CN107353374B - A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier - Google Patents
A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier Download PDFInfo
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- CN107353374B CN107353374B CN201710471959.7A CN201710471959A CN107353374B CN 107353374 B CN107353374 B CN 107353374B CN 201710471959 A CN201710471959 A CN 201710471959A CN 107353374 B CN107353374 B CN 107353374B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/02—Layered materials
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/14—Air permeable, i.e. capable of being penetrated by gases
-
- 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
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a kind of fluorine-containing mixtures for fluorine-containing superoleophobic microporous barrier, which is characterized in that by weight percentage includes following component: component A 50%~90%, B component 3%~25%, component C 0%~35%, D component 0%~3%；Wherein, component A is high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin；B component is containing fluoroalkyl acrylate monomer or mix monomer；Component C is mixture made of a kind of no fluorinated monomer or two or more floride-free crylic acid ester mixtures；D group is divided into high temperature radical initiator.Using the fluorine-containing mixture as raw material, available waterproof with higher, ventilative, resistance to greasy dirt, wash durability, meet waterproof and breathable protective garment of new generation demand fluorine-containing superoleophobic microporous barrier.
Description
Technical field
The present invention relates to windproof precipitation, light, warming, breathable protectives to take the fluorine-containing superoleophobic microporous barrier skill of special type used in fabric
Art field, and in particular to the fluoro containing polymers mixture for fluorine-containing superoleophobic microporous barrier.
Background technique
Homopolymerization, modification or the copolymer resins of fluoro containing polymers, especially tetrafluoroethene have excellent physical mechanical property
And chemical stability, each field such as chemical materials, mechano-electronic, aerospace, military project protection, new material and new energy all
It has a wide range of applications.After high molecular weight polytetrafluoroethyldispersions dispersion resin is blended with lubricating oil, squeezed, squeezed out using paste,
De-oiling is finally formed using uniaxial or biaxial stretching, can get the expanded polytetrafluoroethylsealing material with micro-porous permeable, by
In its property, which becomes a kind of functional fluorine-bearing microcellular polymeric material of high-end applications, is used for example as environmentally friendly mistake
Filter, protective shell fabric for clothing, medical instrument, electronic material and sealed insulating material etc..
Expanded polytetrafluoroethylsealing is fluorine-containing microcellular polymeric material, has height microcellular structure, there is excellent physical chemistry
Performance, mechanical performance, water-proof breathable properties and chemical stability just be used to manufacture wire cable insulating material since the seventies
Material, medical instrument, sealing material, environmental protection filtering and garment material etc..Industrially generally use high-purity (> 99.99%) tetrafluoro
Vinyl monomer is polymerize by dispersion polymerization processes or is copolymerized to prepare dispersion resin.It prepares used in expanded polytetrafluoroethylsealing
Material be usually to use the tetrafluoroethene homopolymerization dispersion or modified resin of super high molecular weight high-crystallinity, usually squeezed by paste
Pressure squeezes out, de-oiling, then uniaxial or biaxial stretching, is finally formed, and the fluorine-containing microporous membrane material of extruding is made, but such microporous barrier holds
Its waterproofness is lost vulnerable to oily pollution, furthermore lubricating oil used is inflammable and explosive in degreasing process, be easy to cause industrial peace
Full hidden danger.W. L. Gore & Associates, Inc. company discloses invention in the eighties and coats the poly- ammonia of hydrophilic on one side in puffed polytetrafluoroethylsealing film
Ester can improve the resistance to oil stains of its one side, but the air permeability of film is sacrificed.W. L. Gore & Associates, Inc. company discloses hair the nineties
It is bright to coat fluorinated acrylate emulsion in puffed polytetrafluoroethylsealing film, to improve its resistance to greasy dirt function and not sacrifice its air permeable
Function.But such production technique is excessively loaded down with trivial details, and water-proof breathable properties also need to be promoted again, is especially applied to space flight
When navigation, performance still has room for improvement.
CN1373792A (publication date: 2002-10-9) discloses a kind of fluororesin for being 20~150 nanometers by average grain diameter
Corpuscle emulsion and elastomer particle lotion coagulate obtained transparent elastic composition altogether, and wherein particulate fluorocarbon resin is by uniform differential
Be dispersed among elastomer, due to particulate fluorocarbon resin in advance by uniform micro disperse in the elastomer, so mechanical strength, resistance to can be provided
The excellent elastomer formed products such as abrasiveness and the transparency, but such elastic composition because fluororesin partial size it is too small, point
Son amount it is not high enough, can not extruding fluorine-containing microporous membrane is made.The enough high fluorine-containing poromerics of extruding of intensity, polytetrafluoroethyl-ne is made
The molecular weight of alkene must enough height, the standard specific gravity of general resin must between 2.14~2.17, average grain diameter must 180~
Between 360 nanometers.
CN104437126A (publication date: 2015-03-25) discloses a kind of system of super-hydrophobicity microporous teflon membran
Preparation Method, film obtained by this method and its application.CN 102294181A (publication date: 2011-12-28) discloses a kind of double
Refuse microporous teflon membran.Two technical solutions are similar, are all open using polytetrafluoroethylene (PTFE), super-hydrophobicity polyphosphazene polymer
Closing object (number-average molecular weight 5000-250000), such as containing fluoroalkyl and inflammable and explosive lubricating oil, mixing goes to make together
Film, resulting film stretching intensity is low < 20MPa, oil resistivity is low (only resistance to No. 3 oil), anti-pollution, the water-wash resistance of composite membrane fabric
Difference.
CN103158310A (publication date: 2013-06-19) discloses that a kind of high to refuse oily waterproof stitchless polytetrafluoroethylbulked bulked
Plate and preparation method thereof, it is open to use polytetrafluoroethylene (PTFE) and inflammable and explosive lubricating oil film, rear addition polymerization urethane resinous coat
Compound, resulting film does not have gas permeability, and without oleophobic property (only resistance to No. 1 oil), composite material penetrability is poor, wears uncomfortable.
CN104760381A (publication date: 2015-07-08) discloses polytetrafluoroethylwaterproof waterproof moisture permeating fabric enhancing vapor transfer rate
A kind of preparation method, it is disclosed that be film-made using polytetrafluoroethylene (PTFE) and inflammable and explosive lubricating oil, afterwards plus micro- porous poly- ammonia
Ester coating, resulting film gas permeability is not high, and without oleophobic property (only resistance to No. 1 oil), anti-flammability is bad, is not suitable for high-end applications.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is intended to provide a kind of fluorine-containing mixing for fluorine-containing superoleophobic microporous barrier
Material, using the fluorine-containing mixture as raw material, available waterproof with higher, wash durability, meets ventilative, resistance to greasy dirt
The fluorine-containing superoleophobic microporous barrier of the demand of waterproof and breathable protective garment of new generation.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier, which is characterized in that by weight percentage include such as
Lower component: component A 50%~90%, B component 3%~25%, component C 0%~35%, D component 0%~3%；Wherein, component A
Including high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin；B component includes one or more containing perfluoroalkyl acrylic
Ester monomer；Component C includes one or more no fluorinated monomers；D component includes high temperature radical initiator.
Further, by the way that component A, B component, component C and D component to be sequentially added into after mixing through without shearing mixing
And it obtains.
Further, the standard specific gravity of the component A is 2.13~2.18.
Further, molecular weight < 3000 of the B component, fusing point is at 80 DEG C or less.
Further, molecular weight < 8000 of the component C, fusing point is at 80 DEG C or less.
Further, the B component include perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate,
Perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group acrylate, perfluoro capryl second
Methyl acrylate, N- methyl perfluoro butyl sulfonic acid amine ethyl propylene acid esters, N- methyl perfluoro butyl sulfonic acid amine ethyl-methyl
Acrylate, N- methyl perfluoro hexyl sulfanilic acid ethyl propylene acid esters, N- methyl perfluoro hexyl sulfanilic acid ethyl methacrylate
Ester, N- methyl perfluoro octyl sulfonic acid amine ethyl propylene acid esters, N- methyl perfluoro octyl sulfonic acid amine ethylmethyl acrylate one
Kind is several.
Further, the high temperature radical initiator includes cumyl peroxide (CAS:80-43-3), 2,5- diformazan
- 2,5- pairs, base-(t-butyl peroxy) hexane (CAS:78-63-7), di-t-butyl peroxide (CAS:110-05-4), 2,5- diformazan
In bis- (the tert-butyl peroxide) -3- hexins (CAS:1068-27-5) of base -2,5-, cumyl hydroperoxide (CAS:80-15-9)
It is one or more of.
Further, the component C is for no fluoroalkyl or polyurethane acrylate prepolymer and without fluoroalkyl
The mixture of acrylate.
The beneficial effects of the present invention are: using the fluorine-containing mixture as raw material, when preparing fluorine-containing superoleophobic microporous barrier
It no longer needs to add inflammable and explosive lubricating oil, avoids the danger for causing detonation to explode when de-oiling, and obtained fluorine-containing microporous membrane
Waterproof with higher, ventilative, resistance to greasy dirt, wash durability, meet the demand of waterproof and breathable protective garment of new generation, oil resistivity is extremely
It less can resistance to No. 5 oil.
Specific embodiment
The invention will be further described below, it should be noted that before following embodiment is with the technical program
It mentions, the detailed implementation method and specific operation process are given, but the scope of the present invention is not limited to the present embodiment.
A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier, which is characterized in that by weight percentage include such as
Lower component: component A 50%~90%, B component 3%~25%, component C 0%~35%, D component 0%~3%；Wherein, component A
Including high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin；B component includes one or more containing perfluoroalkyl acrylic
Ester monomer；Component C includes one or more no fluorinated monomers；D component includes high temperature radical initiator.
Further, by the way that component A, B component, component C and D component to be sequentially added into after mixing through without shearing mixing
And it obtains.
Further, the standard specific gravity of the component A is 2.13~2.18.
Further, molecular weight < 3000 of the B component, fusing point is at 80 DEG C or less.
Further, molecular weight < 8000 of the component C, fusing point is at 80 DEG C or less.
Further, the B component is including (but not limited to) perfluoro butyl ethyl propylene acid esters [CH2=CH COO C2H4
C4F9], perfluoro butyl ethylmethyl acrylate [CH2=C CH3 COO C2H4 C4F9], perfluoro hexyl ethyl propylene acid esters
【CH2=CH COO C2H4 C6F13], perfluoro hexyl ethylmethyl acrylate [CH2=C CH3 COO C2H4 C6F13], perfluor
Octyl ethyl propylene acid esters [CH2=CH COO C2H4 C8F17], perfluorooctylethyl group methacrylate [CH2=C CH3 COO
C2H4C8F17], N- methyl, perfluoro butyl sulfanilic acid ethyl propylene acid esters [CH2=CH COO C2H4NCH3SO2C4F9], N- methyl,
Perfluoro butyl sulfanilic acid ethylmethyl acrylate [CH2=C CH3 COO C2H4NCH3SO2C4F9], N- methyl, perfluoro hexyl sulphur
Acid amide ethyl propylene acid esters [CH2=CH COO C2H4NCH3SO2C6F13], N- methyl, perfluoro hexyl sulfanilic acid ethyl-methyl propylene
Acid esters [CH2=C CH3 COO C2H4NCH3SO2C6F13], N- methyl, perfluoro octyl sulfonic acid amine ethyl propylene acid esters [CH2=CH
COO C2H4NCH3SO2C8F17], N- methyl, perfluoro octyl sulfonic acid amine ethylmethyl acrylate [CH2=C CH3 COO
C2H4NCH3SO2C8F17One or more of].
Further, the high temperature radical initiator includes cumyl peroxide (CAS:80-43-3), 2,5- diformazan
- 2,5- pairs, base-(t-butyl peroxy) hexane (CAS:78-63-7), di-t-butyl peroxide (CAS:110-05-4), 2,5- diformazan
In bis- (the tert-butyl peroxide) -3- hexins (CAS:1068-27-5) of base -2,5-, cumyl hydroperoxide (CAS:80-15-9)
It is one or more of.High temperature radical initiator is organic free machine initiator, half-life period between 100~250 degree, half-life period
Definition refers under some specific temperature after 10 hours that the effective ingredient that free machine initiator at least also possesses half can be produced from
By base.
The high molecular weight polytetrafluoroethyldispersions homopolymerization of component A or the manufacturing method of copolymer dispersion resin have in many documents
It records, in the present embodiment using following preparation method: deionized water and perfluorinated surfactant are added in autoclave,
Deoxygenation is vacuumized in kettle, and is heated up, and stirring is opened；When temperature in the kettle rises to about 50~80 DEG C, toward kettle in be passed through purity > 99.999%
Tetrafluoroethene and can with tetrafluoroethene be copolymerized comonomer；After pressure reaches 11~29 kilograms in kettle, free radical is added and draws
Agent is sent out, polymerization reaction is started, temperature in the kettle maintains 70~110 DEG C；Sustained response reaches 20~39% to emulsion solid content, will
After temperature in the kettle is fallen lower than 50 DEG C, stop stirring, unreacted monomer discharge, high molecular weight polytetrafluoro is made in reactant discharging
Ethylene homo or copolymerization dispersion resin lotion, about 180~390 nanometers of the average grain diameter of primary particle, preferred primary particle
About 220~330 nanometers of average grain diameter.
Wherein, the tetrafluoroethene of purity > 99.999% and optional other comonomers, moderate purity >
It is 95%~99.99% that 99.999% tetrafluoroethene accounts for monomer total amount percent by volume in reaction kettle；And it can be with tetrafluoro second
Alkene copolymerization comonomer, selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, partially
Vinyl fluoride, vinyl fluoride, 3 or are more than at any one monomer in 3,3- trifluoro propylenes, perfluoro alkyl ethylene etc. (C2~C8 alkyl)
A kind of combination more than monomer.Preferably, the high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin are superelevation point
Son amount polytetrafluoroethyl-ne polyamino alkenyl or copolymer dispersion resin, standard specific gravity between 2.13~2.18, preferably 2.135~
2.165, fusing point is between 325 DEG C~350 DEG C.The perfluorinated surfactant is the organic matter containing 6~16 carbon, and is at least contained
The functional group of one carboxylic acid or sulfonic acid.Preferably, surfactant is perfluorinated surfactant.The radical initiator choosing
From in persulfate, hydrogen peroxide or organic peroxide any one or combinations thereof.In polymerization process, pressure in kettle
Maintained at least at 15 kilograms or more.High molecular weight polytetrafluoroethyldispersions homopolymerization or copolymerization dispersion resin are that the high pressure polymerisation is good
High molecular weight polytetrafluoroethyldispersions homopolymerization or copolymerization dispersion resin emulsion coagulation are dried and are obtained.
In the present embodiment, component C is for no fluoroalkyl or polyurethane acrylate prepolymer and without fluoroalkyl
The mixture of acrylate, molecular weight < 8000, preferred molecular weight < 5000, fusing point is at 80 DEG C hereinafter, preferably its fusing point
At 50 DEG C or less.
The polyurethane acrylate prepolymer can be used to be prepared following preparation method: by the row of vacuumizing in reaction kettle
Moisture is added diisocyanate, and heats up, and opens stirring；Temperature in the kettle is risen to about 50~150 DEG C, it is then more toward being passed through in kettle
First alcohol (containing polyether polyol or polyester polyol), the total yield molar ratio of two of them main material is diisocyanate (- NCO
Isocyanate equivalent): polyalcohol (- OH hydroxyl equivalent)=2:1~8:1, kettle interior reaction temperature should maintain about at 50~150 DEG C,
Reaction about 10~180 minutes after, toward kettle in add the acrylate containing hydroxyalkyl or the methacrylate containing hydroxyalkyl, add
The equivalents of the hydroxyalkyl acrylates entered is greater than or equal to unreacted isocyanate equivalent number, and (hydroxyl and isocyanates are worked as
Number is measured than about 2:1~1:1), remaining unreacted isocyanates is completely reacted to by hydroxyalkyl as polyurethane acrylate prepolymer
Aggressiveness, after being stirred, kettle interior reaction temperature maintains to react about 10~180 minutes, cooling discharge, i.e., about at 50~150 DEG C
It can get polyurethane acrylate prepolymer.
When the composition of component C calculates the polyurethane acrylate prepolymer for being 0%~70% by weight percentage；30%~
100% without fluoroalkyl.
The polyurethane acrylate prepolymer is hot melt, and fusing point is at 80 DEG C hereinafter, its preferred fusing point is at 50 DEG C
Hereinafter, its raw material is selected from: aromatic diisocyanate or aliphatic diisocyanate or 2~3 yuan of isocyanates；It is polynary
Alcohol, selected from polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyester polyol, polycarbonate polyol etc., point of all polyalcohols
Son amount is between 600~5000, and between preferably 1000~3000, each molecule contains 2~3 hydroxyls.
The average molecular weight of the no fluoroalkyl less than 1000, its preferred average molecular weight less than 600,
Fusing point at 80 DEG C hereinafter, its preferred fusing point at 50 DEG C hereinafter, atmospheric boiling point is at 160 degree or more, including hydroxyalkyl acrylates,
Hydroxyalkyl methacrylates, C5~C20 alkyl acrylate, C4~C20 alkylmethacrylate and C6~C20 acid second
The one or more of enester；Wherein in hydroxyalkyl acrylates, hydroxyalkyl methacrylates, including hydroxy-ethyl acrylate, first
Base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate.Further, preferably, the no fluoroalkyl third
Olefin(e) acid ester is the monomer or its mix monomer of free redical polymerization, and atmospheric boiling point, can be different pungent using acrylic acid at 200 degree or more
The different nonyl ester of ester, acrylic acid, isodecyl acrylate, different 11 ester of acrylic acid, different 13 ester of acrylic acid, isooctyl acid vinyl acetate, new nonyl
Vinyl acetate, vinyl neodecanoate and other contain C6~C18 alkyl acrylate and other propylene containing C6~C18 alkyl methyl
The one or more of acid esters.
Using above-mentioned fluorine-containing mixture as raw material prepare fluorine-containing superoleophobic microporous barrier the preparation method is as follows:
S1 uses above-mentioned fluorine-containing mixture without shearing uniform stirring, no longer needs to plus lubricating oil is (when can exempt de-oiling
Inflammable and explosive danger), it directly pours into pressure blastostyle bucket, in 20 DEG C~100 DEG C pushing embryos after exhaust, cylindrical paste is made
Mixture blastostyle；
The pasty mixture blastostyle is carried out extruding extrusion by pushing machine at 20 DEG C~100 DEG C by S2, is then rolled
At band, beam thickness is between 50~2000 microns, and preferred 80~800 microns；
The band is done uniaxial or biaxial stretching at 100 DEG C~200 DEG C by S3, and finally heat is fixed at 200 DEG C~390 DEG C
Type is made for fluorine-containing superoleophobic microporous barrier.
In step S1, being added in fluorine-containing mixture includes adding for one or more of active powdered carbon, graphite, inorganic matter
Add material, fluorine-containing mixture and the mixed proportion to add materials are weight ratio 1:0.1~1.0.
About 0.005~1.5 millimeter of thickness of the fluorine-containing superoleophobic micropore membrane material, preferably from about 0.01~0.08 millimeter；
Film weighs about 1~1200 grams per square meter, preferably from about 3~30 grams per square meters.Porosity about 30~95%；The initial oil resistivity of film surface is at least
It is 5 grades；Film stretching intensity > 20MPa；After washing 10 times, film surface oil resistivity is at least 4 grades.Optionally, film gas permeability is used
Gurley surveyed 100 milliliters of air permeable speed of method less than 60 seconds.
This fluorine-containing microporous membrane can be compound with woven face shots patch, and fabric is flat fabric (20~180 grams per square meters) or knitting
Cloth or non-woven fabrics, through dotted joint adhesive that film is compound with cloth, this composite material, water pressure resistance is initially greater than 100kPa；Through washing
After 10 times, water pressure resistance is still greater than 60kPa；Composite material gas permeability Gurley surveys 100 milliliters of air permeable speed of method about 6~90
Second；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Other all properties indexs all meet waterproof and breathable
Garment material standard, testing standard are as shown in table 1.
Table 1
In conclusion when preparing fluorine-containing superoleophobic microporous barrier as raw material using the fluorine-containing mixture, it is inflammable without being added
Explosive lubricating oil, processing technology is highly-safe, added in the homopolymerization of macromolecule tetrafluoroethene or copolymerization dispersion resin to help
Free redical polymerization becomes a part of high molecule micropore film at high temperature for agent, and industry security caused by no three wastes is asked
Topic.The waterproof of obtained fluorine-containing superoleophobic microporous barrier, oil resistant, antifouling property significantly improve, be able to satisfy resist higher hydraulic pressure and
The important need of poisonous and harmful liquid intrusion human body is prevented, and ventilative and penetrability is higher, sealing effect is good at thread
Application requirement.When being applied to protection and taking composite material, there is light, comfortable, ventilative, waterproof and prevent poisonous and harmful
The permanent protective property energy of liquid, with fabric point patch it is compound after, permanent protective property, comfort, warmth retention property, gas permeability etc. can be provided to wearer
Multiple demand.
Embodiment 1 is the preparation that high molecular weight polytetrafluoroethyldispersions are copolymerized dispersion resin
In the horizontal high-pressure reaction kettle of about 1000 liters of internal volumes, be firstly added 500 liters deionized water, 20 kilograms
High-purity paraffin (50 DEG C~85 DEG C of fusing point) and 180 grams of perfluorooctanoic acid, vacuumized in kettle deoxygenation (until oxygen content <
20ppm), it and heats up, opens stirring；When temperature in the kettle rises to about 70 DEG C, the tetrafluoroethene of purity > 99.999% is passed through in kettle
Gas makes pressure in kettle reach about 22 kilograms.Then the perfluoroethylvinyl ether (C of 300 grams of purity > 98%2F5- OCF=
CF2) it is used as comonomer, it is initially added into kettle with 10 grams of speed per minute, while 0.8 gram of ammonium persulfate (thing being added in kettle
It is first dissolved in 500 milliliters of water) as initiator, started copolymer reacts, and temperature in the kettle maintains 80~100 DEG C, in reaction process
Being passed through tetrafluoroethylene gas makes pressure in kettle maintain about 20 kilograms.Sustained response reaches about 30% to emulsion solid content, by kettle
After interior temperature is down to 50 degree or less, stop stirring, unreacted monomer discharge is depressured, reactant blowing, it is poly- to obtain super high molecular weight
Tetrafluoroethene copolymerization dispersion resin lotion, about 280 nanometers of the average grain diameter of primary particle.Lotion is after dilution, high-speed stirred
Suspension polymer sabot is put into 190 degree of high temperature oven drying to get high molecular weight polytetrafluoroethyldispersions copolymerization point by flocculate and break emulsion
Dissipate resin.Through detecting, tetrafluoroethene be copolymerized dispersion resin standard specific gravity, about 2.149, fusing point peak 325~350 DEG C it
Between.
The preparation of 2 polyurethane acrylate prepolymer of embodiment
In the reaction kettle of about 200 liters of internal volumes, collet is first to heat to 100 DEG C, vacuumizes in kettle and rushes nitrogen dehumidifying,
26.2 kilograms of (containing about 200 More-NCO isocyanates) 4,4'- dicyclohexyl methyl hydride diisocyanate HMDI are added, open stirring,
Temperature in the kettle is raised to about 100 DEG C, then toward the polypropylene glycol (molecular weight of 60 kilograms of addition in kettle (containing about 60 More-OH hydroxyls)
About 2000), after reacting about 90 points, 18.2 kilograms of (containing about 140 More-OH hydroxyls) hydroxyethyl methacrylates, temperature in kettle is added
Degree maintains about 100 DEG C, and the polyurethane acrylate prepolymer with viscous liquid is just made after reaction about one hour, cooling
It is afterwards liquid at 50 DEG C, illustrates that fusing point is less than 50 DEG C.
The preparation of embodiment 3 polyurethane acrylate prepolymer and the mixture without fluoroalkyl
(3A) polyurethane acrylate prepolymer and without fluoroalkyl weight ratio be 3:7 when: at one about 100 liters
The polyurethane acrylate prepolymer that 15 kilograms of embodiment 2 obtains is added in the agitator of internal volume, under normal temperature and pressure, then
The isodecyl acrylate (CAS:1330-61-6) for adding 35 kilograms, continuously stir into it is homogeneous, stop stirring, mixture blowing,
Obtain polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
(3B) polyurethane acrylate prepolymer and without fluoroalkyl weight ratio be 5:5 when: at one about 100 liters
Polyurethane acrylate prepolymer made by 25 kilograms of embodiment 2 is added in the agitator of internal volume, under normal temperature and pressure, then
The isodecyl acrylate (CAS:1330-61-6) for adding 25 kilograms, continuously stir into it is homogeneous, stop stirring, mixture blowing,
Obtain polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
The preparation of the fluorine-containing mixture of embodiment 4
Scheme 1: the component A high molecular weight polytetrafluoroethyldispersions that embodiment 1 is obtained are copolymerized dispersion resin, and B component is two kinds
Or above perfluor alkyl ethyl acrylate mixture (average molecular weight < 1000, fusing point less than 35 DEG C, perfluoroalkyl
Distribution is about C4:10%, C6；30%, C8；50%, C10:10%) and embodiment 3 in the obtained component C polyurethane of scheme 3A
Acrylate prepolymer body and mixture and D component high temperature radical initiator hydrogen peroxide isopropyl without fluoroalkyl
Benzene (CAS:80-15-9) is blended about using mild without shearing method with the weight ratio of (A:B:C:D)=(70:10:19:1)
Half an hour obtains fluoro containing polymers opaque white color mixture, as fluorine-containing mixture.The standard specific gravity of the fluorine-containing mixture
About 1.89g/cm3.
Scheme 2: being copolymerized dispersion resin for the component A high molecular weight polytetrafluoroethyldispersions of embodiment 1, B component be two kinds or with
On the mixture of perfluor alkyl ethyl acrylate (average molecular weight < 1000, fusing point is less than 30 DEG C, the distribution of perfluoroalkyl
About C4:10%, C6；60%, C8；And D component high temperature radical initiator cumyl hydroperoxide (CAS:80- 30%)
15-9) with the weight ratio of (A:B:C:D)=(80:19:0:1), about half an hour is blended without shearing method using mild, obtains
Extraordinary fluoro containing polymers white mixture.The standard specific gravity of the special type fluoro containing polymers mixture is about 2.03g/cm3.
Scheme 3: being copolymerized dispersion resin for the component A high molecular weight polytetrafluoroethyldispersions of embodiment 1, is two kinds or more complete
Fluoroalkyl ethyl propylene acid esters mixture (average molecular weight < 1000, for fusing point less than 35 DEG C, the distribution of perfluoroalkyl is about C4:
10%, C6；30%, C8；50%, C10:10%) and embodiment 3 in the obtained component C polyurethane acrylate prepolymer of scheme 3B it is poly-
Body and mixture and D component high temperature radical initiator cumyl hydroperoxide (CAS:80-15- without fluoroalkyl
9) with the weight ratio of (A:B:C:D)=(65:11:23:1), about half an hour is blended without shearing method using mild, is contained
Fluorine macromolecule opaque white color mixture, i.e., the described fluorine-containing mixture.The standard specific gravity of the fluorine-containing mixture is about 1.85g/
cm3。
Scheme 4: being copolymerized dispersion resin for the component A high molecular weight polytetrafluoroethyldispersions of embodiment 1, B component be two kinds or with
On the mixture of perfluor alkyl ethyl acrylate (average molecular weight < 1000, fusing point is less than 30 DEG C, the distribution of perfluoroalkyl
About C4:10%, C6；60%, C8；30%), component C isodecyl acrylate (CAS:1330-61-6) and D component high temperature from
By base initiator cumyl hydroperoxide (CAS:80-15-9) with the weight ratio of (A:B:C:D)=(78:10:11:1), using temperature
About half an hour is blended with without shearing method, obtains extraordinary fluoro containing polymers opaque white color mixture, i.e., it is described fluorine-containing mixed
Close material.The standard specific gravity of the special type fluoro containing polymers mixture is about 1.98g/cm3。
The manufacture of the fluorine-containing microporous membrane of embodiment 5 and its composite material
After the fluorine-containing mixture that scheme 1 in embodiment 4 is obtained is used without shearing stirring, first it is pressed into advance at 70 DEG C
Columned paste mixture, then at about 70 DEG C by pushing machine the paste mixture be squeezed into rodlike, then it presses
Prolong into band, about 0.45 millimeter of thickness, about 180 millimeters of width.Longitudinal quickly drawing under the conditions of about 130 DEG C of temperature by the band
About 4 times are stretched, then again quick about 12 times of cross directional stretch under about 180 DEG C of hot conditions, finally in about 370 DEG C of hot conditions
Lower setting about 11 seconds, that is, obtains fluorine-containing superoleophobic microporous membrane.
Through detecting, about 0.036 millimeter of thickness of the extraordinary fluorine-containing microporous membrane of gained, about 1800 millimeters of breadth, film weighs about 15
Grams per square meter, porosity about 80~83%, film stretching intensity > 20MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method
About 10~13 seconds.
It, will through dotted polyurethane fitting glue point by the fluorine-containing superoleophobic microporous membrane and 6 flat fabric of nylon (96 grams per square meters)
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 200kPa, and after washing 10 times, water pressure resistance is still greater than 100kPa；
Film surface oil resistivity is initially 7 grades, and after washing 10 times, film surface oil resistivity still has 6 grades；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 15~20 seconds；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Its
Its all properties index all meets waterproof breathable garment fabric standard, and testing standard is as shown in table 1.
The manufacture of the fluorine-containing superoleophobic microporous membrane of embodiment 6 and its composite material
The fluorine-containing mixture that scheme 2 in embodiment 4 is obtained is used without the shearing first precompressed at 70 DEG C after mixing evenly
At columned paste mixture, by pushing machine the paste mixture be squeezed at about 70 DEG C it is rodlike, then
It is rolled into band, about 0.45 millimeter of thickness, about 180 millimeters of width.The band is longitudinal quick under the conditions of about 140 DEG C of temperature
About 4 times are stretched, then again quick about 12 times of cross directional stretch under about 190 DEG C of hot conditions, finally in about 370 DEG C of high temperature item
It is formed under part, about 11 seconds, that is, obtains fluorine-containing superoleophobic microporous membrane.
Through detecting, about 0.031 millimeter of the thickness of the fluorine-containing superoleophobic microporous membrane of gained, about 1800 millimeters of breadth, film is weighed about
15 grams per square meters, porosity about 86~89%, film stretching intensity > 25MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method
Degree about 8~10 seconds.
It, will through dotted polyurethane fitting glue point by the fluorine-containing superoleophobic microporous membrane and 6 flat fabric of nylon (96 grams per square meters)
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 200kPa, and after washing 10 times, water pressure resistance is still greater than 150kPa；
Film surface oil resistivity is initially 8 grades, and after washing 10 times, film surface oil resistivity still has 7 grades；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 13~17 seconds；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Its
Its all properties index all meets waterproof breathable garment fabric standard, and testing standard is as shown in aforementioned table 1.
The manufacture of the fluorine-containing superoleophobic microporous membrane of embodiment 7 and its composite material
The fluorine-containing mixture that scheme 3 in embodiment 4 obtains first is pressed into circle at 70 DEG C after mixing evenly without shearing in advance
Columnar paste mixture, then at about 70 DEG C by pushing machine the paste mixture be squeezed into rodlike, then roll
At band, about 0.45 millimeter of thickness, about 180 millimeters of width.By the band under the conditions of about 130 DEG C of temperature longitudinal Rapid stretching
About 4 times, then again quick about 12 times of cross directional stretch under about 190 DEG C of hot conditions, finally under about 370 DEG C of hot conditions
Sizing shape 11 seconds, that is, obtain fluorine-containing superoleophobic microporous membrane.
Through detecting, about 0.039 millimeter of the thickness of the fluorine-containing superoleophobic microporous membrane of gained, about 1800 millimeters of breadth, film is weighed about
16 grams per square meters, porosity about 76~80%, gas permeability Gurley is surveyed 100 milliliters of air permeable speed of method about 13~16 seconds.
It, will be thin through dotted polyurethane fitting glue point by fluorine-containing superoleophobic microporous membrane and 6 flat fabric of nylon (96 grams per square meters)
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 200kPa, and after washing 10 times, water pressure resistance is still greater than 100kPa；Film
Face oil resistivity is initially 7 grades, and after washing 10 times, film surface oil resistivity still has 5 grades；Film stretching intensity > 20MPa, composite material are saturating
Gas Gurley is surveyed 100 milliliters of air permeable speed of method about 19~23 seconds；The sealing effect that sealing rod is pasted at thread is good, full
Sufficient application requirement.Other all properties indexs all meet waterproof breathable garment fabric standard, and testing standard list is in rear.
The manufacture of the fluorine-containing superoleophobic microporous membrane of embodiment 8 and its composite material
By the fluorine-containing mixture manufactured in the scheme 4 of embodiment 4 without shearing first at about 70 DEG C after mixing evenly
It is pressed into columned paste mixture in advance, then carries out the paste mixture by pushing machine at about 70 DEG C to be squeezed into stick
Shape, then it is rolled into band, about 0.45 millimeter of thickness, about 180 millimeters of width.The band is indulged under the conditions of about 140 DEG C of temperature
To about 4 times of Rapid stretching, then again quick about 12 times of cross directional stretch under about 190 DEG C of hot conditions, finally at about 370 DEG C
It is formed shape 12 seconds under hot conditions, that is, obtains fluorine-containing superoleophobic microporous membrane.
Through detecting, about 0.032 millimeter of the thickness of the fluorine-containing superoleophobic microporous membrane of gained, about 1800 millimeters of breadth, film is weighed about
15 grams per square meters, porosity about 86~89%, film stretching intensity > 20MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method
Degree about 6~8 seconds.
It, will through dotted polyurethane fitting glue point by the fluorine-containing superoleophobic microporous membrane and 6 flat fabric of nylon (96 grams per square meters)
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 200kPa, and after washing 10 times, water pressure resistance is still greater than 100kPa；
Film surface oil resistivity is initially 7 grades, and after washing 10 times, film surface oil resistivity still has 6 grades；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 10~13 seconds；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Its
Its all properties index all meets waterproof breathable garment fabric standard, and testing standard is as shown in aforementioned table 1.
Embodiment 9 is containing the fluorine-containing superoleophobic microporous membrane of activated carbon and its preparation of composite material
The fluorine-containing mixture and decyl acrylate (component C) that the scheme 2 of embodiment 4 is obtained
And active micropowder with the weight ratio of about 7:1:2 without shearing mixing, be then first pressed into cylinder in advance at about 70 DEG C
The paste mixture of shape, then at about 70 DEG C by pushing machine the paste mixture be squeezed into rodlike, then it is rolled into
It is band-like, about 0.9 millimeter of thickness, about 180 millimeters of width.By the dry band under about 140 DEG C of hot conditions longitudinal Rapid stretching about 8
Times,
Then lateral about 12 times of the Rapid stretching under about 190 DEG C of hot conditions again, finally in about 370 DEG C of hot conditions
Lower sizing shape 16 seconds, i.e. the acquisition fluorine-containing superoleophobic microporous membrane of grey.In the present embodiment, the effect for adding component C is mainly
The viscosity for avoiding direct plus active micropowder that from may occurring is excessively high, mixes more non-uniform problem.
Through detecting, about 0.048 millimeter of the thickness of the fluorine-containing superoleophobic microporous membrane of gained, about 1800 millimeters of breadth, film is weighed about
17 grams per square meters, porosity about 77~81%, gas permeability Gurley is surveyed 100 milliliters of air permeable speed of method about 5~7 seconds.
By fluorine-containing superoleophobic microporous membrane with containing continuous flat fabric (150 grams per square meters), being bonded glue point through dotted polyurethane will
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 100kPa, and after washing 10 times, water pressure resistance is still greater than 70kPa；
Film surface oil resistivity is initially 7 grades, and after washing 10 times, film surface oil resistivity still has 6 grades；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 9~13 seconds；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Containing work
Property carbon fluorine-containing superoleophobic microporous membrane have resist toxic liquid intrusion and absorb toxic gas ability, other all properties
Index all meets hunting dress fabric standard, and testing standard is as shown in aforementioned table 1.
The fluorine-containing varicosity film of special type of 10 graphitiferous of embodiment and its manufacture of composite material
The fluorine-containing mixture and different 13 ester (component C) of acrylic acid and graphite microparticles that scheme 2 in embodiment 4 is obtained are with about
Then the weight ratio of 8:1:1 is first pressed into columned paste mixture without shearing mixing in advance at about 70 DEG C, then at about 70 DEG C
Down the paste mixture be squeezed by pushing machine rodlike, then rolls and become band, about 0.45 millimeter of thickness, width is about
180 millimeters.By the dry band under about 140 DEG C of hot conditions longitudinal about 4 times of Rapid stretching, then again in about 200 DEG C of high temperature
Under the conditions of lateral about 12 times of Rapid stretching, finally be formed shape 13 seconds under about 370 DEG C of hot conditions, i.e., acquisition grey is fluorine-containing surpasses
Oleophobic microporous films.In the present embodiment, the effect for adding component C mainly avoids direct plus active micropowder that from may occurring
Viscosity is excessively high, mixes more non-uniform problem.
Through detecting, about 0.039 millimeter of the thickness of the fluorine-containing superoleophobic microporous membrane of gained, about 1800 millimeters of breadth, film is weighed about
15 grams per square meters, porosity about 81~86%, film stretching intensity > 20MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method
Degree about 3~5 seconds.
It, will be thin through dotted polyurethane fitting glue point by fluorine-containing superoleophobic microporous membrane and terylene flat fabric (70 grams per square meters)
Film is compound with cloth, this composite material, water pressure resistance is initially greater than 100kPa, and after washing 10 times, water pressure resistance is still greater than 70kPa；Film
Face oil resistivity is initially 7 grades, and after washing 10 times, film surface oil resistivity still has 5 grades；Composite material gas permeability Gurley surveys method 100
Milliliter air permeable speed about 8~10 seconds；The sealing effect that sealing rod is pasted at thread is good, meets application requirement.Containing activity
The fluorine-containing superoleophobic microporous membrane of carbon has the ability for removing electrostatic, and other all properties indexs all meet industrial protection garment material
Standard, testing standard is as shown in aforementioned table 1.
Comparative example 1 (without special blend is dosed)
The polytetrafluoroethyldispersion dispersion resin powder that standard specific gravity is about 2.156 (is derived from into great Jing company, Japan, resin grade
106) it is mixed with Mobi l senior lubricant (trade mark Isopar M) with the weight ratio of about 4:1, is first pressed into circle in advance after mixing evenly
Columnar paste mixture, then at about 70 DEG C by pushing machine the paste mixture be squeezed into rodlike, then roll
Become band, about 0.60 millimeter of thickness, about 180 millimeters of width.By the band, de-oiling obtains dry band in about 230 DEG C of baking oven, will
The dry band about 6 times of longitudinal stretching under about 250 DEG C of hot conditions, the then cross directional stretch under about 300 DEG C of hot conditions again
It about 12 times, is finally formed shape 18 seconds under about 370 DEG C of hot conditions, that is, obtains expanding microporous fluorine film.
Through detecting, about 0.036 millimeter of the thickness of the expanding microporous fluorine film of gained, about 1800 millimeters of breadth, film weigh about 14 grams/it is flat
Rice, porosity about 80~85%, film stretching intensity > 20MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method about 12
~16 seconds.
This expanding microporous fluorine film and 6 flat fabric of nylon (96 grams per square meters) are bonded glue point for film and cloth through dotted polyurethane
Compound, this composite material, initial water pressure resistance is greater than 200kPa, and after washing 10 times, water pressure resistance is less than 10kPa；Film surface oil resistivity
It is initially 1 grade, after washing 10 times, film surface oil resistivity is 0 grade (not oil resistant completely)；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 17~22 seconds；The sealing effect that sealing rod is pasted at thread is bad, is unable to satisfy to apply and want
It asks.Such membrane material does not meet waterproof breathable garment fabric standard, and testing standard list is in rear.
Comparative example 2 (is mixed into polyurethane according to CN103158310A, be not added containing fluoroalkyl)
The polytetrafluoroethyldispersion dispersion resin powder that standard specific gravity is about 2.156 (is derived from into great Jing company, Japan, resin grade
106) polyurethane acrylate prepolymer and the mixing without fluoroalkyl obtained by scheme 3A in first and embodiment 3
Object, high temperature radical initiator di-t-butyl peroxide (CAS:110-05-4), with weight ratio (A:B:C:D)=(66:0:33:
1) it is blended, is first pressed into columned paste mixture in advance after mixing evenly, then pass through pushing machine for the paste at about 70 DEG C
Mixture be squeezed into rodlike, then rolls and becomes band, and about 0.45 millimeter of thickness, about 180 millimeters of width.By the dry band about
About 4 times of longitudinal stretching under 140 DEG C of hot conditions, then about 12 times of cross directional stretch under about 190 DEG C of hot conditions again, finally
It is formed shape 11 seconds under about 370 DEG C of hot conditions, that is, obtains fluorine-containing microporous membrane.
Through detecting, about 0.038 millimeter of the thickness of the fluorine-containing microporous membrane of gained, about 1800 millimeters of breadth, film weigh about 13 grams/it is flat
Rice, porosity about 77~82%, film stretching intensity > 20MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method about 18
~23 seconds.
By this fluorine-containing microporous membrane and 6 flat fabric of nylon (96 grams per square meters), through dotted polyurethane fitting glue point by film with
Cloth is compound, this composite material, water pressure resistance is initially less than 150kPa, and after washing 10 times, water pressure resistance is less than 10kPa；Film surface oil resistant
Property be initially 0 grade, through washing 10 times after, film surface oil resistivity be 0 grade (oil resistivity is poor)；Composite material gas permeability Gurley surveys method
100 milliliters air permeable speed about 12~17 seconds；The sealing effect that sealing rod is pasted at thread is bad, is unable to satisfy to apply and want
It asks.Such membrane material does not meet waterproof breathable garment fabric standard, and testing standard list is in rear.
Comparative example 3 (polymer is mixed into containing fluoroalkyl according to CN102294181A, number-average molecular weight >
10000)
Fluorine-containing microporous membrane is prepared according to the method for CN102294181A embodiment two (containing inflammable and explosive solvent, to gather
Close object and contain fluoroalkyl, number-average molecular weight > 10000), through detecting, about 0.020 milli of thickness of the fluorine-containing microporous membrane of gained
Rice, porosity about 80~84%, film stretching intensity < 15MPa, gas permeability Gurley survey 100 milliliters of air permeable speed of method about 12
~18 seconds.This fluorine-containing microporous membrane and 6 flat fabric of nylon (96 grams per square meters) are bonded glue point for film and cloth through dotted polyurethane
Compound, this composite material, water pressure resistance is initially less than 150kPa, and after washing 10 times, water pressure resistance is less than 50kPa；Film surface oil resistivity
It is initially 3 grades, after washing 10 times, film surface oil resistivity is 2 grades (oil resistivity is poor)；Composite material gas permeability Gurley surveys method 100
Milliliter air permeable speed about 20~27 seconds；The sealing effect that sealing rod is pasted at thread is bad, is unable to satisfy application requirement.This
The membrane material of sample does not meet waterproof breathable garment fabric standard, and all testing standards are as shown in aforementioned table 1.
Based on the above embodiments with comparative example it follows that using fluorine-containing mixture of the invention as raw material system
Standby fluorine-containing superoleophobic microporous barrier, it is not necessary that inflammable and explosive lubricating oil is added, can directly be squeezed out by paste, be pressed into band, unidirectionally or
Safeguard function more preferably fluorine-containing superoleophobic microporous membrane can be then made in biaxial tension, sizing.Its processing technology is highly-safe, nothing
Three wastes problem, the waterproofness of film product, oil resistivity, water-wash resistance, pollution resistance are higher, and the fluorine-containing microporous membrane of special type can be resisted
High hydraulic pressure, and poisonous and harmful liquid intrusion human body is prevented, air permeable and moisture vapor permeability are excellent, and sealing effect is good at thread,
The requirement applied needed for being able to satisfy.When being applied to production protective garment, there is high anti-hydraulic pressure and prevent what poisonous and harmful liquid penetrated
Protective function has both light, comfortable, warming, gas permeability, can greatly promote the fight protection of wearer.
For those skilled in the art, it can be provided various corresponding according to above technical solution and design
Change and modification, and all these change and modification, should be construed as being included within the scope of protection of the claims of the present invention.
Claims (7)
1. a kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier, which is characterized in that by weight percentage include as follows
Component: component A 50%~90%, B component 3%~25%, component C 0%~35%, D component 1%~3%；Wherein, component A packet
Include high molecular weight proplast or copolymer dispersion resin；Component C includes one or more no fluorinated monomers；D group
Dividing includes high temperature radical initiator；
B component includes perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethylacrylic acid
Ester, perfluoro hexyl ethylmethyl acrylate, perfluorooctylethyl group acrylate, perfluorooctylethyl group methacrylate, N-
Methyl perfluoro butyl sulfonic acid amine ethyl propylene acid esters, N- methyl perfluoro butyl sulfonic acid amine ethylmethyl acrylate, N- methyl are complete
Fluorine hexyl sulfanilic acid ethyl propylene acid esters, N- methyl perfluoro hexyl sulfanilic acid ethylmethyl acrylate, N- methyl perfluoro octyl
The one or more of sulfanilic acid ethyl propylene acid esters, N- methyl perfluoro octyl sulfonic acid amine ethylmethyl acrylate；
The fluorine-containing mixture does not include lubricating oil.
2. the fluorine-containing mixture according to claim 1 for fluorine-containing superoleophobic microporous barrier, which is characterized in that by by A
Component, B component, component C and D component are sequentially added into after mixing through being obtained by mixing without shearing.
3. the fluorine-containing mixture according to claim 1 for fluorine-containing superoleophobic microporous barrier, which is characterized in that the A group
The standard specific gravity divided is 2.13~2.18.
4. the fluorine-containing mixture according to claim 1 for fluorine-containing superoleophobic microporous barrier, which is characterized in that the B group
The fusing point divided is at 80 DEG C or less.
5. the fluorine-containing mixture according to claim 1 for fluorine-containing superoleophobic microporous barrier, which is characterized in that the C group
Molecular weight < 8000 divided, fusing point is at 80 DEG C or less.
6. the fluorine-containing mixture according to claim 1 or 2 for fluorine-containing superoleophobic microporous barrier, which is characterized in that described
High temperature radical initiator includes cumyl peroxide, 2,5- dimethyl -2,5- pairs-(t-butyl peroxy) hexane, peroxidating
One or more of bis- (the tert-butyl peroxide) -3- hexins of di-t-butyl, 2,5- dimethyl -2,5-, cumyl hydroperoxide.
7. the fluorine-containing mixture according to claim 1 for fluorine-containing superoleophobic microporous barrier, which is characterized in that the C group
It is divided into no fluoroalkyl or polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
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| CN201710471959.7A CN107353374B (en) | 2017-06-20 | 2017-06-20 | A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier |
| PCT/CN2018/081857 WO2018233346A1 (en) | 2017-06-20 | 2018-04-04 | Fluorine-containing mixture material and fluorine-containing super-oleophobic microporous membrane using same as raw material, and preparation method therefor and use thereof |
| US16/624,939 US11702494B2 (en) | 2017-06-20 | 2018-04-04 | Fluorine-containing mixture material and fluorine-containing super-oleophobic microporous membrane using same as raw material, and preparation method therefor and use thereof |
| US18/205,020 US20230303742A1 (en) | 2017-06-20 | 2023-06-02 | Fluorine-containing Mixture Material and Fluorine-containing Super-oleophobic Microporous Membrane Using Same as Raw Material, and Preparation Method therefor and Use thereof |
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| CN112980118A (en) * | 2021-02-07 | 2021-06-18 | 浙江汉丞科技有限公司 | Fluorine-containing polymer mixture for high-moisture-permeability super-breathable microporous membrane and application thereof |
| CN113150333A (en) * | 2021-02-07 | 2021-07-23 | 浙江汉丞科技有限公司 | Preparation method of fluorine-containing super-oleophobic microporous membrane with high moisture permeability |
| CN115819912B (en) * | 2022-10-12 | 2023-07-14 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretched film and preparation method thereof |
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| CN103341328A (en) * | 2013-06-27 | 2013-10-09 | 广州中国科学院先进技术研究所 | Fluorinated acrylate copolymer pervaporation composite film and preparation method thereof |
| CN104437126A (en) * | 2013-09-23 | 2015-03-25 | 上海碧科清洁能源技术有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene microporous membrane, membrane prepared by preparation method and application of super-hydrophobic polytetrafluoroethylene microporous membrane |
| KR20170022691A (en) * | 2015-08-21 | 2017-03-02 | 한국과학기술원 | Method of Preparing Membrane Controlled Surface Energy and Use Thereof |
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