CN103897309B - A kind of preparation method of high temperature resistant type fluoropolymer poromerics - Google Patents

A kind of preparation method of high temperature resistant type fluoropolymer poromerics Download PDF

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CN103897309B
CN103897309B CN201410140142.8A CN201410140142A CN103897309B CN 103897309 B CN103897309 B CN 103897309B CN 201410140142 A CN201410140142 A CN 201410140142A CN 103897309 B CN103897309 B CN 103897309B
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poromerics
fluoropolymer
temperature resistant
high temperature
resistant type
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CN103897309A (en
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刘富
薛立新
沈剑辉
林海波
向艳慧
王益
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461—Combinations of dissimilar mixers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92514—Pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/926—Flow or feed rate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention discloses a kind of preparation method of high temperature resistant type fluoropolymer poromerics. The method is by even to fluoropolymer, microphase-separated induced polymer, pore-foaming agent, helper-inducer agent high-speed mixing, through overcritical-double screw extruder film-forming system extrusion molding operation, obtain initial poromerics, immerse again in coagulating bath, and be immersed in oscillation cleaning in cleaner bath after drawing stretching with certain speed, obtain high temperature resistant type fluoropolymer poromerics. The present invention adopts the plasticizing adjuvant of supercritical carbon dioxide as system, can reduce the melt viscosity of fluoropolymer, can make the processing temperature of fluoropolymer at least reduce by 20 DEG C; Adopt supercritical carbon dioxide as green solvent, avoided adopting a large amount of organic solvents, and make prepared poromerics can not have the problem of dissolvent residual, can be to environment yet.

Description

A kind of preparation method of high temperature resistant type fluoropolymer poromerics
Technical field
The present invention relates to a kind of polymer microporous material technology of preparing, be specially a kind of high temperature resistant type fluorine-containingThe preparation method of polymer microporous material.
Background technology
China explicitly points out in 12 planning, and high performance membrane material is seven great strategies as new materialOne of new industry, is put into 863 major projects. Compared with traditional polymer perforated membrane, fluorine-containing poly-Compound poromerics has the advantage in some performances, mainly contains chemical resistance, high temperature resistant, resistance toRadiativity, electric insulation and mechanical strength etc., therefore, fluoropolymer is widely used in blood placeReason, organic liquid filter, have oxidisability reagent and filter purification, water-oil separating and insulated wire cableIn field. Fluoropolymer mainly comprise polytetrafluoroethylene (PTFE), Kynoar (PVDF),Perfluoroethylene-propylene (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorinatedCopolymer (ECTFE), polyvinyl fluoride (PVF), tetrafluoroethene-perfluoro propyl vinyl ether copolymer(PFA), tetrafluoroethene-perfluoro methyl vinyl ether copolymer (MFA), polytrifluorochloroethylene (PCTFE)Deng, wherein with the consumption maximum of PTFE, PVDF and these 3 kinds of fluoroplastics of FEP. PETF is due to " noMolten molten " characteristic, this has limited usual melt extrusion or the employing of molding technology. PVDF hasThe good characteristics of " solvable fusible ", the preparation method of PVDF microporous barrier mainly adopts solution phase at presentConversion method, is mainly to adopt organic solvent dissolution PVDF, forms thermodynamically stable homogeneous system, thenInduce and form the film forming that is separated by non-solvent. Solution phase conversion method film forming system has adopted a large amount of organicSolvent, this is unfavorable for environmental protection, membrane product also can cause at some great because of dissolvent residual simultaneouslyField is limited the use of. FEP has the nearly all excellent properties of PETF, and its unique advantage is to enterRow melt-processed, by injection moulding or extrusion molding. This makes application and the study on the modification of people to FEPMore and more come into one's own. Meanwhile, most of fluoropolymers have all embodied that fusing point is high, viscosity is large, phaseThe problems such as the poor and difficulty of processing height of capacitive, it is poly-that this has limited many plasticizer or diluent and the second monomerThe use of compound.
Supercritical fluid mainly contains carbon dioxide, nitrogen, water, ethane, cyclohexane etc., wherein to surpassCritical carbon dioxide is the most conventional. Supercritical carbon dioxide has fine solvent borne, seeing through property and transmissionProperty, and polymer is had to good plasticization, be widely used in foaming and extraction field.Carbon dioxide has colourless nontoxic, environmental friendliness, wide material sources, the advantage such as cheap, and it facesBoundary's temperature is that 31.1 DEG C, critical pressure are 7.38MPa, makes it reach critical condition and easily realizes, thereforeSupercritical carbon dioxide is one of current most widely used Green Additives.
Mainly solution phase partition method or thermic phase to the research of fluoropolymer perforated membrane both at home and abroad at presentPartition method, has both used a large amount of organic solvents, diluent, and for utilizing overcritical dioxyChanging carbon extrudes continuously the research of preparing fluoropolymer microporous barrier and does not substantially have. Application number isThe Introduction To Cn Patent of " 201210051376.6 " people such as Xiao Changfa taking (per) fluoropolymer as film forming baseBody, organic solvent are diluent, then have added polystyrene, polymeric additive, composite pore-forming,Adopt double screw extruder to carry out melt spinning, then through extraction and sulfonation processing, obtain (per) fluoropolymerHollow-fibre membrane; Application number be " 201210553794.5 " Introduction To Cn Patent amphipathic copolymerizationThe new method of thing modification PVDF Hollow Fiber Ultrafiltration filter membrane, the method is by PVDF, amphipathic commonPolymers, pore-foaming agent, non-solvent fully mix with solvent, dissolve and obtain casting solution, then pass through spinning-drawing machineExtrude and obtain PVDF hollow-fibre membrane. Above two kinds of methods have all applied to a large amount of organic solvents and have doneFor diluent or lytic agent, this has limited fluoropolymer at bio-medical, blood treatment, drinking waterThe extensive utilization of the aspects such as purification, also there is environment potential problem in the post processing of the waste liquid that produces. CauseThis, the green low-temperature environment-friendly technology of preparing of developing a kind of fluoropolymer high-performance poromerics has heavilyLarge meaning.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of high temperature resistant type fluoropolymer is providedThe preparation method of poromerics, is specially and utilizes supercritical carbon dioxide secondary process high temperature modification fluorine-containing poly-Compound poromerics. The advantages such as this preparation method has the processing temperature of reduction, pollution-free, technique is simple.
The inventive method comprises the following steps:
Step (1). by fluoropolymer, microphase-separated induced polymer, pore-foaming agent, helper-inducerAgent high-speed mixing is even, obtains compound; Then by the overcritical-double screw extruder of compound processFilm-forming system extrusion molding operation, obtains initial poromerics;
Prepare the compound of 100 parts by weight, the parts by weight of each raw material are: fluoropolymer 50～90 parts, 0～30 part of microphase-separated induced polymer, 5～30 parts of pore-foaming agents, helper-inducer agent 0～5 parts;
Described overcritical-double screw extruder film-forming system extrusion molding operation be by compound with 3～The speed of 25kg/h feeds the double screw extruder of 250～350 DEG C, before double screw extruderTwoth district to compound carry, fusion plastification, obtain polymer melt; Then at twin-screw extrusionSupercritical carbon dioxide, the overcritical titanium dioxide in four～seven district and the Section Eight thermal treatment zone are injected by Ji 3rd districtCarbon is uniform dissolution, diffusion in polymer melt, then, by regulating Melt Pump, produces pressure differential,Make head pressure at least reach 5Mpa, then extrusion die, initial poromerics finally obtained.
The implantation temperature of described supercritical carbon dioxide is 35～65 DEG C, and pressure is 8～15MPa,Output flow is 0.1～10ml/min, with double screw extruder coupling, is independent injected system.
Described fluoropolymer is for having thermoplasticity, melt temperature more than 200 DEG C, processing temperaturePolymer more than 250 DEG C, comprises perfluoroethylene-propylene (FEP), ethylene-tetrafluoroethylene copolymer(ETFE), tetrafluoroethene-perfluoro propyl vinyl ether copolymer (PFA), tetrafluoroethene-perfluor firstOne in base vinyl ether co-polymer (MFA);
Described microphase-separated induced polymer is that decomposition temperature is not less than fluoropolymer processing temperaturePolymer, comprise polytetrafluoroethylene (PTFE), PEKK (PEKK), polyamide 12(PA12),A kind of in polyimides (PI), PEO (PEO), polyvinylpyrrolidone (PVP) orMultiple;
Described pore-foaming agent be potassium A molecular sieve, sodium A molecular sieve, sodium Y molecular sieve, calcium X molecular sieve,ZSM type molecular sieve, sodalite type methylimidazole zinc (ZIF-8), zeolite imidazoles metal organic frame-90(ZIF-90), sodium chloride, calcium carbonate, glass fibre, zinc oxide, boron nitride fiber, season pentaOne or more in tetrol stearate, granularity is less than 3 microns.
Described helper-inducer agent is for having suitable boiling point and appropriate volatility, can producing with polymerBetween stronger Van der Waals force, hydrogen bond equimolecular, the small molecule solvent of active force, comprises water, ethanol, thirdOne in ketone, triethyl phosphate.
Step (2). initial poromerics is immersed in the coagulating bath of 20～50 DEG C, and with 5～30The speed of m/min is drawn stretching, is then immersed in that in cleaner bath, to carry out oscillation cleaning 0～48 littleTime, obtain high temperature resistant type fluoropolymer poromerics.
Described coagulating bath is the 1-METHYLPYRROLIDONE that deionized water, mass content are less than 50 ﹪(NMP) aqueous solution, mass content are less than dimethylacetylamide (DMAC) aqueous solution or the matter of 50 ﹪Amount content is less than the ethanol water of 30 ﹪, and temperature is 20～50 DEG C, and Main Function is to initially micro-Hole material cooled sizing and dissolving part water-soluble polymer or pore-foaming agent.
Described cleaner bath is that dilute hydrochloric acid solution or the concentration that deionized water, concentration are less than 5 ﹪ is less than 5The sodium hydroxide solution of ﹪, mainly plays extraction and washes effect, and wherein bath temperature is 30～80 DEG C, watery hydrochloric acidBath temperature is 20～40 DEG C, and NaOH bath temperature is 20～40 DEG C.
The high temperature resistant type fluoropolymer poromerics that the present invention prepares has open-celled structureHollow-fibre membrane, flat sheet membrane, its aperture is greater than 0.01 micron, and micro-foaming cable of hole-closing structure,Film, its aperture is greater than 10 microns.
Compared with existing masking technique, the present invention has following feature:
1, adopt the plasticizing adjuvant of supercritical carbon dioxide as system, can reduce the molten of fluoropolymerBody viscosity, can make the processing temperature of fluoropolymer at least reduce by 20 DEG C.
2, introduced microphase-separated induced polymer, degree of crystallinity or the melt that can reduce fluoropolymer are strongDegree, thus dissolving and the diffusivity of supercritical carbon dioxide in Crystalline plastics improved.
3, introduced helper-inducer agent, in the process that adjustable micropore forms, supercritical carbon dioxide is with moltenInterfacial tension between body, and further on macropore inwall, form meticulousr micropore, fromAnd increase the contiguity between porosity and Kong Yukong.
4, adopt supercritical carbon dioxide as green solvent, avoided adopting a large amount of organic solvents, andThe helper-inducer agent adopting can be by supercritical carbon dioxide extracting out in extrusion, therebyCan there is not the problem of dissolvent residual in prepared poromerics, can be to environment yet.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph that embodiment 1 prepares high temperature resistant type fluoropolymer poromerics;
Fig. 2 is the electromicroscopic photograph that embodiment 2 prepares high temperature resistant type fluoropolymer microporous barrier;
Fig. 3 is the surperficial electromicroscopic photograph that embodiment 2 prepares high temperature resistant type fluoropolymer microporous barrier.
Detailed description of the invention
In order to further illustrate the present invention, high temperature resistant to one provided by the invention below in conjunction with embodimentThe preparation method of type fluoropolymer poromerics further describes, but protection scope of the present invention is notOnly limit to this.
Be below the conventional machining temperature of fusing point, twin-screw extrusion of described fluoropolymer as following table:
Embodiment 1
Step 1: by 1700g perfluoroethylene-propylene, 50g nano-calcium carbonate, 250g boron nitride fiberIn high mixer, mix, obtain compound.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: compound is fed into double screw extruder one district with the speed of 5kg/h, premenstrual twoth districtConveying, fusion plastification after, by temperature be 60 DEG C, the pressure supercritical carbon dioxide that is 10MPa withSpeed 3rd district of 3.5ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 14.6MPa, head unloads fastPress.
Step 5: by extruding after die head, bathe moulding through the pure water of 20 DEG C, and with the speed of 12m/minRate stretching and drawing, obtains high temperature resistant type fluoropolymer poromerics, can be used as FEP foamed cable.
Through electronic microscope photos, as shown in Figure 1, the foam structure of gained FEP foaming product is closed pore,Distribution of cells is more even, approximately 10～70 microns of its average-sizes.
Embodiment 2
Step 1: by 750g perfluoroethylene-propylene, 30g polytetrafluoroethylene (PTFE), 10g zinc oxide, 140gSodium chloride and 70g PEO mix in high mixer, obtain compound.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: compound is fed into double screw extruder one district, premenstrual two with the speed of 3.5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 60 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 5.8MPa, head pressure reaches12.5MPa, fast pressure relief.
Step 5: by extruding after hollow spinneret assembly, bathe moulding through the pure water of 20 DEG C, and withThe speed stretching and drawing of 10m/min, immerses subsequently in 45 DEG C of water and carries out oscillation cleaning 48 hours,To the high temperature resistant type fluoropolymer poromerics with mutual through hole structure, can be used as FEP hollowTunica fibrosa.
Experiment confirmation, the introducing of supercritical carbon dioxide can reduce the processing temperature of FEP resin; Through electricityMirror is analyzed, and as shown in accompanying drawing 2,3, gained FEP hollow-fibre membrane has the pore structure of mutual perforation,Its aperture is about 0.05～5 micron.
Embodiment 3
Step 1: by 740g perfluoroethylene-propylene, 50g PEKK, 10g zinc oxide, 140g nitrogenChange boron fibre, 50g polyvinylpyrrolidone and 10g triethyl phosphate, in high mixer, mix allEven.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 60 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 3ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make the front pressure of pump reach 5.8MPa, head pressure reaches12.5MPa, fast pressure relief.
Step 5: by extruding after hollow spinneret assembly, bathe moulding through the pure water of 25 DEG C, and withThe speed stretching and drawing of 10m/min, immerses subsequently in 30 DEG C of dilute hydrochloric acid solutions and carries out oscillation cleaning 48Hour, obtain having the high temperature resistant type fluoropolymer poromerics of mutual through hole structure, can be used asFEP hollow-fibre membrane.
Embodiment 4
Step 1: by 1420g ethylene-tetrafluoroethylene copolymer, 200g polyamide 12,30g season penta 4Alcohol stearate, 300g glass fibre and 50g water high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district with the speed of 15kg/h, premenstrualAfter the conveying in twoth district, fusion plastification, be the overcritical titanium dioxide that 65 DEG C, pressure are 15MPa by temperatureCarbon injects in machine barrel with speed 3rd district of 8ml/min.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 13MPa, head fast pressure relief.
Step 5: by extruding after die head, bathe moulding through the pure water of 25 DEG C, and with the speed of 15m/minRate stretching and drawing, immerses subsequently in 45 DEG C of water and carries out oscillation cleaning 24 hours, obtains high temperature resistant type and containsFluoropolymer polymer poromerics, can be used as ETFE film material.
Embodiment 5
Step 1: by 1200g tetrafluoroethene-perfluoro propyl vinyl ether copolymer, 150g polyimides,35g boron nitride fiber, 100g nano-calcium carbonate and 15g ethanol high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 15.4MPa, head unloads fastPress.
Step 5: by extruding after die head, bathe moulding through the pure water of 25 DEG C, and with the speed of 15m/minRate stretching and drawing, immerses subsequently in 25 DEG C of dilute hydrochloric acid solutions and carries out oscillation cleaning 24 hours, after warpContinuous processing obtains high temperature resistant type fluoropolymer poromerics, can be used as PFA film material.
Embodiment 6
Step 1: by 850g tetrafluoroethene-perfluoro methyl vinyl ether copolymer, 80g potassium A, 10gZIF8,50g nano-calcium carbonate and 10g acetone high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 8kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 60 DEG C, pressure are 15MPa by temperatureSpeed 3rd district with 8ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 25 DEG C, and with the speed of 12m/minRate stretching and drawing, immerses subsequently in 25 DEG C of dilute hydrochloric acid solutions and carries out oscillation cleaning 12 hours, after warpContinuous processing obtains high temperature resistant type fluoropolymer poromerics, can be used as MFA film material.
Embodiment 7
Step 1: by 900g tetrafluoroethene-perfluoro methyl vinyl ether copolymer, 50g potassium A, 50gAcetone high-speed mixing in high mixer is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 3kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 35 DEG C, pressure are 8MPa by temperatureSpeed 3rd district with 10ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 50 DEG C, and with the speed of 5m/minStretching and drawing, immerses subsequently in 20 DEG C of dilute hydrochloric acid solutions and carries out oscillation cleaning 48 hours, through follow-upProcessing obtains high temperature resistant type fluoropolymer poromerics.
Embodiment 8
Step 1: by 900g tetrafluoroethene-perfluoro methyl vinyl ether copolymer, 50g sodium A, 50gWater high-speed mixing in high mixer is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 0.1ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, through the ethanol water coagulating bath moulding of 25 DEG C, and withThe speed stretching and drawing of 30m/min, immerses that in 40 DEG C of dilute hydrochloric acid solutions, to carry out oscillation cleaning 5 little subsequentlyTime, obtain high temperature resistant type fluoropolymer poromerics through subsequent treatment.
Embodiment 9
Step 1: by 500g perfluoroethylene-propylene, 100g polytetrafluoroethylene (PTFE), 100g PEO,250g sodium Y, 50g ethanol high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 40 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 1ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 20Mpa, head is quickRelease.
Step 5: by extruding after die head, through the NMP aqueous coagulation bath moulding of 40 DEG C, and withThe speed stretching and drawing of 30m/min, immerses subsequently in 30 DEG C of water and carries out oscillation cleaning 48 hours, warpCross subsequent treatment and obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 10
Step 1: by 500g perfluoroethylene-propylene, 300g polyamide 12,150g calcium X, 50g ethanolIn high mixer, high-speed mixing is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 50 DEG C, pressure are 15MPa by temperatureSpeed 3rd district with 0.5ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make before pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 50 DEG C, and with the speed of 20m/minRate stretching and drawing, immerses subsequently in 80 DEG C of water and carries out oscillation cleaning 5 hours, obtains through subsequent treatmentHigh temperature resistant type fluoropolymer poromerics.
Embodiment 11
Step 1: by 900g perfluoroethylene-propylene, 40g PEKK, 50gZSM type molecular sieve, 10gEthanol high-speed mixing in high mixer is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 10Mpa, head fast pressure relief.
Step 5: by extruding after die head, bathe moulding through the pure water of 25 DEG C, and with the speed of 15m/minRate stretching and drawing, immerses subsequently in 20 DEG C of sodium hydroxide solutions and carries out oscillation cleaning 48 hours, processSubsequent treatment obtains high temperature resistant type fluoropolymer poromerics.
Embodiment 12
Step 1: by 900g perfluoroethylene-propylene, 40g PEKK, 50gZIF-8,10g ethanolIn high mixer, high-speed mixing is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 8Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 25 DEG C, and with the speed of 15m/minRate stretching and drawing, immerses subsequently in 40 DEG C of NaOH and carries out oscillation cleaning 10 hours, through follow-upProcessing obtains high temperature resistant type fluoropolymer poromerics.
Embodiment 13
Step 1: by 600g perfluoroethylene-propylene, 300g polyvinylpyrrolidone, 100gZIF-90In high mixer, high-speed mixing is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 12MPa, head fast pressure relief.
Step 5: by extruding after die head, through the DMAC aqueous coagulation bath moulding of 25 DEG C, and withThe speed stretching and drawing of 15m/min, immerses subsequently in 30 DEG C of sodium hydroxide solutions and carries out oscillation cleaning 15Hour, obtain high temperature resistant type fluoropolymer poromerics through subsequent treatment.
Embodiment 14
Step 1: 600g ethylene-tetrafluoroethylene copolymer, 50g polyvinylpyrrolidone, 50g are gatheredOxirane, 300g sodium chloride high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 5kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make pump after pressure reach 11MPa, head fast pressure relief.
Step 5: by extruding after die head, through the NMP aqueous coagulation bath moulding of 25 DEG C, and withAfter the speed stretching and drawing of 15m/min, obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 15
Step 1: 600g ethylene-tetrafluoroethylene copolymer, 50g polyvinylpyrrolidone, 30g are gatheredOxirane, 20g polyimides, 300g calcium carbonate high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, through the NMP coagulating bath moulding of 50 DEG C, and with 13m/minSpeed stretching and drawing after obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 16
Step 1: 600g ethylene-tetrafluoroethylene copolymer, 50g polyvinylpyrrolidone, 30g are gatheredTetrafluoroethene, 20g polyimides, 300g glass fibre high-speed mixing in high mixer are even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 50 DEG C, and with the speed of 15m/minAfter rate stretching and drawing, obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 17
Step 1: by 600g ethylene-tetrafluoroethylene copolymer, 100g PEO, 300g oxidationZinc high-speed mixing in high mixer is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 50 DEG C, and with the speed of 15m/minAfter rate stretching and drawing, obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 18
Step 1: by 600g ethylene-tetrafluoroethylene copolymer, 400g boron nitride fiber in high mixerHigh-speed mixing is even.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 10Mpa, head is quickRelease.
Step 5: by extruding after die head, bathe moulding through the pure water of 50 DEG C, and with the speed of 15m/minAfter rate stretching and drawing, obtain high temperature resistant type fluoropolymer poromerics.
Embodiment 19
Step 1: 750g ethylene-tetrafluoroethylene copolymer, 50g polyvinylpyrrolidone, 30g are gatheredTetrafluoroethene, 120g polyimides, 50g pentaerythritol stearate high-speed mixing in high mixer are equalEven.
Step 2: open the heating system of double screw extruder, intensification preheating 2 hours, processing temperatureAs follows:
Step 3: mixed material is fed into double screw extruder one district, premenstrual two with the speed of 25kg/hAfter the conveying in district, fusion plastification, be the supercritical carbon dioxide that 65 DEG C, pressure are 10MPa by temperatureSpeed 3rd district with 2ml/min are injected in machine barrel.
Step 4: under HTHP and strong shearing force effect, supercritical carbon dioxide and polymer shapeBecome to melt altogether system, by regulating Melt Pump, make after pump more than pressure reaches 8Mpa, head is quickRelease.
Step 5: by extruding after die head, through the ethanol water coagulating bath moulding of 20 DEG C, and withAfter the speed stretching and drawing of 15m/min, obtain high temperature resistant type fluoropolymer poromerics.
Potassium A molecular sieve, sodium A molecular sieve, sodium Y molecular sieve, calcium X used in above-described embodiment divideSon sieve, ZSM type molecular sieve, sodalite type methylimidazole zinc (ZIF-8), zeolite imidazoles metal haveMachine frame-90(ZIF-90), sodium chloride, calcium carbonate, glass fibre, zinc oxide, boron nitride fiber,The granularity of pentaerythritol stearate is all less than 3 microns; In NMP aqueous coagulation bath, NMP quality containsAmount is less than 50 ﹪, and in DMAC aqueous coagulation bath, DMAC mass content is less than 50 ﹪, ethanol waterEthanol mass content is less than 30 ﹪; Dilute hydrochloric acid solution concentration is less than 5 ﹪, and concentration of sodium hydroxide solution is littleIn 5 ﹪.
Above-described embodiment is not for restriction of the present invention, and the present invention is not limited only to above-mentioned enforcementExample, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.

Claims (6)

1. a preparation method for high temperature resistant type fluoropolymer poromerics, is characterized in that the method bagDraw together following steps:
Step (1). by fluoropolymer, microphase-separated induced polymer, pore-foaming agent, helper-inducer agentMix, obtain compound; Then compound is squeezed through overcritical-double screw extruder film-forming systemMould operation, obtain initial poromerics;
Prepare the compound of 100 parts by weight, the parts by weight of each raw material are: fluoropolymer 50～90Part, 4～30 parts of microphase-separated induced polymers, 5～30 parts of pore-foaming agents, 1～5 part of helper-inducer agent;
Described overcritical-double screw extruder film-forming system extrusion molding operation is with 3～25kg/h by compoundThe double screw extruder of 250～350 DEG C of speed feedings, by double screw extruder Qian Liang district to mixingMaterial is carried, fusion plastification, obtains polymer melt; Then inject in double screw extruder San districtSupercritical carbon dioxide, four～seven district and Section Eight thermal treatment zone supercritical carbon dioxide are at polymer meltMiddle uniform dissolution, diffusion, then, by regulating Melt Pump, produce pressure differential, makes head pressure at leastReach 5MPa, then extrusion die, initial poromerics finally obtained;
The implantation temperature of described supercritical carbon dioxide is 35～65 DEG C, and pressure is 8～15MPa, outputFlow is 0.1～10ml/min;
Step (2). initial poromerics is immersed in the coagulating bath of 20～50 DEG C, and with 5～30m/minSpeed draw stretching, be then immersed in cleaner bath and carry out oscillation cleaning 0～48 hour, obtainHigh temperature resistant type fluoropolymer poromerics;
Microphase-separated induced polymer be polytetrafluoroethylene (PTFE), PEKK, polyamide 12, polyimides,One or more in PEO, polyvinylpyrrolidone.
2. the preparation method of a kind of high temperature resistant type fluoropolymer poromerics as claimed in claim 1,It is characterized in that fluoropolymer be perfluoroethylene-propylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethene-One in perfluoro propyl vinyl ether copolymer, tetrafluoroethene-perfluoro methyl vinyl ether copolymer.
3. the preparation method of a kind of high temperature resistant type fluoropolymer poromerics as claimed in claim 1,It is characterized in that pore-foaming agent be potassium A molecular sieve, sodium A molecular sieve, sodium Y molecular sieve, calcium X molecular sieve,ZSM type molecular sieve, sodalite type methylimidazole zinc, zeolite imidazoles metal organic frame-90, sodium chloride,One in calcium carbonate, glass fibre, zinc oxide, boron nitride fiber, pentaerythritol stearate or manyKind, granularity is less than 3 microns.
4. the preparation method of a kind of high temperature resistant type fluoropolymer poromerics as claimed in claim 1,It is characterized in that helper-inducer agent is the one in water, ethanol, acetone, triethyl phosphate.
5. the preparation method of a kind of high temperature resistant type fluoropolymer poromerics as claimed in claim 1,It is characterized in that coagulating bath be deionized water, the mass content 1-METHYLPYRROLIDONE aqueous solution that is less than 50 ﹪,Mass content is less than the dimethylacetylamide aqueous solution of 50 ﹪ or mass content, and to be less than the ethanol of 30 ﹪ water-solubleLiquid.
6. the preparation method of a kind of high temperature resistant type fluoropolymer poromerics as claimed in claim 1,It is characterized in that cleaner bath is that dilute hydrochloric acid solution or the concentration that deionized water, concentration are less than 5 ﹪ is less than 5 ﹪'sSodium hydroxide solution, wherein deionized water temperature is 30～80 DEG C, dilute hydrochloric acid solution temperature is 20～40 DEG C,Sodium hydroxide solution temperature is 20～40 DEG C.
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