CN106977640A - A kind of fluorine-containing chloride conducting polymer one side filled composite film and preparation method thereof - Google Patents

A kind of fluorine-containing chloride conducting polymer one side filled composite film and preparation method thereof Download PDF

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Publication number
CN106977640A
CN106977640A CN201710251601.3A CN201710251601A CN106977640A CN 106977640 A CN106977640 A CN 106977640A CN 201710251601 A CN201710251601 A CN 201710251601A CN 106977640 A CN106977640 A CN 106977640A
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fluorine
containing chloride
microporous membrane
resin
preparation
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CN201710251601.3A
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CN106977640B (en
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吴慧生
杨颖�
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Shanghai Hancheng Industrial Co ltd
Zhejiang Hancheng New Energy Co ltd
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Zhejiang Han Cheng Technology Co Ltd
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Priority to CN201710251601.3A priority Critical patent/CN106977640B/en
Publication of CN106977640A publication Critical patent/CN106977640A/en
Priority to PCT/CN2018/081864 priority patent/WO2018192368A1/en
Priority to DE112018002056.8T priority patent/DE112018002056B4/en
Priority to US16/605,668 priority patent/US11136424B2/en
Priority to GB1916736.0A priority patent/GB2575951B/en
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    • 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
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    • 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
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Abstract

The invention discloses fluorine-containing chloride conducting polymer one side filled composite film of one kind and preparation method thereof, the fluorine-containing chloride conducting polymer one side filled composite thin-film material includes microporous membrane skeleton and fluorine-containing chloride conducting polymer, the hole of the one side of the microporous membrane skeleton is filled more than 85% by fluorine-containing chloride conductive polymer resin, its physical mechanical strength is high, waterproof, oil resistant, pollution resistance are higher, and it is higher that this film can meet, penetrability higher to resistance water and the poisonous and harmful chemicals intrusion performance of prevention；When being applied to biochemical protective clothes, with light and permanent protective property energy to water and poisonous and harmful chemicals, fighting capacity comfortable, warming, that soldier can be greatly promoted；For the application of fuel cell, because its electrical conductivity is high, the electrical property of acquisition is preferable, and fuel such as hydrogen or alcohol are compared with the utilization that can burn more completely.

Description

A kind of fluorine-containing chloride conducting polymer one side filled composite film and preparation method thereof
Technical field
The present invention relates to fluorine-containing chloride conductive polymer resin filled composite thin-film material, and in particular to fluorine-containing chloride conduction Macromolecule resin filled composite thin-film material and preparation method thereof.
Background technology
Homopolymerization, modification or the copolymerized macromolecule resin of fluoro containing polymerses, especially tetrafluoroethene all have excellent physics Mechanical performance and chemical stability, in chemical materials, mechano-electronic, Aero-Space, military project protection, new material and new energy etc. Each field suffers from being widely applied；The homopolymerization of chloride macromolecule, such as CTFE, modification or copolymerized macromolecule resin are equal With excellent physical and mechanical properties and anti-chemical penetrability, there is significant contribution in chemical protection.Fluorine-containing conducting polymer is such as The Nafion resins of Du Pont, there is excellent electric conductivity and chemical stability, in being widely used for fuel cell and chlor-alkali cell, but Many shortcomings are still suffered from, such as electric conductivity is high not enough, the electrical conductivity at room temperature (Conductivity) of its monofilm<0.1(S/cm)； Chemical penetrability is high, it is impossible to effectively obstructs poisonous and harmful chemicals and penetrates.
Prepared by expanded PTFE is the polytetrafluoroethyldispersion dispersion resin for using high-crystallinity, is obtained through biaxial tension is expanded , the microcellular structure combined closely with height micron or nanofiber has excellent physical and chemical performance, and mechanical performance is prevented Water gas permeability and chemical stability, manufacture wire cable insulating material, artificial blood vessel, sealing have just been used for since the seventies Band, environmental protection filtering and garment material etc.；But it has the disadvantage that the paracentesis resistance of these microns or nanofiber is bad, and by These microns or nanofiber may proceed to be elongated and pull loose after power, cause membrane tissue to deform, and cause feature to decline, and have a strong impact on Film integral protection sexual function.
The preparation of micron or nanofibers structure can be also used in method of electrostatic spinning or ultracentrifugation spin processes, document There are many records, but how selection, spinneret prepare the techniques such as method, setting and need further to develop.
The content of the invention
In view of the shortcomings of the prior art, the present invention is directed to propose a kind of fluorine-containing chloride conducting polymer one side filled composite is thin Membrane material, with higher mechanical strength and waterproof, moisture-inhibiting, resistance to greasy dirt, water-fastness, fire-retardant, antibiotic weapon is penetrated and height is led The outstanding physical and chemical performance such as electrical.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of fluorine-containing chloride conducting polymer one side filled composite film, including microporous membrane skeleton and fluorine-containing chloride conduction Macromolecule resin, the pore volume of the one side of the microporous membrane skeleton is more than 85% by fluorine-containing chloride conductive polymer resin institute Filling；
The fluorine-containing chloride conductive polymer resin is prepared via a method which to obtain：First by weight percentage can be free Base polymerization fluorine-containing band sulfuryl fluoride liquid monomer 1%~20%, pure water 79%~98%, fluorine-containing surfactant 0.01%~ High-speed stirred is carried out in 1% addition reactor, pre-polymerization precursor emulsion is obtained；Then toward being passed through tetrafluoroethene, inclined fluorine second in reactor The gas phase mix monomer of one or both of alkene and CTFE, reaction pressure is 5 kilograms or more；Then pass to freedom Base initiator, reaction temperature is at 20-120 DEG C, and reaction pressure is at 5-25 kilograms, and the reaction time is 15-180min, obtains reaction production The fluorine-containing chloride macromolecule emulsion with sulfuryl fluoride of thing；The fluorine-containing band sulfuryl fluoride liquid monomer is actual with the gas phase mix monomer It is 1 to participate in the ratio between gross weight of Raolical polymerizable：3~3：1；Radical initiator is passed through gross weight and fluorine-containing band sulphonyl The weight ratio of fluorine liquid monomer is 0.01%~3.0%；Finally the fluorine-containing chloride macromolecule emulsion with sulfuryl fluoride is hydrolyzed, Again fluorine-containing chloride conductive polymer resin is obtained after condensing, washing, dry.
A kind of preparation method of above-mentioned fluorine-containing chloride conducting polymer one side filled composite film, comprises the following steps：
By microporous membrane skeleton to be coated with or immersion process, fluorine-containing chloride conductive polymer resin is packed into microporous membrane Composite is obtained in the hole of skeleton one side；Composite is dried, fluorine-containing chloride conducting polymer one side filling is made multiple Close film.
It should be noted that the weight ratio of microporous membrane skeleton and fluorine-containing chloride conducting polymer one side filled composite film For (25:75)-(75:25).
It should be noted that microporous membrane skeleton is prepared via a method which：
First by heat-fusible property fluorine resin or chlorinated and fluorinated resin, the fluorine-containing chloride conductive polymer resin, carbon fiber Precursor and its copolymer or the one kind that can be derivatized in the resin of carbon fiber, polyimides, polyamide, polyester, aramid fiber, polyether-ketone Spinning is carried out, through heating spinneret or wet method spinneret, random reticulated macroporous structure is equably collected into, obtains micro- after heat setting Hole film skeleton.
It should be noted that microporous membrane skeleton is to be coated with or immersion process, by activated carbon powder, graphite powder, graphene, dilute There are the one or more in metal powder, mixed with fluorine-containing chloride conductive polymer resin and be packed into its microporous membrane one side in the lump In hole.
Need further exist for explanation, the activated carbon powder, graphite powder, graphene, one kind in rare metal powder or several 25% of the gross weight planted no more than the weight of fluorine-containing chloride conductive polymer resin.
Explanation is needed further exist for, the rare metal powder is silver, Bo Huo Palladium.
It should be noted that in step S1, heat-fusible property fluorine resin or chlorinated and fluorinated resin include heat-fusible property poly- four One or more in fluoride copolymers, polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer.
It should be noted that the sulfonic acid or the acid equivalent number (meq/g) of carboxylic acid of the fluorine-containing chloride conductive polymer resin In 400-1600.
It should be noted that using wet type phase change method, temperature difference phase change method, dry type solvent method, method of electrostatic spinning or super High speed centrifugation spin processes carry out spinning.
The beneficial effects of the present invention are：The fluorine-containing chloride conducting polymer one side filled composite thin-film material, its thing High mechanical strength is managed, waterproof, oil resistant, pollution resistance are higher, this film can meet to resistance water and prevent poisonous and harmful chemicals from invading Enter that performance is higher, penetrability is higher；When being applied to biochemical protective clothes, with light and to water and poisonous and harmful chemicals Permanent protective property energy, fighting capacity comfortable, warming, that soldier can be greatly promoted；For the application of fuel cell, because of its electrical conductivity Height, the electrical property of acquisition is preferable, and fuel such as hydrogen or alcohol are compared with the utilization that can burn more completely.
Embodiment
The invention will be further described below, it is necessary to explanation, the present embodiment premised on the technical program, Detailed embodiment and specific operating process are given, but protection scope of the present invention is not limited to the present embodiment.
A kind of fluorine-containing chloride conducting polymer one side filled composite film, is microporous membrane skeleton and fluorine-containing chloride conductive height The hole of the filled composite film of molecule resin, wherein microporous membrane skeleton one side it is most of (>85%, preferably>95%, most Excellent>99%) filled by fluorine-containing chloride conductive polymer resin.
The fluorine-containing chloride conductive polymer resin is prepared via a method which to obtain：First by weight percentage can be free Base polymerization fluorine-containing band sulfuryl fluoride liquid monomer 1%~20%, pure water 79%~98%, fluorine-containing surfactant 0.01%~ High-speed stirred is carried out in 1% addition reactor, pre-polymerization precursor emulsion is obtained；Then toward being passed through tetrafluoroethene, inclined fluorine second in reactor The gas phase mix monomer of one or both of alkene and CTFE, reaction pressure is 5 kilograms or more；Then pass to freedom Base initiator, reaction temperature is at 20-120 DEG C, and reaction pressure is at 5-25 kilograms, and the reaction time is 15-180min, obtains reaction production The fluorine-containing chloride macromolecule emulsion with sulfuryl fluoride of thing；The fluorine-containing band sulfuryl fluoride liquid monomer is actual with the gas phase mix monomer It is 1 to participate in the ratio between gross weight of Raolical polymerizable：3~3：1；Radical initiator is passed through gross weight and fluorine-containing band sulphonyl The weight ratio of fluorine liquid monomer is 0.01%~3.0%；Finally the fluorine-containing chloride macromolecule emulsion with sulfuryl fluoride is hydrolyzed, Again fluorine-containing chloride conductive polymer resin is obtained after condensing, washing, dry.
Further, the fluorine-containing band sulfuryl fluoride liquid monomer includes CF2=CF-O-Rf-SO2F、CF2=CF-O-Rf1-O- Rf2-SO2F、CF2=CF-CF2-O-Rf3-SO2It is one or more of in F, wherein Rf、Rf1、Rf2It is that 1-6 carbon contains fluoroalkyl, Rf3 It is that 0-5 carbon contains fluoroalkyl.
Further, the fluorine-containing band sulfuryl fluoride liquid monomer includes CF2=CF-O-CF2CF2-SO2F, CF2=CF-O- CF2CFCF3-O-CF2CF2-SO2F、CF2=CF-CF2-O-SO2F、CF2=CF-CF2-O-CF2CF2-SO2One kind or several in F Kind.
Further, when the fluorine-containing chloride conductive polymer resin is applied to field of batteries, fluorine-containing band sulfuryl fluoride Liquid monomer is constituted with following percentage by weight：CF2=CF-O-CF2CF2-SO2F0-80%, CF2=CF-O-CF2CFCF3-O- CF2CF2-SO2F 20%-99%, CF2=CF-CF2-O-SO2F0%-20%, CF2=CF-CF2-O-CF2CF2-SO2F 0%- 80%.
Further, when the fluorine-containing chloride conductive polymer resin is applied to NBC protection membrane material, fluorine-containing band Sulfuryl fluoride liquid monomer is constituted with following percentage by weight：CF2=CF-O-CF2CF2-SO2F 0-80%, CF2=CF-O- CF2CFCF3-O-CF2CF2-SO2F 0%-20%, CF2=CF-CF2-O-SO2F 20%-100%, CF2=CF-CF2-O- CF2CF2-SO2F 0%-80%.
Further, can be described fluorine-containing containing fluorine-containing without sulphonyl fluorine reagent in the fluorine-containing band sulfuryl fluoride liquid monomer It is less than or equal to 30% without sulphonyl fluorine reagent and the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer.
Further, it is described it is fluorine-containing without sulphonyl fluorine reagent include contain fluoroalkyl, fluorine-containing alkyl ether, perfluoromethylvinyl Base ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, 3,3,3- trifluoro propylenes or one kind in perfluoro alkyl ethylene or It is a variety of.
Further, the gas phase mix monomer is contained with molar ratio computing：25%-90% tetrafluoroethene, 0%-70% The CTFE of vinylidene, 5%-50%.
Further, the fluorine-containing surfactant include the organic matter containing 6-16 carbon, and at least contain a carboxylic acid or The functional group of person's sulfonic acid.
Further, the radical initiator include persulfate, hydrogen peroxide, organic per-compounds in one kind or It is a variety of.
The preparation method of fluorine-containing chloride conducting polymer one side filled composite film includes following process：
Step 1: making microporous membrane skeleton：First by raw material with wet type phase change method, temperature difference phase change method, dry type solvent Method, method of electrostatic spinning or ultracentrifugation spin processes spinning, through heating spinneret or wet method (containing solvent or water) spinneret, gush out About 50-1000 nanometers of its diameter of silk, can uniformly collect into random reticulated macroporous structure, this reticulated macroporous structure is through heat setting Feasible into nanometer micropore film afterwards, this microporous membrane skeleton weighs about 1-50 grams per square meters, 3-25 grams per square meters preferably, its perforate gap Rate about 50%-95%, 70%-90% preferably；
The material of the microporous membrane skeleton is selected from：(I) fluorine-containing (chloride) resin of heat-fusible property, selected from heat-fusible property poly- four Fluoride copolymers, polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer；(II) fluorine-containing chloride conductive polymer Subtree fat (equivalents (meq/g) of its sulfonic acid or carboxylic acid in 1000-2000, preferably in 1200-1600)；(III) carbon fiber Precursor such as polyacrylonitrile and its copolymer or other resins for being derivatized to carbon fiber, it is preferred that what carbon fiber precursor was made The processing procedures such as microporous membrane can be pre-oxidized through high temperature, graphitization, carbonization, as carbon nano-fiber microporous membrane；(IV) it is other senior Engineering material is selected from：Polyimides, polyamide (nylon), polyester (PET), aramid fiber, polyether-ketone (PEEK) etc.；
Step 2: fluorine-containing chloride conductive polymer resin is packed into the hole of microporous membrane skeleton one side：By step Conducting polymer, with one side coating or one side immersion process, is packed into microporous membrane skeleton by the microporous membrane skeleton of one gained In the hole of one side, the fluorine-containing chloride conductive polymer resin, the acid equivalent number (meq/g) of its sulfonic acid or carboxylic acid is in 400- 1600, preferably in 600-1200, more preferably in 800-1100, the electrical conductivity at room temperature (Conductivity) of its monofilm>0.05 (S/cm), preferably>0.1 (S/cm), more preferably>0.15(S/cm)；Composite is dried, composite is dried, is made Fluorine-containing (chloride) macromolecule one side filled composite film；
Fluorine-containing (chloride) the macromolecule one side filled composite film, its microporous membrane skeleton and fluorine-containing chloride conductive polymer The weight ratio of subtree fat is (25:75)-(75:25), preferably (35:65)-(65:35).
This fluorine-containing (chloride) macromolecule one side filled composite film gross weight in 10-200 grams per square meters, preferably 20-100 grams/ Square meter, it is optimal in 25-90 grams per square meters, its thickness at 1 micron -100 microns, preferably at 3 microns -50 microns, it is optimal 5 microns -30 microns；The hole of microporous membrane skeleton one side it is most of (>85%, preferably>95%, it is optimal>99%) by containing The chloride conductive polymer resin of fluorine is filled, and fluorine-containing chloride conductive polymer resin one side filled composite film air permeable rate is low, The time allowed with Gurley Permeability gauge measurements needed for 100 milliliters of air permeable laminated films>3 minutes, preferably>10 minutes.
Alternatively, the step 2, by microporous membrane skeleton described in step one, with one side coating or one side immersion process, Fluorine-containing chloride conductive polymer resin (the acid equivalent number (meq/g) of its sulfonic acid or carboxylic acid in 400-1600, preferably in 600- 1200, more preferably in 800-1100), and a small amount of activated carbon powder, graphite powder, graphene or rare metal powder, it is packed into micropore In the hole of film skeleton one side, composite is dried, fluorine-containing (chloride) macromolecule one side filled composite film is made；It is described A small amount of activated carbon powder, graphite powder, the gross weight of graphene or rare metal powder are no more than fluorine-containing chloride conductive polymer resin 25% weight, is preferably no more than the weight of fluorine-containing chloride conductive polymer resin 11%；It is preferred that the rare metal powder Selected from silver-colored (Ag), platinum (Pt), Palladium (Pd)；
This fluorine-containing (chloride) macromolecule one side filled composite film, its gross weight in 10-250 grams per square meters, preferably in 20- 150 grams per square meters, it is optimal in 25-100 grams per square meters, its thickness at 2 microns -100 microns, preferably at 3 microns -50 microns, It is optimal at 5 microns -30 microns, the hole of its microporous membrane skeleton one side it is most of (>85%, preferably>95%, most Excellent>99%) by fluorine-containing chloride conductive polymer resin, and a small amount of activated carbon powder, graphite powder, graphene or rare metal powder Filled, fluorine-containing chloride conductive polymer resin one side filled composite film air permeable rate is low, is allowed with Gurley Permeability gauge measurements Time needed for 100 milliliters of air permeable laminated films>3 minutes, preferably>10 minutes.
Embodiment 1：
In the closed pre-emulsification reactor A of about 100 liters of internal volumes, 39000g pure water, 100g are added under normal temperature Perfluorooctanoic acid, open high shear agitation, then compare 70%CF toward the weight that 5000g is slowly added into kettle2=CF-O- CF2CFCF3-O-CF2CF2-SO2F and 30%CF2=CF-O-CF2CF2-SO2The fluorine-containing band sulfuryl fluoride liquid monomer of F mixing compositions, After about 30 points of continuous high speed shear agitation, pre-polymerization precursor emulsion is made；
In the reactor B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content is less than 20ppm in kettle, Then add in the whole pre-polymerization precursor emulsions come from reactor A, kettle and be passed through gas phase mix monomer, its mol ratio is 90% tetrafluoro second Alkene and 10% CTFE, are warming up to 70 degree, and pressure maintains 11 kilograms in kettle, add 2.5 grams of ammonium persulfates and are pre-dissolved in 1 liter Deionized water, start radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable Weight ratio is about 4:5；The gross weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer 0.05%；
Reaction temperature is controlled at 70~75 degree, in one hour reaction time, temperature in the kettle is down to after room temperature, stops stirring, Reactant blowing, the fluorine-containing chloride conducting polymer emulsion of acquisition, about 100 nanometers of the average grain diameter of its primary particle, emulsion contains admittedly Amount about 19%, the fluorine-containing chloride conducting polymer emulsion of gained is through sulfuryl fluoride (- SO2F) hydrolyze after obtain fluorine-containing chloride band sulfonic acid (- SO3H conducting polymer), after drying, it is than weighing about 1.99, acid equivalent number (meq/g) about 900, the electrical conductivity at room temperature of its monofilm (Conductivity)>0.15(S/cm)。
Embodiment 2
In the closed pre-emulsification reactor A of about 100 liters of internal volumes, 39000g deionized waters are added under normal temperature, 100g perfluorooctanoic acid, opens high shear agitation, then compares 80%CF toward the weight that 5000g is slowly added into kettle2=CF-O- CF2CFCF3-O-CF2CF2-SO2F and 20%CF2=CF-O-CF2CF2-SO2F mixture, about 30 points of continuous high speed shear agitation Afterwards, pre-polymerization precursor emulsion is made；In the reactor B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content in kettle Less than 20ppm, then add and be passed through gaseous mixture in the whole pre-polymerization precursor emulsions come from reactor A, kettle and mix monomer, its mole Than for 75% tetrafluoroethene, 20% vinylidene and 5% CTFE, being warming up to 70 degree, pressure maintains 9 kilograms in kettle, The deionized water that 2.5 grams of ammonium persulfates are pre-dissolved in 1 liter is added, starts radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable Weight ratio is about 5:4；The gross weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer 0.05%；
Reaction temperature is controlled at 70~75 degree, in about one hour reaction time, temperature in the kettle is down to after room temperature, stops stirring Mix, reactant blowing, the fluorine-containing chloride conducting polymer emulsion of acquisition, about 120 nanometers of the average grain diameter of its primary particle, emulsion is solid Content about 21%, the fluorine-containing chloride conducting polymer emulsion of gained is through sulfuryl fluoride (- SO2F fluorine-containing chloride band sulfonic acid is obtained after) hydrolyzing (-SO3H conducting polymer), after drying, it is than weighing about 1.91, acid equivalent number (meq/g) about 800, the normal temperature conductance of its monofilm Rate (Conductivity)>0.20(S/cm).
Embodiment 3：
In the closed pre-emulsification kettle A of about 100 liters of internal volumes, 39000g pure water is added under normal temperature, 100g's is complete Fluorine ammonium caprylate, opens high shear agitation, then compares 50% toward the weight that 3000g is slowly added into kettle【CF2=CF-O- CF2CFCF3-O-CF2CF2-SO2F】And 50%【CF2=CF-CF2-O-CF2CF2-SO2F】Mixture, continuous high speed shearing stir Mix after about 30 points, pre-polymerization precursor emulsion is made；In the reactor B of another about 100 liters of internal volumes, first deoxygenation in kettle, until kettle In oxygen content be less than 20ppm, then add the whole pre-polymerization precursor emulsions come from reactor A, be passed through gas phase mix monomer in kettle, its Mol ratio is 50% tetrafluoroethene and 50% CTFE, is warming up to 70 degree, and pressure maintains 14 kilograms in kettle, adds 1.5 Gram ammonium persulfate is pre-dissolved in 1 liter of deionized water, starts radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable Weight ratio is about 1:3；The gross weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer 0.05%；
Reaction temperature is controlled at 70~75 degree, in about one hour reaction time, temperature in the kettle is down to after room temperature, stops stirring Mix, reactant blowing, the fluorine-containing chloride conducting polymer emulsion of acquisition, about 150 nanometers of the average grain diameter of its primary particle, emulsion is solid Content about 22%, the fluorine-containing chloride conducting polymer emulsion of gained is through sulfuryl fluoride (- SO2F fluorine-containing chloride band sulfonic acid is obtained after) hydrolyzing (-SO3H conducting polymer), after drying, it is than weighing about 2.02, acid equivalent number (meq/g) about 1500, the normal temperature electricity of its monofilm Conductance (Conductivity)>0.02(S/cm).
Embodiment 4：
In the closed pre-emulsification reactor A of about 100 liters of internal volumes, 39000g deionized waters are added under normal temperature, 300g perfluorooctanoic acid, opens high shear agitation, then compares 20% toward the weight that 6000g is slowly added into kettle【CF2=CF- O-CF2CFCF3-O-CF2CF2-SO2F】And 80%【CF2=CF-CF2-O-CF2CF2-SO2F】Mixture, continuous high speed shearing After 30 points of stir about, pre-polymerization precursor emulsion is made；In the reactor B of another about 100 liters of internal volumes, first deoxygenation in kettle, until Oxygen content is less than 20ppm in kettle, then adds in the whole pre-polymerization precursor emulsions come from reactor A, kettle and is passed through gas phase mix monomer, Its mol ratio is 70% tetrafluoroethene and 30% CTFE, is warming up to 70 degree, and pressure maintains 10 kilograms in kettle, adds 3 Gram ammonium persulfate is pre-dissolved in 1 liter of deionized water, starts radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable Weight ratio is about 3:1；The gross weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer 0.05%；
Reaction temperature is controlled at 70~75 degree, in about one hour reaction time, temperature in the kettle is down to after room temperature, stops stirring Mix, reactant blowing, the fluorine-containing chloride conducting polymer emulsion of acquisition, about 70 nanometers of the average grain diameter of its primary particle, emulsion is solid Content about 19.5%, the fluorine-containing chloride conducting polymer emulsion of gained obtains fluorine-containing chloride band sulphur after being hydrolyzed through sulfuryl fluoride (- SO2F) The conducting polymer of sour (- SO3H), after drying, it is than weighing about 1.97, acid equivalent number (meq/g) about 500, the normal temperature electricity of its monofilm Conductance (Conductivity)>0.35(S/cm).
Embodiment 5
In the closed pre-emulsification kettle A of about 100 liters of internal volumes, 39000g deionized waters are added under normal temperature, 300g's Perfluorooctanoic acid, opens high shear agitation, then compares 60%CF toward the weight that 3 kilograms are slowly added into kettle2=CF-CF2-O- SO2F and 40%CF2=CF-CF2-O-CF2CF2-SO2After F mixture, about 30 points of continuous high speed shear agitation, performed polymer is made Emulsion；In the reactor B of another about 100 liters of internal volumes, first deoxygenation in kettle, until oxygen content is less than 20ppm in kettle, then Add the whole pre-polymerization precursor emulsions come from reactor A, be passed through gas phase mix monomer in kettle, its mol ratio be 25% tetrafluoroethene, 70% vinylidene, 5% CTFE, are warming up to 80 degree, and pressure maintains 17 kilograms in kettle, add 1.5 grams of ammonium persulfates 1 liter of deionized water is pre-dissolved in, starts radical polymerization.
It is described fluorine-containing total with sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation Raolical polymerizable Weight ratio is about 1:2.5；The gross weight that is passed through of radical initiator is with the fluorine-containing weight ratio with sulfuryl fluoride liquid monomer 0.05%；
Reaction temperature is controlled at 80~85 degree, in about 45 minutes reaction time, temperature in the kettle is down to after room temperature, stops stirring Mix, reactant blowing, obtain fluorine-containing conducting polymer emulsion, about 50 nanometers of the average grain diameter of its primary particle, emulsion solid content About 20%, the fluorine-containing conducting polymer emulsion of gained is through sulfuryl fluoride (- SO2F) it is hydrolyzed into sulfonic acid (- SO3H), (- CF2-O-SO2F) water Solution contains sulfonic acid/carboxylic acid conducting polymer into the fluorine-containing of carboxylic acid (- COOH), and after drying, it is than weighing about 1.72, acid equivalent number (meq/ G) about 950, the electrical conductivity at room temperature (Conductivity) of its monofilm>0.10(S/cm).
Embodiment 6
By the fluorine-containing chloride conductive polymer resin being made in embodiment 3 and dimethyl acetamide with about 1：4 weight Than mixing, heating stirring after resin dissolving, nanofibers is sprayed with method of electrostatic spinning, about 5 grams of production capacity per minute is produced to receive Rice filament is collected with release shape paper, and obtained nanofibers are deposited on strippable paper, and strippable paper is with 0.1 meter per minute Speed is advanced, and collected is the nanofiber cortina of about 1 meter of a breadth, and this cortina is gradually dried under about 90 DEG C of hot blast processing Dry nanofibers film, final line is into about 20 microns of thickness, the nanofibers film that about 100 centimetres of width, fiber it is flat Equal about 170 nanometers of diameter, after testing, film weigh about 10 grams per square meters, porosity about 78-82%, and proportion is 0.39, gas permeability Gurley surveys 100 milliliters of air permeable speed of method about 7~12 seconds.
Embodiment 7
Polyacrylonitrile (PAN) resin (is generated into copolymerization poly- third by acrylonitrile and a small amount of acrylic acid first vinegar, the fat copolymerization of methene fourth two Alkene nitrile resin, molecular weight is higher than 6 to 8 ten thousand) with dimethyl alum with about 1：4 weight is than mixing, heating stirring, resin dissolving Afterwards, nanofibers are sprayed with ultracentrifugation spin processes, about 20 grams of production capacity per minute, produced nanofibers are with release shape paper Collect, obtained nanofibers are deposited on strippable paper, strippable paper obtains speed with 0.1 meter per minute and advanced, collected Be about 1 meter of a breadth nanofiber cortina, this cortina under the processing of about 160 DEG C of hot blasts is gradually dried into nanofibers thin Film, final line is into about 70 microns of thickness, and the nanofibers film that about 100 centimetres of width, the average diameter about 350 of fiber is received Rice；After testing, film weighs about 39 grams per square meters, porosity about 82-86%, and proportion is 0.28, and gas permeability Gurley surveys 100 milliliters of method Air permeable speed about 13~17 seconds.
Embodiment 8
Obtained polyacrylonitrile nano microporous membrane will be manufactured in embodiment 7,270 DEG C, insulation are heated to about under air 2h, the color of polyacrylonitrile (PAN) resin nano microporous membrane gradually becomes yellow, brown by white, eventually forms the pre- of black Microporous membrane is aoxidized, is polyacrylonitrile linear polymeric by after thermal oxide, occurring a series ofization such as oxidation, pyrolysis, crosslinking, cyclisation Learn reaction and form the high molecular result of heat-resisting ladder type, pre-oxidation microporous membrane is then subjected to 1600 DEG C of high-temperature process in nitrogen Carbonization treatment, then nanofiber further produces the reactions such as crosslinking cyclisation, aromatisation and polycondensation, and it is former to remove hydrogen, nitrogen, oxygen Son, eventually forms the PAN base nano carbon fibres of Two-dimensional Carbon plane of a loop network structure and the coarse parallel random graphits structure of synusia Film, final line is into about 15 microns of thickness, and the nanofibers film that about 100 centimetres of width, the average diameter about 160 of fiber is received Rice, after testing, film weigh about 7 grams per square meters, porosity about 89-93%, and proportion is 0.27, and gas permeability Gurley surveys 100 milliliters of skies of method Gas penetration speed about 7~9 seconds.
Embodiment 9
ECTFE resins (ethene and chlorotrifluoroethylene, from Su Wei companies) melt spinning method is sprayed into ECTFE fibres Dimension nano wire, about 20 grams of spinneret per minute, produced nanofibers are collected with release shape paper, obtained nanofibers heap Product is on strippable paper, and strippable paper is advanced with 1 meter per minute of speed, and collected is the ECTFE Nanowires of about 1 meter of a breadth Tie up cortina, final line is into about 45 microns of thickness, the nanofibers film that about 100 centimetres of width, the average diameter about 450 of fiber Nanometer, after testing, film weigh about 20 grams per square meters, porosity about 75-80%, and proportion is 0.42, and gas permeability Gurley surveys the milli of method 100 Litres of air penetration speed about 12~15 seconds.
Embodiment 10
By PET polyester resin and ethylene carbonate with about 1：4 weight is than mixing, heating stirring, after resin dissolving, slightly Be coated on comprehensively on strippable paper under solution temperature more than 200 DEG C, the PET film generated through being rapidly cooled to room temperature, tear off from Shape paper, PET film is gradually dried by this PET film under the processing of about 170 DEG C of hot blasts, and final line is into about 50 microns of thickness, width about 160 Centimetre nanometer micropore film, after testing, the film of the fluorine-containing chloride microporous membrane of gained weighs about 15 grams per square meters, porosity about 68- 72%, proportion is 0.29, and gas permeability Gurley surveys 100 milliliters of air permeable speed of method about 17~23 seconds.
Embodiment 11
Obtained fluorine-containing chloride conducting polymer (acid equivalent number 950) will be manufactured in embodiment 5 and is first dissolved in dimethyl methyl Acid amides/ethanol (1:1) in solution, concentration of the conducting polymer in solution about 20% adds the activity of solution weight about 5% Carbon dust, by the ECTFE microporous membrane skeletons being made in embodiment 9, normal temperature one side is immersed in solution Rio one minute, takes out single The film of face immersion, gently scrapes off one side immersion film excess surface liquid, is slowly dried under 90 degree, that is, obtain laminated film； After testing, about 47 microns of gained laminated film final thickness, the transparent membrane that about 100 centimetres of width, film weighs about 39 grams per square meters, The grams per square meter of spread about 19, gas permeability Gurley surveys 100 milliliters of air permeable speed of method and is more than 3 minutes.
The mechanical strength (tensile strength is more than 50MPa) of this laminated film is much better than individually with fluorine-containing chloride conducting polymer Film obtained by (acid equivalent number 950) (tensile strength is less than 20MPa).
This extraordinary laminated film and the flat fabric of nylon 6 (90 grams per square meter), glue point is fitted by film and cloth through point-like polyurethane Compound, this composite material, water pressure resistance (JIS L1092 methods) is initially greater than 200kPa, after washing 10 times, water pressure resistance still greater than 100kPa；Moisture vapor permeable rate>4000g/m2/day, imitative rotten to the corn poison is surveyed according to U.S. military discipline MIL-DTL-32102 3April 2002 Gas：Dichloroethyl ether (ClCH2CH2OCH2CH2Cl) penetrance is qualified<4 μ g/cm2/day, it was demonstrated that the antibiotic war agent of this composite membrane is penetrated Ability is strong.
Embodiment 12
Obtained fluorine-containing chloride conducting polymer (acid equivalent number 950) will be manufactured in embodiment 5 and is first dissolved in dimethyl methyl Acid amides/ethanol (1:1) in solution, concentration of the conducting polymer in solution about 20% gathers the PET being made in embodiment 10 Ester microporous membrane skeleton, normal temperature one side is immersed in fluorine-containing chloride conducting polymer (the acid equivalent number 950) solution of made 20% About one minute, the film of one side immersion immersion is taken out, one side immersion film excess surface liquid is gently scraped off, is slowly dried under 90 degree It is dry, that is, obtain extraordinary laminated film；After testing, the extraordinary fluorine-containing chloride macromolecule one side filled composite film final thickness of gained is about 53 microns, the transparent membrane that about 100 centimetres of width, film weighs about 33 grams per square meters, the grams per square meter of spread about 18, gas permeability Gurley 100 milliliters of air permeable speed of survey method are more than 3 minutes.The mechanical strength (tensile strength is more than 30MPa) of this laminated film is remote excellent In individually with the film obtained by fluorine-containing chloride conducting polymer (acid equivalent number 950) (tensile strength is less than 20MPa).
This extraordinary laminated film and the flat fabric of nylon 6 (90 grams per square meter), glue point is fitted by film and cloth through point-like polyurethane Compound, this composite material, water pressure resistance (JIS L1092 methods) is initially greater than 200kPa, after washing 10 times, water pressure resistance still greater than 100kPa；Moisture vapor permeable rate>4000g/m2/day, imitative rotten to the corn poison is surveyed according to U.S. military discipline MIL-DTL-32102 3April 2002 Gas：Dichloroethyl ether (ClCH2 CH2O CH2 CH2Cl) penetrance is qualified<4 μ g/cm2/day, it was demonstrated that the antibiotic war agent of this composite membrane is worn Saturating ability is strong.
Comparative example 1：(perfluor conducting polymer film is not suitable for NBC protection clothes)
By the perfluor conducting polymer film (Nafion NR-211,25 microns of thickness) of Du Pont and the flat fabric of nylon 6 (90 grams/ Square meter), film is combined with cloth through point-like polyurethane laminating glue point, this composite material, water pressure resistance (JIS L1092 methods) is initial big In 200kPa, after washing 10 times, film is kept completely separate with cloth, it is impossible to water pressure resistance；Moisture vapor permeable rate>4000g/m2/day, according to U.S. State military discipline MIL-DTL-32102 3April 2002 survey imitative vesicating gas：Dichloroethyl ether (ClCH2 CH2O CH2 CH2Cl) penetrance It is qualified>60 μ g/cm2/day, it was demonstrated that the antibiotic penetration capacity of this composite membrane is poor.
Comparative example 2：(perfluor conducting polymer film is not suitable for NBC protection clothes)
By the perfluor conducting polymer film (Nafion NR-212,50 microns of thickness) of Du Pont and the flat fabric of nylon 6 (90 grams/ Square meter), film is combined with cloth through point-like polyurethane laminating glue point, this composite material, water pressure resistance (JIS L1092 methods) is initial big In 200kPa, after washing 10 times, film is kept completely separate with cloth, it is impossible to water pressure resistance；Moisture vapor permeable rate>4000g/m2/day, according to U.S. State military discipline MIL-DTL-32102 3April 2002 survey imitative vesicating gas：Dichloroethyl ether (ClCH2 CH2O CH2 CH2Cl) penetrance It is qualified>40 μ g/cm2/day, it was demonstrated that the antibiotic war agent penetration capacity of this composite membrane is poor.
The antibiotic war agent ability of perfluor conducting polymer film is not as good as fluorine-containing chloride conducting polymer film as can be seen here.
For those skilled in the art, technical scheme that can be more than and design, make various corresponding Change and deform, and all these change and deformation should be construed as being included within the protection domain of the claims in the present invention.

Claims (10)

1. a kind of fluorine-containing chloride conducting polymer one side filled composite film, it is characterised in that including microporous membrane skeleton with containing The chloride conductive polymer resin of fluorine, the pore volume of the one side of the microporous membrane skeleton is high by fluorine-containing chloride conduction more than 85% Molecule resin is filled；
The fluorine-containing chloride conductive polymer resin is prepared via a method which to obtain：First free redical is gathered by weight percentage The fluorine-containing band sulfuryl fluoride liquid monomer 1%~20% of conjunction, pure water 79%~98%, fluorine-containing surfactant 0.01%~1% Add in reactor and carry out high-speed stirred, obtain pre-polymerization precursor emulsion；Then toward being passed through in tetrafluoroethene, vinylidene in reactor One or two and the gas phase mix monomer of CTFE, reaction pressure is 5 kilograms or more；Free radical is then passed to draw Agent is sent out, reaction temperature is at 20-120 DEG C, and reaction pressure is at 5-25 kilograms, and the reaction time is 15-180min, obtains reaction product and contains The chloride macromolecule emulsion with sulfuryl fluoride of fluorine；The fluorine-containing band sulfuryl fluoride liquid monomer and the gas phase mix monomer actual participation The ratio between gross weight of Raolical polymerizable is 1：3~3：1；Radical initiator is passed through gross weight and fluorine-containing band sulfuryl fluoride liquid The weight ratio of phase monomer is 0.01%~3.0%；Finally the fluorine-containing chloride macromolecule emulsion with sulfuryl fluoride is hydrolyzed, then passed through Fluorine-containing chloride conductive polymer resin is obtained after cohesion, washing, drying.
2. a kind of preparation method of fluorine-containing chloride conducting polymer one side filled composite film as claimed in claim 1, it is special Levy and be, comprise the following steps：
By microporous membrane skeleton to be coated with or immersion process, fluorine-containing chloride conductive polymer resin is packed into microporous membrane skeleton Composite is obtained in the hole of one side；Composite is dried, fluorine-containing chloride conducting polymer one side filled composite is made thin Film.
3. preparation method according to claim 2, it is characterised in that microporous membrane skeleton and fluorine-containing chloride conducting polymer The weight ratio of one side filled composite film is (25:75)-(75:25).
4. preparation method according to claim 2, it is characterised in that microporous membrane skeleton is prepared via a method which：
First by heat-fusible property fluorine resin or chlorinated and fluorinated resin, the fluorine-containing chloride conductive polymer resin, carbon fiber precursor And its copolymer or a kind of progress that can be derivatized in the resin of carbon fiber, polyimides, polyamide, polyester, aramid fiber, polyether-ketone Spinning, through heating spinneret or wet method spinneret, equably collects into random reticulated macroporous structure, micropore is obtained after heat setting thin Membrane bone frame.
5. preparation method according to claim 2, it is characterised in that microporous membrane skeleton, will to be coated with or immersion process One or more in activated carbon powder, graphite powder, graphene, rare metal powder, are mixed with fluorine-containing chloride conductive polymer resin In the hole for being packed into its microporous membrane one side in the lump.
6. preparation method according to claim 5, it is characterised in that the activated carbon powder, graphite powder, graphene, rare One or more of gross weights in metal powder are no more than the 25% of the weight of fluorine-containing chloride conductive polymer resin.
7. preparation method according to claim 5, it is characterised in that the rare metal powder is silver, Bo Huo Palladium.
8. preparation method according to claim 4, it is characterised in that heat-fusible property fluorine resin or chlorinated and fluorinated resin bag Include one in heat-fusible property teflon-copolymers, polytrifluorochloroethylene or its copolymer, Kynoar or its copolymer Plant or several.
9. preparation method according to claim 2, it is characterised in that the sulfonic acid of the fluorine-containing chloride conductive polymer resin Or the acid equivalent number (meq/g) of carboxylic acid is in 400-1600.
10. preparation method according to claim 2, it is characterised in that using wet type phase change method, temperature difference phase change method, Dry type solvent method, method of electrostatic spinning or ultracentrifugation spin processes carry out spinning.
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