洗10次后，耐水压仍大于100kPa；透湿气率>4000g/m 2/day，氯乙醚穿透率合格<4μg/cm 2/day，证明此复合膜抗有毒有害化学物质穿透能力强。
实施例2
将制备例5中制造得到的含氟含氯导电高分子(酸当量数950)先溶解在二甲基甲酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，将实施例10中制得到的PET聚酯微孔薄膜骨架，常温单面浸泡在所制的20％含氟含氯导电高分子(酸当量数950)溶液里约一分钟，取出单面浸泡浸泡的薄膜，轻轻刮去单面浸泡膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得含氟含氯高分子单面填充复合薄膜最终厚度约53微米，宽度约100厘米的透明薄膜，膜重约33克/平米，上胶量约18克/平米，透气性Gurley测法100毫升空气透过速度大于3分钟。此复合薄膜的机械强度(拉伸强度大于30MPa)远优于单独用制备例5所得的含氟含氯导电高分子(酸当量数950)所制得的膜(拉伸强度小于20MPa)。
将此复合薄膜与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复 合，此复合面料，耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，耐水压仍大于100kPa；透湿气率>4000g/m 2/day，氯乙醚(ClCH 2CH 2OCH 2CH 2Cl)穿透率合格<4μg/cm 2/day，证明此复合膜抗抗有毒有害化学物质穿透能力强。
(4)含氟含氯导电高分子双面复合薄膜
实施例3
将制备例1中制造得到的含氟含氯导电高分子树脂先溶解在二甲基乙酰胺/乙醇(1:1)溶液里，含氟含氯导电高分子树脂在溶液里的浓度约20％，将制备例6中制得到的含氟含氯导电高分子(酸当量数1500)微孔薄膜骨架，常温双面浸泡在所制的20％含氟含氯导电高分子(酸当量数900)溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，复合薄膜最终厚度约25微米，宽度约100厘米的透明薄膜，膜重约45克/平米，上胶量约35克/平米，比重为1.81，透气性Gurley测法100毫升空气透过速度大于3分钟，复合膜导电度约0.11(S/cm)。此复合膜的机械强度(拉伸强度大于30MPa)远优于单独用制备例1得到的含氟含氯导电高分子(酸当量数900)所制得的膜(拉伸强度小于20MPa)，适合做燃料电池应用。
实施例4
将制备例4中制造得到的含氟含氯导电高分子树脂先溶解在二甲基乙酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，再加入溶液重量约5％的石墨粉及1ppm金属铂的纳米颗粒，将制备例6中制得到的含氟含氯导电高分子(酸当量数1500)微孔薄膜骨架，常温双面浸泡在所制的溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得复合薄膜最终厚度约25微米，宽度约100厘米的透明薄膜，膜重约47克/平米，上胶量约37克/平米，比重为1.83，透气性Gurley测法100毫升空气透过速度大于3分钟；复合膜导电度约0.23(S/cm)。此复合膜的机械强度(拉伸强度大于30MPa)远优于单独用制备例4得到的含氟含氯导电高分子(酸当量数500)所制得的膜(拉伸强度小于10MPa，完全无强度)，适合做燃料电池应用。
实施例5
将制备例1中制造得到的含氟含氯导电高分子树脂(酸当量数900)先溶解在二甲基乙酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，再加入10ppm石墨烯，将制备例8中制得到的碳纤维微孔薄膜骨架，常温双面浸泡在所制的溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经 检测，所得复合薄膜最终厚度约19微米，宽度约100厘米的透明薄膜，膜重约37克/平米，上胶量约12克/平米，比重约为1.93，透气性Gurley测法100毫升空气透过速度大于3分钟，复合膜导电度约0.19(S/cm)。此复合膜的机械强度(拉伸强度大于60MPa)远优于单独用制备例1所得的含氟含氯导电高分子(酸当量数900)所制得的膜(拉伸强度小于20MPa)，适合做燃料电池应用。
实施例6
将制备例4中制造得到的含氟含氯导电高分子树脂(酸当量数500)先溶解在二甲基乙酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，将实施例9中制得到的ECTFE微孔薄膜骨架，常温双面浸泡在所制的20％含氟含氯导电高分子(酸当量数500)溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得复合薄膜最终厚度约50微米，宽度约100厘米的透明薄膜，膜重约98克/平米，上胶量约78克/平米，比重为1.96，透气性Gurley测法100毫升空气透过速度大于3分钟，复合膜导电度约0.17(S/cm)。此复合膜的机械强度(拉伸强度大于50MPa)远优于单独用制备例4所得的含氟含氯导电高分子(酸当量数500)所制得的膜(拉伸强度小于10MPa，完全无强度)，适合做燃料电池应用。
实施例7
将制备例5中制造得到的含氟含氯导电高分子树脂(酸当量数950)先溶解在二甲基甲酰胺/乙醇(1:1)溶液里，导电高分子在溶液里的浓度约20％，将制备例8中制得到的碳纤维微孔薄膜骨架，常温双面浸泡在所制的20％含氟含氯导电高分子(酸当量数950)溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得复合薄膜最终厚度约21微米，宽度约100厘米的透明薄膜，膜重约39克/平米，上胶量约32克/平米，比重约为1.86，透气性Gurley测法100毫升空气透过速度大于3分钟，此复合薄膜导电度约0.13(S/cm)，此复合薄膜的机械强度(拉伸强度大于1000MPa)远优于单独用制备例5所得的含氟含氯导电高分子(酸当量数950)所制得的膜。
此复合薄膜与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复合，此复合面料，耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，耐水压仍大于100kPa；透湿气率>4000g/m 2/day，根据美国军规MIL-DTL-32102 3April 2002测仿糜烂毒气：氯乙醚(ClCH 2CH 2OCH 2CH 2Cl)穿透率合格<4μg/cm 2/day，证明此复合薄膜抗有毒有害化学物质穿透能力强。
(5)对比实施例
对比实施例1：
将杜邦的全氟导电高分子膜(Nafion NR-211，膜厚25微米)与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复合，此复合面料，耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，膜与布完全分离，无法耐水压；透湿气率>4000g/m 2/day，氯乙醚穿透率合格>60μg/cm 2/day，证明此复合膜抗有毒有害化学物质穿透能力差。
对比实施例2：
将杜邦的全氟导电高分子膜(Nafion NR-212，膜厚50微米)与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复合，此复合面料，耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，膜与布完全分离，无法耐水压；透湿气率>4000g/m 2/day，氯乙醚穿透率合格>40μg/cm 2/day，证明此复合膜抗有毒有害化学物质穿透能力差。
对比实施例3：
将杜邦Nafion的D520全氟磺酸树脂溶液抽真空浓缩，直到全氟磺酸导电高分子Nafion在溶液里的浓度约20％，以网购来的膨化聚四氟乙烯薄膜做微孔薄膜骨架，常温双面浸泡在所制的20％全氟导电高分子溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得特种含氟含氯双面填充复合薄膜最终厚度约25微米，宽度约100厘米的透明薄膜，膜重约50克/平米，比重为1.98，透气性Gurley测法100毫升空气透过速度大于3分钟，复合膜常温电导率约0.08(S/cm)，此复合膜的常温电导率小于0.1(S/cm)，不能被燃料电池膜市场应用所接受。
对比实施例4：
将杜邦Nafion的D520全氟磺酸树脂溶液抽真空浓缩，直到全氟磺酸导电高分子在溶液里的浓度约20％，将制备例8中制得到的碳纤维微孔薄膜骨架，常温双面浸泡在所制的20％全氟导电高分子溶液里约一分钟，取出浸泡的薄膜，轻轻刮去膜表面多余液体，在90℃下慢慢烘干，即获得复合薄膜；经检测，所得特种含氟含氯导电高分子双面填充复合薄膜最终厚度约21微米，宽度约100厘米的透明薄膜，膜重约40克/平米，比重约为1.89，透气性Gurley测法100毫升空气透过速度大于3分钟，此含氟含氯导电高分子双面填充复合薄膜常温电导率约0.09(S/cm)。
此复合薄膜与尼龙6平织布(90克/平米)，经点状聚氨酯贴合胶点将薄膜与布复合，此复合面料，耐水压(JIS L1092法)初始大于200kPa，经水洗10次后，膜与布分离，无法为市场接受；透湿气率>4000g/m 2/day，氯乙醚穿透率合格>40μg/cm 2/day，说明此复合薄膜抗有毒有害化学物质穿透能力差。
以上实施例及对比例明显看出全氟导电高分子膜的抗有毒有害化学物质能力不及含氟含氯导电高分子膜，含氟含氯导电高分子单面或双面复合薄膜的机械强度远优于单独用含氟含氯导电高分子所制得的膜，并且具有优异的透气性、导电性，使用复合薄膜制备得到的复合面料的耐水性优异、透湿气率高、抗有毒有害化学物质穿透能力强。含氟含氯导电高分子双面填充复合薄膜的性能优于全氟导电高分子双面填充复合薄膜。
本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。

Claims (27)

  1. 一种含氟含氯导电高分子树脂的制备方法，其特征在于，包括如下步骤：
    S1按重量百分比将可自由基聚合的含氟带磺酰氟液相单体1％～20％、纯净水79％～98％、含氟表面活性剂0.01％～1％加入反应釜中进行高速搅拌，得到预聚体乳液；
    S2往反应釜内通入四氟乙烯、偏氟乙烯中的一种或两种与三氟氯乙烯的气相混合单体，反应压力为5公斤或以上；然后通入自由基引发剂，反应温度在20～120℃，反应压力在5～25公斤，反应时间为15～180min，得到反应产物为含氟含氯带磺酰氟的高分子乳液；所述含氟带磺酰氟液相单体与所述气相混合单体实际参与自由基聚合反应的总重量之比为1：3～3：1；自由基引发剂的通入总重量与含氟带磺酰氟液相单体的重量比为0.01％～3.0％；
    S3对含氟含氯带磺酰氟的高分子乳液进行水解，再经凝聚、水洗、干燥后得到含氟含氯导电高分子树脂。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述含氟带磺酰氟液相单体包括CF 2＝CF-O-R f-SO 2F、CF 2＝CF-O-R f1-O-R f2-SO 2F、CF 2＝CF-CF 2-O-R f3-SO 2F中一种或几种，其中R f、R f1、R f2是1～6个碳的含氟烷基，R f3是0～5个碳的含氟烷基，优选地，所述含氟带磺酰氟液相单体包括CF 2＝CF-O-CF 2CF 2-SO 2F、CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F、CF 2＝CF-CF 2-O-SO 2F、CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F中的一种或几种。
  3. 根据权利要求1或2所述的制备方法，其特征在于，当所述含氟含氯导电高分子树脂应用于电池领域时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0～80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F 20％～99％，CF 2＝CF-CF 2-O-SO 2F 0％～20％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，以上物质重量百分比之和为100％。
  4. 根据权利要求1或2所述的制备方法，其特征在于，当所述含氟含氯导电高分子树脂应用于核生化防护膜材时，含氟带磺酰氟液相单体以如下重量百分比组成：CF 2＝CF-O-CF 2CF 2-SO 2F 0～80％，CF 2＝CF-O-CF 2CF(CF 3)-O-CF 2CF 2-SO 2F 0％～20％，CF 2＝CF-CF 2-O-SO 2F 20％～100％，CF 2＝CF-CF 2-O-CF 2CF 2-SO 2F 0％～80％，以上物质重量百分比之和为100％。
  5. 根据权利要求1-4中任一项所述的制备方法，其特征在于，所述含氟带磺酰氟单体里含有含氟不带磺酰氟试剂，所述含氟不带磺酰氟试剂与含氟带磺酰氟单体的重量比小于或等于30％。
  6. 根据权利要求5所述的制备方法，其特征在于，所述含氟不带磺酰氟试剂包括含氟烷基、含氟烷基醚、全氟甲基乙烯基醚、全氟乙基乙烯基醚、全氟丙基乙烯基醚、3，3，3-三氟丙烯或全氟烷基乙烯中的一种或多种。
  7. 根据权利要求1-6中任一项所述的制备方法，其特征在于，所述气相混合单体以摩尔比计含：25％～90％的四氟乙烯、0％～70％的偏氟乙烯、5％～50％的三氟氯乙烯。
  8. 根据权利要求1-7中任一项所述的制备方法，其特征在于，所述含氟表面活性剂包括含6～16个碳的有机物，并至少含一个羧酸或者磺酸的官能团。
  9. 根据权利要求1-8中任一项所述的制备方法，其特征在于，所述自由基引发剂包括过硫酸盐、双氧水、有机过氧化合物中的一种或多种。
  10. 一种含氟含氯导电高分子单面填充复合薄膜，其特征在于，包括微孔薄膜骨架与根据权利要求1-9中任一项制备方法所得到的含氟含氯导电高分子树脂，所述微孔薄膜骨架的单面的孔隙体积超过85％被所述含氟含氯导电高分子树脂所填充。
  11. 根据权利要求10所述的一种含氟含氯导电高分子单面填充复合薄膜的制作方法，其特征在于，包括如下步骤：
    将微孔薄膜骨架以涂布或浸泡方法，把所述含氟含氯导电高分子树脂填充入微孔薄膜骨架单面的孔隙里得到复合材料；将复合材料烘干，制得含氟含氯导电高分子单面填充复合薄膜。
  12. 根据权利要求11所述的制作方法，其特征在于，微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(25:75)～(75:25)。
  13. 根据权利要求11所述的制作方法，其特征在于，微孔薄膜骨架通过如下方法制备：
    先将可热熔性含氟树脂或可热熔性含氯含氟树脂、权利要求1-9中任一项制备方法所得到的含氟含氯导电高分子树脂、碳纤维前体、聚酰亚胺、聚酰胺、聚酯、芳纶、聚醚酮中的一种进行纺丝，经热熔喷丝或湿法喷丝，均匀地收集成无规则网状微孔结构，经热定形后得到微孔薄膜骨架。
  14. 根据权利要求11所述的制作方法，其特征在于，微孔薄膜骨架以涂布或浸泡方法，将活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种，与含氟含氯导电高分子树脂混合一并填充入其微孔薄膜单面的孔隙里，优选地，所述活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种的总重量不超过含氟含氯导电高分子树脂的重量的25％。
  15. 根据权利要求14所述的制作方法，其特征在于，所述稀有金属粉为银、铂或钯。
  16. 根据权利要求13所述的制作方法，其特征在于，可热熔性含氟树脂或含氯含氟树脂包括可热熔性聚四氟乙烯共聚物、聚三氟氯乙烯或其共聚物、聚偏氟乙烯或其共聚物中的一种或几种。
  17. 根据权利要求11-16中任一项所述的制作方法，其特征在于，所述含氟含氯导电高分子树脂的磺酸或羧酸的酸当量数(meq/g)在400～1600。
  18. 根据权利要求11-17中任一项所述的制作方法，其特征在于，采用湿式相变化法、温差相变化法、干式溶剂法、静电纺丝法或超高速离心纺丝法进行纺丝。
  19. 一种含氟含氯导电高分子双面填充复合薄膜，其特征在于，包括微孔薄膜骨架与根据权利要求1-9中任一项制备方法所得到的含氟含氯导电高分子树脂，所述微孔薄膜骨架的双面的孔隙体积超过60％被含氟含氯导电高分子树脂所填充。
  20. 根据权利要求19所述的一种含氟含氯导电高分子双面填充复合薄膜的制作方法，其特征在于，包括如下步骤：
    将微孔薄膜骨架以涂布或浸泡的方式，把所述含氟含氯导电高分子树脂填充入微孔薄膜骨架双面的孔隙里得到复合材料；将复合材料烘干，制得含氟含氯导电高分子双面填充复合薄膜。
  21. 根据权利要求20所述的制作方法，其特征在于，微孔薄膜骨架与含氟含氯导电高分子树脂的重量比为(5:95)～(40:60)。
  22. 根据权利要求20所述的制作方法，其特征在于，微孔薄膜骨架通过如下方法制备：
    先将可热熔性含氟树脂或可热熔性含氯含氟树脂、权利要求1-9中任一项制备方法所得到的含氟含氯导电高分子树脂、碳纤维前体、聚酰亚胺、聚酰胺、聚酯、芳纶、聚醚酮中的一种进行纺丝，经热熔喷丝或湿法喷丝，均匀地收集成无规则网状微孔结构，经热定形后得到微孔薄膜骨架。
  23. 根据权利要求20所述的制作方法，其特征在于，微孔薄膜骨架以涂布或浸泡方法，将活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种，与所述含氟含氯导电高分子树脂混合一并填充入其微孔薄膜双面的孔隙里；优选地，所述活性炭粉、石墨粉、石墨烯、稀有金属粉中的一种或几种的总重量不超过含氟含氯导电高分子树脂的重量的25％。
  24. 根据权利要求23所述的制作方法，其特征在于，所述稀有金属粉为银、铂或钯。
  25. 根据权利要求22所述的制作方法，其特征在于，可热熔性含氟树脂或含氯含氟树脂包括可热熔性聚四氟乙烯共聚物、聚三氟氯乙烯或其共聚物、聚偏氟乙烯或其共聚物中的一种或几种。
  26. 根据权利要求22-25中任一项所述的制作方法，其特征在于，所述含氟含氯导电高分子树脂的酸当量数(meq/g)在400～1500。
  27. 根据权利要求22-26中任一项所述的制作方法，其特征在于，采用湿式相变化法、温差相变化法、干式溶剂法、静电纺丝法或超高速离心纺丝法进行纺丝。
PCT/CN2018/081864 2017-04-18 2018-04-04 一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法 WO2018192368A1 (zh)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB1916736.0A GB2575951B (en) 2017-04-18 2018-04-04 Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same
DE112018002056.8T DE112018002056B4 (de) 2017-04-18 2018-04-04 Verfahren zur Herstellung eines fluorhaltigen chlorhaltigen elektrisch leitenden Polymerharzes und ein damit hergestellter einseitig oder beidseitig gefüllter Verbundfilm sowie Verfahren zur Herstellung desselben
US16/605,668 US11136424B2 (en) 2017-04-18 2018-04-04 Preparation method for fluorine- and chlorine-containing conductive polymer resin and single- or double-sided filled composite thin film prepared using same and the preparation method therefor

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN201710251603.2 2017-04-18
CN201710251603.2A CN106968110B (zh) 2017-04-18 2017-04-18 一种含氟含氯导电高分子双面填充复合薄膜及其制备方法
CN201710251601.3A CN106977640B (zh) 2017-04-18 2017-04-18 一种含氟含氯导电高分子单面填充复合薄膜及其制备方法
CN201710251601.3 2017-04-18
CN201710251598.5A CN106947027B (zh) 2017-04-18 2017-04-18 一种含氟含氯导电高分子树脂的制备方法
CN201710251598.5 2017-04-18

Publications (1)

Publication Number Publication Date
WO2018192368A1 true WO2018192368A1 (zh) 2018-10-25

Family

ID=63856950

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/081864 WO2018192368A1 (zh) 2017-04-18 2018-04-04 一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法

Country Status (4)

Country Link
US (1) US11136424B2 (zh)
DE (1) DE112018002056B4 (zh)
GB (1) GB2575951B (zh)
WO (1) WO2018192368A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030148158A1 (en) * 1999-12-29 2003-08-07 Ameduri Bruno Michel Fluorosulphonated elastomers with low glass transition based on vinylidene fluoride
CN103087251A (zh) * 2011-10-28 2013-05-08 上海三爱富新材料股份有限公司 共聚调聚物的制备方法
CN106947027A (zh) * 2017-04-18 2017-07-14 浙江汉丞科技有限公司 一种含氟含氯导电高分子树脂的制备方法
CN106968110A (zh) * 2017-04-18 2017-07-21 浙江汉丞科技有限公司 一种含氟含氯导电高分子双面填充复合薄膜及其制备方法
CN106977640A (zh) * 2017-04-18 2017-07-25 浙江汉丞科技有限公司 一种含氟含氯导电高分子单面填充复合薄膜及其制备方法

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5082472A (en) 1990-11-05 1992-01-21 Mallouk Robert S Composite membrane for facilitated transport processes
DE69835649T2 (de) 1997-10-15 2007-09-13 E.I. Dupont De Nemours And Co., Wilmington Copolymere aus Maleinsäure oder dessen Anhydrid und fluorierten Olefinen
ITMI991516A1 (it) * 1999-07-09 2001-01-09 Ausimont Spa Sintesi dei copolimeri peralogenati termoprocesabili del clorotrifluoroetilene
ITMI20010383A1 (it) 2001-02-26 2002-08-26 Ausimont Spa Membrane idrofiliche porose
US6713567B2 (en) * 2001-07-13 2004-03-30 E. I. Du Pont De Nemours And Company Method for forming fluorinated ionomers
WO2004018527A1 (ja) * 2002-06-17 2004-03-04 Daikin Industries, Ltd. 含フッ素ポリマー分散体及び含フッ素ポリマー分散体製造方法
ITMI20050444A1 (it) 2005-03-17 2006-09-18 Solvay Solexis Spa Membrana ionomerica
US20070281198A1 (en) * 2006-06-01 2007-12-06 Lousenberg Robert D Membranes electrode assemblies prepared from fluoropolymer dispersions
CN100519594C (zh) 2006-12-25 2009-07-29 山东东岳神舟新材料有限公司 一种含氟聚合物及其作为离子交换纤维材料的应用
US8088491B2 (en) 2007-08-20 2012-01-03 Huey-Shen Wu Fluorochloro ionomers
CN101692496B (zh) 2008-07-29 2013-09-25 山东华夏神舟新材料有限公司 一种多层含氟交联离子膜及其制备方法
CN101764232B (zh) 2008-11-14 2012-07-04 山东东岳高分子材料有限公司 具有交联网络结构的含氟质子交换膜及其制备
EP2493940B2 (en) * 2009-10-29 2018-08-29 Solvay Specialty Polymers Italy S.p.A. Process for the isolation of sulfonyl fluoride polymers and polymers obtained therefrom
CN101798365B (zh) 2009-12-11 2012-09-19 山东华夏神舟新材料有限公司 一种全氟离子交换树脂及其制备方法和应用
CN101709102B (zh) 2009-12-15 2012-11-14 山东华夏神舟新材料有限公司 高交换容量全氟树脂及其制备方法和用途
CN102633688A (zh) 2012-04-13 2012-08-15 华东理工大学 全氟乙烯基醚磺酸盐及其制备方法和用途
EP2882705B1 (en) 2012-08-10 2018-02-21 Solvay Specialty Polymers Italy S.p.A. Allyl-bearing fluorinated ionomers
CN103204961B (zh) 2013-04-18 2014-11-05 山东东岳高分子材料有限公司 一种使用混合含氟表面活性剂制备含氟聚合物的方法
CN105683222B (zh) 2013-07-18 2018-11-16 紧密薄膜系统公司 烯烃和链烷烃混合物的膜分离
CN103483748B (zh) 2013-07-23 2015-10-21 中大鑫新材料科技（厦门）有限公司 特种含氟分散树脂混合料及其微孔薄膜的制备方法
CN105111351A (zh) 2015-08-12 2015-12-02 江苏梅兰化工有限公司 一种特种氟醚表面活性剂的制备方法
CN106366230B (zh) 2016-08-23 2018-11-23 金华永和氟化工有限公司 一种用于控制含氟聚合物乳液粒径的混合表面活性剂及其制备含氟聚合物的方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030148158A1 (en) * 1999-12-29 2003-08-07 Ameduri Bruno Michel Fluorosulphonated elastomers with low glass transition based on vinylidene fluoride
CN103087251A (zh) * 2011-10-28 2013-05-08 上海三爱富新材料股份有限公司 共聚调聚物的制备方法
CN106947027A (zh) * 2017-04-18 2017-07-14 浙江汉丞科技有限公司 一种含氟含氯导电高分子树脂的制备方法
CN106968110A (zh) * 2017-04-18 2017-07-21 浙江汉丞科技有限公司 一种含氟含氯导电高分子双面填充复合薄膜及其制备方法
CN106977640A (zh) * 2017-04-18 2017-07-25 浙江汉丞科技有限公司 一种含氟含氯导电高分子单面填充复合薄膜及其制备方法

Also Published As

Publication number Publication date
GB201916736D0 (en) 2020-01-01
GB2575951B (en) 2022-07-13
US11136424B2 (en) 2021-10-05
DE112018002056B4 (de) 2021-12-09
GB2575951A (en) 2020-01-29
GB2575951A8 (en) 2020-03-04
US20200131290A1 (en) 2020-04-30
DE112018002056T5 (de) 2020-01-02

Similar Documents

Publication Publication Date Title
CN106968110B (zh) 一种含氟含氯导电高分子双面填充复合薄膜及其制备方法
US3692569A (en) Surface-activated fluorocarbon objects
CA2932016C (en) Polymer electrolyte membrane
TWI713443B (zh) 雙軸拉伸多孔質膜
US6156451A (en) Process for making composite ion exchange membranes
CA2932014C (en) Polymer electrolyte film
US6692858B2 (en) Electrolyte membrane for polymer electrolyte fuel cell and producing method thereof
CN105829415B (zh) 多孔质体、高分子电解质膜、过滤器用滤材和过滤器单元
JP5855093B2 (ja) ポリイミド多孔性ウェブ、その製造方法、及びそれを含む電解質膜
DE60206573T2 (de) Verfahren zum Imprägnieren von Trägern
JP2009245639A (ja) 固体高分子形燃料電池用電解質膜、その製造方法及び固体高分子形燃料電池用膜電極接合体
CA1209528A (en) Fluorpolymer membrane with microporous stretched sheet reinforcement
CN100595960C (zh) 一种微孔膜增强的多层含氟交联离子膜及其制备方法
CN106947027B (zh) 一种含氟含氯导电高分子树脂的制备方法
CN106977640B (zh) 一种含氟含氯导电高分子单面填充复合薄膜及其制备方法
CN104134812A (zh) 一种纤维网增强的聚合物电解质膜及其制备方法
WO2018233346A1 (zh) 一种含氟混合料和以其为原料的含氟超疏油微孔膜及制备方法和应用
WO2018192368A1 (zh) 一种含氟含氯导电高分子树脂的制备方法及其制备的单面或双面填充复合薄膜和制备方法
WO1998051733A1 (en) Process for making composite ion exchange membranes
JP2008238134A (ja) イオン交換性フィルタおよびその製造方法
JP2005179447A (ja) 膜体、膜・電極接合体及び固体高分子型燃料電池
CN115404722A (zh) 一种合成石墨烯改性水性聚氨酯蓄热织物覆膜的制备方法及应用
CN116948333A (zh) 一种填充改性微孔膜及其制备方法和应用
CN117024840A (zh) 一种表面改性微孔膜及其制备方法和应用
CN112501713A (zh) 一种含氟聚合物复合纤维的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18788429

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 201916736

Country of ref document: GB

Kind code of ref document: A

Free format text: PCT FILING DATE = 20180404

122 Ep: pct application non-entry in european phase

Ref document number: 18788429

Country of ref document: EP

Kind code of ref document: A1