CN107216431A - A kind of preparation method of fluorine-containing superoleophobic microporous barrier - Google Patents
A kind of preparation method of fluorine-containing superoleophobic microporous barrier Download PDFInfo
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- CN107216431A CN107216431A CN201710470817.9A CN201710470817A CN107216431A CN 107216431 A CN107216431 A CN 107216431A CN 201710470817 A CN201710470817 A CN 201710470817A CN 107216431 A CN107216431 A CN 107216431A
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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
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
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- 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
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- 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
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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
- 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
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- 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
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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
- 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
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- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
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Abstract
The invention discloses a kind of preparation method of fluorine-containing superoleophobic microporous barrier, using the fluorine-containing compound specially developed as raw material, fluorine-containing compound includes following component by weight percentage：Component A 50%~90%, B component 3%~25%, component C 0%~35%, D components 0%~3%；Wherein, component A includes high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin；B component includes one or more containing fluoroalkyl acrylate monomer；Component C includes one or more without fluorinated monomer；D components include high temperature radical initiator, and without adding, inflammable and explosive lubricating oil, safe, and obtained fluorine-containing superoleophobic microporous barrier has higher waterproof, ventilative, resistance to greasy dirt, wash durability, the demand for meeting waterproof and breathable protective garment of new generation.
Description
Technical field
Extraordinary fluorine-containing superoleophobic microporous barrier skill used in fabric is taken the present invention relates to windproof precipitation, light, warming, breathable protective
A kind of art field, and in particular to preparation method of fluorine-containing superoleophobic microporous barrier.
Background technology
Homopolymerization, modification or the copolymer resins of fluoro containing polymerses, especially tetrafluoroethene have excellent physical and mechanical properties
And chemical stability, in each fields such as chemical materials, mechano-electronic, Aero-Space, military project protection, new material and new energy all
Have a wide range of applications.After high molecular weight polytetrafluoroethyldispersions dispersion resin and lubricating oil blending, extruded, extruded using pasty state,
De-oiling, then by uniaxial or biaxial stretching, finally shape, the expanded polytetrafluoroethylsealing material with micro-porous permeable can be obtained, by
In its property, the material turns into 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, medicine equipment, electronic material and sealed insulating material etc..
Expanded polytetrafluoroethylsealing is fluorine-containing microcellular polymeric material, with height microcellular structure, there is excellent physical chemistry
Performance, mechanical performance, water-proof breathable properties and chemical stability, just be used to since the seventies manufacture wire cable insulating material
Material, medicine equipment, sealing material, environmental protection filtering and garment material etc..It is industrial generally using high-purity (>99.99%) tetrafluoro
Vinyl monomer, is polymerize by dispersion polymerization processes or copolymerization prepares dispersion resin.Prepare used in expanded polytetrafluoroethylsealing
Material be usually, with the tetrafluoroethene homopolymerization of super high molecular weight high-crystallinity is scattered or modified resin, to be squeezed typically by pasty state
Pressure, extrusion, de-oiling, then uniaxial or biaxial stretching, finally shape, and expanded fluorine-containing microporous membrane material is made, but such a microporous barrier holds
Its water proofing property is easily lost by oily pollution, lubricating oil used is inflammable and explosive in degreasing process in addition, easily causes industrial peace
Full hidden danger.W. L. Gore ＆ Associates, Inc. company discloses invention in the eighties and coats the poly- ammonia of hydrophilic in the one side of expanded 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 expanded polytetrafluoroethylsealing film, its air permeable is not sacrificed to improve its resistance to greasy dirt function
Function.But such production technique is excessively loaded down with trivial details, its water-proof breathable properties also needs to be lifted again, is especially applied to space flight
During navigation, its performance still has room for improvement.
CN1373792A (publication date：2002-10-9) disclose it is a kind of by average grain diameter be 20~150 nanometers of fluorine tree
Fat corpuscle emulsion and elastomer particle emulsion coagulate obtained transparent elastic composition altogether, and wherein particulate fluorocarbon resin is by homogeneous micro-
Be dispersed among elastomer, due to particulate fluorocarbon resin in advance by homogeneous differential dissipate in the elastomer, so can provide mechanical strength,
The excellent elastomer formed products such as wear resistance and the transparency, but such elastic composition because fluororesin particle diameter it is too small,
Molecular weight is not high enough, it is impossible to expanded that fluorine-containing microporous membrane is made.The enough high expanded fluorine-containing poromerics of intensity, polytetrafluoro is made
The molecular weight of ethene must be enough high, and the standard specific gravity of general resin must be between 2.14~2.17, and average grain diameter must be 180
Between~360 nanometers.
CN104437126A (publication date：2015-03-25) disclose 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) disclose a kind of double
Refuse microporous teflon membran.Two technical schemes are similar, are all that disclosure uses polytetrafluoroethylene (PTFE), super-hydrophobicity polyphosphazene polymer
Compound (number-average molecular weight 5000-250000) such as contains fluoroalkyl, and batch mixing goes system to inflammable and explosive lubricating oil together
Film, the film stretching low intensity of gained<20MPa, oil resistivity is low (only resistance to No. 3 oil), anti-soil, the water-wash resistance of its composite membrane fabric
Difference.
CN103158310A (publication date：2013-06-19) disclosing a kind of height, to refuse oily waterproof stitchless polytetrafluoroethylbulked bulked
Sheet material and preparation method thereof, open to use polytetrafluoroethylene (PTFE) and inflammable and explosive lubricating oil film, rear addition polymerization urethane resinous coat
Compound, the film of gained does not have gas permeability, and without oleophobic property (only resistance to No. 1 oil), its composite material penetrability is poor, wears uncomfortable.
CN104760381A (publication date：2015-07-08) disclose 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, the film gas permeability of gained is not high, and without oleophobic property (only resistance to No. 1 oil), anti-flammability is bad, is not suitable for high-end applications.
The content of the invention
In view of the shortcomings of the prior art, the present invention is intended to provide a kind of preparation method of fluorine-containing superoleophobic microporous barrier, with special
The fluorine-containing compound of door research and development is raw material, and without adding, inflammable and explosive lubricating oil, safe, and obtain it is fluorine-containing super
Oleophobic microporous film has higher waterproof, ventilative, resistance to greasy dirt, wash durability, the need for meeting waterproof and breathable protective garment of new generation
Ask.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of preparation method of fluorine-containing superoleophobic microporous barrier comprises the following steps：
S1 uniform stirrings by the way of without shearing by fluorine-containing compound, it is not necessary to add lubricating oil, directly pour into pressure embryo
In post bucket, embryo is pushed at 20 DEG C~100 DEG C after exhaust, the pasty mixture blastostyle of cylinder is made；
S2 is extruded pasty mixture blastostyle extruding by pushing machine at 20 DEG C~100 DEG C, is then rolled into bar
Band；
The band is done uniaxial or biaxial stretching by S3 at 100 DEG C~200 DEG C, finally hot at 200 DEG C~390 DEG C
Sizing, produces fluorine-containing superoleophobic microporous barrier；
The fluorine-containing compound includes following component by weight percentage：Component A 50%~90%, B component 3%~
25%, component C 0%~35%, D components 0%~3%；Wherein, component A includes high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymerization
Thing dispersion resin；B component includes one or more containing fluoroalkyl acrylate monomer；Component C includes one or more free-florides third
Olefin(e) acid ester；D components include high temperature radical initiator.
Further, in step S1, being added in fluorine-containing compound includes one kind in activated carbon powder, graphite, inorganic matter
Or it is several add materials, fluorine-containing compound and the mixed proportion that adds materials are weight ratio 1:0.1~1.0.Further,
The inorganic matter is titanium dioxide or silica.
Further, the fluorine-containing compound by component A, B component, component C and D components by being sequentially added into mixing
It is obtained by mixing by without shearing.
Further, the standard specific gravity of the component A is 2.13~2.18.
Further, the molecular weight of the B component<3000, fusing point is below 80 DEG C.
Further, the molecular weight of the component C<8000, fusing point is below 80 DEG C.
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 propylenes acid esters, N- methyl perfluoro butyl sulfonic acid amine ethyl-methyls
Acrylate, N- methyl perfluoro hexyl sulfanilic acid ethyl propylenes acid esters, N- methyl perfluoro hexyl sulfanilic acid ethyl methacrylates
Ester, N- methyl perfluoro octyl sulfonic acid amine ethyl propylenes acid esters, the one of N- methyl perfluoro octyl sulfonic acid amine ethylmethyl acrylates
Plant or several.
Further, the high temperature radical initiator includes cumyl peroxide (CAS：80-43-3), 2,5- bis-
- 2,5- couples-(t-butyl peroxy) hexane (CAS of methyl：78-63-7), di-t-butyl peroxide (CAS：110-05-4), 2,5- bis-
Double (the tert-butyl peroxide) -3- hexins (CAS of methyl -2,5-：1068-27-5), cumyl hydroperoxide (CAS：80-15-9)
In one or more.
Further, the component C is or the polyurethane acrylate prepolymer and without fluoroalkyl without fluoroalkyl
The mixture of acrylate.
The beneficial effects of the present invention are：It is inflammable and explosive without adding using the fluorine-containing compound specially researched and developed as raw material
Lubricating oil, it is to avoid the danger for causing detonation to explode during de-oiling, it is safe, and obtained fluorine-containing superoleophobic microporous barrier has
Higher waterproof, ventilative, resistance to greasy dirt, wash durability, the demand for meeting waterproof and breathable protective garment of new generation.
Embodiment
The invention will be further described below, it is necessary to which explanation, following examples are using the technical program before
Carry, give detailed embodiment and specific operating process, but the scope of the present invention is not limited to the present embodiment.
A kind of preparation method of fluorine-containing superoleophobic microporous barrier comprises the following steps：
S1 uniform stirrings by the way of without shearing by fluorine-containing compound, it is not necessary to add lubricating oil, directly pour into pressure embryo
In post bucket, embryo is pushed at 20 DEG C~100 DEG C after exhaust, the pasty mixture blastostyle of cylinder is made；
S2 is extruded pasty mixture blastostyle extruding by pushing machine at 20 DEG C~100 DEG C, is then rolled into bar
Band；
The band is done uniaxial or biaxial stretching by S3 at 100 DEG C~200 DEG C, finally hot at 200 DEG C~390 DEG C
Sizing, produces fluorine-containing superoleophobic microporous barrier；
The fluorine-containing compound includes following component by weight percentage：Component A 50%~90%, B component 3%~
25%, component C 0%~35%, D components 0%~3%；Wherein, component A includes high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymerization
Thing dispersion resin；B component includes one or more containing fluoroalkyl acrylate monomer；Component C includes one or more free-florides third
Olefin(e) acid ester；D components include high temperature radical initiator.
Further, in step S1, being added in fluorine-containing compound includes one kind in activated carbon powder, graphite, inorganic matter
Or it is several add materials, fluorine-containing compound and the mixed proportion that adds materials are weight ratio 1:0.1~1.0.Further,
The inorganic matter is titanium dioxide or silica.
Further, the fluorine-containing compound by component A, B component, component C and D components by being sequentially added into mixing
It is obtained by mixing by without shearing.
Further, the standard specific gravity of the component A is 2.13~2.18.
Further, the molecular weight of the B component<3000, fusing point is below 80 DEG C.
Further, the molecular weight of the component C<8000, fusing point is below 80 DEG C.
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 group 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
C2H4NCH3SO2C8F17】, or and other fluorine-containing alkyl (from C5~C16) acrylate or methacrylate.
Further, the high temperature radical initiator includes cumyl peroxide (CAS：80-43-3), 2,5- bis-
- 2,5- couples-(t-butyl peroxy) hexane (CAS of methyl：78-63-7), di-t-butyl peroxide (CAS：110-05-4), 2,5- bis-
Double (the tert-butyl peroxide) -3- hexins (CAS of methyl -2,5-：1068-27-5), cumyl hydroperoxide (CAS：80-15-9)
In one or more.High temperature radical initiator is organic free machine initiator, its half-life period between 100~250 degree, half
The phase definition that declines refers under some specified temp after 10 hours that the effective ingredient that free machine initiator at least also possesses half can be produced
Raw free radical.
The high molecular weight polytetrafluoroethyldispersions homopolymerization of component A or the manufacture method of copolymer dispersion resin have in many documents
Record, 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, 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 be with tetrafluoroethene copolymerization comonomer；Pressure is reached after 11~29 kilograms in kettle, is added free radical and is drawn
Agent is sent out, starts polymerisation, 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 less than 50 DEG C, stop stirring, HMW polytetrafluoro is made in unreacted monomer discharge, reactant discharging
Ethylene homo or copolymerization dispersion resin emulsion, about 180~390 nanometers of the average grain diameter of its primary particle, primary particle preferably
About 220~330 nanometers of average grain diameter.
Wherein, the purity>99.999% tetrafluoroethene and optional other comonomers, its moderate purity>
It is 95%~99.99% that 99.999% tetrafluoroethene accounts for monomer total amount percent by volume in reactor；And can be with tetrafluoro second
The comonomer of alkene copolymerization, selected from perfluoro methyl vinyl ether, perfluoroethylvinyl ether, perfluoro propyl vinyl ether, partially
Any one monomer in PVF, PVF, 3,3,3- trifluoro propylenes, perfluoro alkyl ethylene etc. (C2~C8 alkyl) exceedes
A kind of combination more than monomer.It is preferred that the high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer dispersion resin are superelevation point
Son amount polytetrafluoroethyl-ne polyamino alkenyl or copolymer dispersion resin, its 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.It is preferred that, surfactant is perfluorinated surfactant.The radical initiator choosing
From any one in persulfate, hydrogen peroxide or organic peroxide or its combination.In polymerization process, pressure in kettle
Maintained at least at more than 15 kilograms.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, drying and obtain.
In the present embodiment, component C is or the polyurethane acrylate prepolymer and without fluoroalkyl without fluoroalkyl
The mixture of acrylate, molecular weight<8000, molecular weight preferably<5000, its fusing point is below 80 DEG C, preferably its fusing point
Below 50 DEG C.
The polyurethane acrylate prepolymer can be prepared using following preparation method：By the row of vacuumizing in reactor
Moisture, adds diisocyanate, and heats up, and opens stirring；Temperature in the kettle is risen to about 50~150 DEG C, it is then many toward being passed through in kettle
First alcohol (containing PPG or PEPA), the total yield mol ratio of two of which main material is, diisocyanate (- NCO
Isocyanate equivalent)：Polyalcohol (- OH hydroxyl equivalents)=2：1~8：1, kettle interior reaction temperature should be maintained 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, plus
The equivalents of the hydroxyalkyl acrylates entered is more than or equal to unreacted isocyanate equivalent number, and (hydroxyl and isocyanates are worked as
Measure number ratio about 2：1~1：1), remaining unreacted isocyanates is completely reacted to as polyurethane acrylate prepolymer by hydroxyalkyl
Aggressiveness, after stirring is mixed, kettle interior reaction temperature is maintained about at 50~150 DEG C, is reacted about 10~180 minutes, cooling discharge, i.e.,
Polyurethane acrylate prepolymer can be obtained.
When the composition of component C calculates the polyurethane acrylate prepolymer for 0%~70% by weight percentage；30%~
100% without fluoroalkyl.
The polyurethane acrylate prepolymer is hot melt, and its fusing point is below 80 DEG C, and its fusing point preferably 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, PEPA, polycarbonate polyol etc., point of all polyalcohols
Son amount is between 600~5000, between preferably 1000~3000, and each molecule is containing 2~3 hydroxyls.
The mean molecule quantity without fluoroalkyl is less than 1000, and its mean molecule quantity preferably is less than 600, its
Fusing point below 80 DEG C, its fusing point preferably below 50 DEG C, atmospheric boiling point more than 160 degree, including hydroxyalkyl acrylates,
Hydroxyalkyl methacrylates, C5~C20 alkyl acrylates, C4~C20 alkylmethacrylates, and the sour second of C6~C20
The one or more of alkene ester；Wherein in hydroxyalkyl acrylates, hydroxyalkyl methacrylates, including hydroxy-ethyl acrylate, first
Base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate.Further, preferably, described without 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 more than 200 degree
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 alkyl acrylates containing C6~C18, and other are containing C6~C18 alkyl methyls third
The one or more of olefin(e) acid ester.
About 0.005~1.5 millimeter, preferably from about 0.01~0.08 millimeter of the thickness of the fluorine-containing superoleophobic micropore membrane material；
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 surveys 100 milliliters of air permeable speed of method and is 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 meter) or pin
Weave cotton cloth or non-woven fabrics, be combined film with cloth through point-like glue, this composite material, water pressure resistance is initially greater than 100kPa；Through water
Wash after 10 times, water pressure resistance is still greater than 60kPa；100 milliliters of air permeable speed of composite material gas permeability Gurley survey methods about 6~
90 seconds；The sealing effectiveness that sealing rod is pasted at thread is good, meets application requirement.It is saturating that other all properties indexs all meet waterproof
Gas garment material standard, testing standard is as shown in table 1.
Table 1
In summary, it is inflammable without adding when preparing fluorine-containing superoleophobic microporous barrier by raw material of the fluorine-containing compound
Explosive lubricating oil, its processing technology is safe, added in the homopolymerization of macromolecule tetrafluoroethene or copolymerization dispersion resin to help
Free redical polymerization turns into a part for high molecule micropore film at high temperature for agent, is asked without the industry security caused by the three wastes
Topic.The waterproof of obtained fluorine-containing superoleophobic microporous barrier, oil resistant, antifouling property are significantly improved, can meet the higher hydraulic pressure of resistance and
Poisonous and harmful liquid is prevented to invade the important need of human body, and ventilative and penetrability is higher, sealing effectiveness is good at thread
Application requirement.When being applied to protective garment composite material, with light, comfortable, ventilative, waterproof and anti-poisonous and harmful
The permanent protective property energy of liquid, after being combined with fabric point patch, can provide permanent protective property, comfortableness, warmth retention property, gas permeability etc. to wearer
Multiple demand.
The preparation of the high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin of embodiment 1
In the horizontal high-pressure reactor 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, vacuumizing deoxygenation in kettle (until oxygen content<
20ppm), and heat up, open stirring；When temperature in the kettle rises to about 70 DEG C, toward kettle in be passed through purity ＞ 99.999% tetrafluoroethene
Gas, makes pressure in kettle reach about 22 kilograms.Then 300 grams of purity ＞ 98% perfluoroethylvinyl ether (C2F5- OCF=
CF2) as comonomer, it is initially added into 10 grams per minute of speed in kettle, while adding 0.8 gram of ammonium persulfate (thing in kettle
It is first dissolved in 500 milliliters of water) as initiator, started copolymer reaction, temperature in the kettle maintains 80~100 DEG C, in course of reaction
Being passed through tetrafluoroethylene gas makes pressure in kettle maintain about 20 kilograms.Sustained response reaches about 30% to emulsion solid content, by kettle
Interior temperature is down to after less than 50 degree, stops stirring, and unreacted monomer discharge, decompression, reactant blowing obtains super high molecular weight and gathered
Tetrafluoroethene copolymerization dispersion resin emulsion, about 280 nanometers of the average grain diameter of its primary particle.Emulsion is after dilution, high-speed stirred
Flocculate and break emulsion, by suspension polymer sabot, is put into 190 degree of drying of high temperature oven, produces high molecular weight polytetrafluoroethyldispersions copolymerization point
Dissipate resin.After testing, the standard specific gravity of tetrafluoroethene copolymerization dispersion resin, about 2.149, fusing point peak 325~350 DEG C it
Between.
The preparation of the polyurethane acrylate prepolymer of embodiment 2
In the reactor of about 200 liters of internal volumes, chuck is first to heat to 100 DEG C, is vacuumized 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, stirring is opened,
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), react after about 90 points, add temperature in 18.2 kilograms of (containing about 140 More-OH hydroxyls) hydroxyethyl methacrylates, kettle
Degree maintains about 100 DEG C, and the polyurethane acrylate prepolymer with viscous liquid, cooling is just made in reaction after about one hour
It is afterwards liquid at 50 DEG C, illustrates that fusing point is less than 50 DEG C.
The preparation of the polyurethane acrylate prepolymer of embodiment 3 and the mixture without fluoroalkyl
(3A) polyurethane acrylate prepolymer and without fluoroalkyl weight ratio be 3：When 7：At one about 100
The polyurethane acrylate prepolymer that 15 kilograms of embodiment 2 is obtained is added in the agitator for rising internal volume, under normal temperature and pressure, so
35 kilograms of isodecyl acrylate (CAS is added afterwards：1330-61-6), continuously stir into homogeneous, stop stirring, mixture puts
Material, obtains polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
(3B) polyurethane acrylate prepolymer and without fluoroalkyl weight ratio be 5：When 5：At one about 100
The polyurethane acrylate prepolymer that 25 kilograms of embodiment 2 is made is added in the agitator for rising internal volume, under normal temperature and pressure, so
25 kilograms of isodecyl acrylate (CAS is added afterwards：1330-61-6), continuously stir into homogeneous, stop stirring, mixture puts
Material, obtains polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
The preparation of the fluorine-containing compound of embodiment 4
Scheme 1：The component A high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin that embodiment 1 is obtained, B component is two kinds
Or more perfluor alkyl ethyl acrylate mixture (mean molecule quantity<1000, fusing point is less than 35 DEG C, perfluoroalkyl
Distribution is about C4：10%, C6；30%, C8；50%, C10：And scheme 3A is obtained in embodiment 3 component C polyurethane 10%)
Acrylate prepolymer body and the mixture without fluoroalkyl, and D component high temperature radical initiator hydrogen peroxide isopropyls
Benzene (CAS：80-15-9) with (A:B:C:D)=(70：10：19：1) weight ratio, is blended about using gentle without shearing method
Half an hour, obtain fluoro containing polymerses opaque white color compound, as fluorine-containing compound.The standard specific gravity of the fluorine-containing compound
About 1.89g/cm3.
Scheme 2：By the component A high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin of embodiment 1, B component be two kinds or with
On perfluor alkyl ethyl acrylate mixture (mean molecule quantity<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 hydroperoxides (CAS 30%)：80-
15-9) with (A:B:C:D)=(80：19：0：1) weight ratio, using gentle without shearing method blending about half an hour, is obtained
To the white compound of extraordinary fluoro containing polymerses.The standard specific gravity of the extraordinary fluoro containing polymerses compound is about 2.03g/cm3.
Scheme 3：It is two kinds or more complete by the component A high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin of embodiment 1
Mixture (the mean molecule quantity of fluoroalkyl ethyl propylene acid esters<1000, fusing point is less than 35 DEG C, and the distribution of perfluoroalkyl is about C4：
10%, C6；30%, C8；50%, C10：And scheme 3B is obtained in embodiment 3 component C polyurethane acrylate prepolymer 10%)
Aggressiveness and the mixture without fluoroalkyl, and D component high temperature radical initiator cumyl hydroperoxides (CAS：80-
15-9) with (A:B:C:D)=(65：11：23：1) weight ratio, using gentle without shearing method blending about half an hour, is obtained
To fluoro containing polymerses opaque white color compound, i.e., described fluorine-containing compound.The standard specific gravity of the fluorine-containing compound is about
1.85g/cm3。
Scheme 4：By the component A high molecular weight polytetrafluoroethyldispersions copolymerization dispersion resin of embodiment 1, B component be two kinds or with
On perfluor alkyl ethyl acrylate mixture (mean molecule quantity<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 components high temperature from
By base initiator cumyl hydroperoxide (CAS：80-15-9) with (A:B:C:D)=(78： 10：11：1) weight ratio, is used
It is gentle to obtain extraordinary fluoro containing polymerses opaque white color compound without shearing method blending about half an hour, i.e., it is described fluorine-containing
Compound.The standard specific gravity of the extraordinary fluoro containing polymerses compound is about 1.98g/cm3。
The manufacture of the fluorine-containing microporous membrane of embodiment 5 and its composite material
After the fluorine-containing compound 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 bar-shaped, then press
Prolong into band, about 0.45 millimeter of thickness, about 180 millimeters of width.The quick drawing in longitudinal direction under about 130 DEG C of temperature conditionss by the band
About 4 times are stretched, then quick about 12 times of the cross directional stretch under about 180 DEG C of hot conditions again, finally in about 370 DEG C of hot conditions
Lower setting, about 11 seconds, that is, obtains fluorine-containing superoleophobic microporous membrane.
After testing, about 0.036 millimeter of the 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.
, will through point-like polyurethane laminating glue point by the fluorine-containing superoleophobic microporous membrane and the flat fabric of nylon 6 (96 grams per square meter)
Film and cloth are combined, and this composite material, water pressure resistance is initially greater than 200kPa, after washing 10 times, water pressure resistance 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 100 milliliters of air permeable speed of method about 15~20 seconds；The sealing effectiveness that sealing rod is pasted at thread is good, meets
Application requirement.Other all properties indexs all meet waterproof breathable garment fabric standard, and testing standard is as shown in table 1.
The manufacture of embodiment 6 fluorine-containing superoleophobic microporous membrane and its composite material
The fluorine-containing compound that scheme 2 in embodiment 4 is obtained is used without the first precompressed at 70 DEG C after shearing stir
Into columned paste mixture, at about 70 DEG C by pushing machine by the paste mixture carry out be squeezed into it is bar-shaped, then
It is rolled into band, about 0.45 millimeter of thickness, about 180 millimeters of width.By the band, longitudinal direction is quick under about 140 DEG C of temperature conditionss
About 4 times of stretching, then quick about 12 times of the cross directional stretch under about 190 DEG C of hot conditions again, finally in about 370 DEG C of high temperature bar
Shaped under part, about 11 seconds, that is, obtain fluorine-containing superoleophobic microporous membrane.
After testing, 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.
, will through point-like polyurethane laminating glue point by the fluorine-containing superoleophobic microporous membrane and the flat fabric of nylon 6 (96 grams per square meter)
Film and cloth are combined, and this composite material, water pressure resistance is initially greater than 200kPa, after washing 10 times, water pressure resistance 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 100 milliliters of air permeable speed of method about 13~17 seconds；The sealing effectiveness that sealing rod is pasted at thread is good, meets
Application requirement.Other all properties indexs all meet waterproof breathable garment fabric standard, and testing standard is as shown in foregoing table 1.
The manufacture of embodiment 7 fluorine-containing superoleophobic microporous membrane and its composite material
The fluorine-containing compound that scheme 3 in embodiment 4 is obtained is pressed into circle in advance without first after shearing stir at 70 DEG C
The paste mixture of column, then at about 70 DEG C by pushing machine the paste mixture be squeezed into bar-shaped, then roll
Into band, about 0.45 millimeter of thickness, about 180 millimeters of width.By the band under about 130 DEG C of temperature conditionss longitudinal Rapid stretching
About 4 times, then quick about 12 times of the cross directional stretch under about 190 DEG C of hot conditions again, finally in about 370 DEG C of hot conditions
Lower sizing shape 11 seconds, that is, obtain fluorine-containing superoleophobic microporous membrane.
After testing, 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 surveys 100 milliliters of air permeable speed of method about 13~16 seconds.
By fluorine-containing superoleophobic microporous membrane and the flat fabric of nylon 6 (96 grams per square meter), fitting glue point through point-like polyurethane will be thin
Film is combined with cloth, and this composite material, water pressure resistance is initially greater than 200 kPa, 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 5 grades；Film stretching intensity>20MPa, composite material
Gas permeability Gurley surveys 100 milliliters of air permeable speed of method about 19~23 seconds；The sealing effectiveness that sealing rod is pasted at thread is good,
Meet application requirement.Other all properties indexs all meet waterproof breathable garment fabric standard, and testing standard list is in rear.
The manufacture of embodiment 8 fluorine-containing superoleophobic microporous membrane and its composite material
Obtained fluorine-containing compound will be manufactured in the scheme 4 of embodiment 4 without first at about 70 DEG C after shearing stir
It is pressed into columned paste mixture in advance, then by pushing machine carries out the paste mixture at about 70 DEG C being squeezed into rod
Shape, then it is rolled into band, about 0.45 millimeter of thickness, about 180 millimeters of width.The band is indulged under about 140 DEG C of temperature conditionss
To about 4 times of Rapid stretching, then quick about 12 times of the cross directional stretch under about 190 DEG C of hot conditions again, finally at about 370 DEG C
Shape of being shaped under hot conditions 12 seconds, that is, obtain fluorine-containing superoleophobic microporous membrane.
After testing, 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.
, will through point-like polyurethane laminating glue point by the fluorine-containing superoleophobic microporous membrane and the flat fabric of nylon 6 (96 grams per square meter)
Film and cloth are combined, and this composite material, water pressure resistance is initially greater than 200kPa, after washing 10 times, water pressure resistance 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 100 milliliters of air permeable speed of method about 10~13 seconds；The sealing effectiveness that sealing rod is pasted at thread is good, meets
Application requirement.Other all properties indexs all meet waterproof breathable garment fabric standard, and testing standard is as shown in foregoing table 1.
The preparation of fluorine-containing superoleophobic microporous membrane and its composite material of the embodiment 9 containing activated carbon
Fluorine-containing compound that the scheme 2 of embodiment 4 is obtained and decyl acrylate (component C) and activated carbon micro mist with
About 7：1：Then 2 weight ratio is first pressed into columned paste mixture in advance without shearing mixing at about 70 DEG C, then about 70
By pushing machine the paste mixture be squeezed into bar-shaped at DEG C, then roll and become band, about 0.9 millimeter of thickness, width
About 180 millimeters.By the dry band under about 140 DEG C of hot conditions longitudinal about 8 times of Rapid stretching, then again in about 190 DEG C of height
Horizontal about 12 times of Rapid stretching under the conditions of temperature, shape of finally being shaped under about 370 DEG C of hot conditions 16 seconds obtains grey fluorine-containing
Superoleophobic microporous membrane.In the present embodiment, the effect for adding component C is mainly and avoids directly adding activated carbon micro mist to occur
Viscosity it is too high, mix it is less uniform the problem of.
After testing, 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 surveys 100 milliliters of air permeable speed of method about 5~7 seconds.
, will through point-like polyurethane laminating glue point by fluorine-containing superoleophobic microporous membrane and the flat fabric (150 grams per square meter) containing silk floss
Film is combined with cloth, and this composite material, water pressure resistance is initially greater than 100 kPa, 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 of air permeable speed about 9~13 seconds；The sealing effectiveness that sealing rod is pasted at thread is good, meets application requirement.Containing work
Property charcoal fluorine-containing superoleophobic microporous membrane have resistance 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 foregoing table 1.
The manufacture of extraordinary fluorine-containing the varicosity film and its composite material of the graphitiferous of embodiment 10
The fluorine-containing compound that scheme 2 in embodiment 4 is obtained is with different 13 ester (component C) of acrylic acid and graphite microparticles with about
8：1：Then 1 weight ratio is first pressed into columned paste mixture in advance without shearing mixing at about 70 DEG C, then about 70
By pushing machine the paste mixture be squeezed into bar-shaped at DEG C, then roll and become band, about 0.45 millimeter of thickness, width
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 height
Horizontal about 12 times of Rapid stretching under the conditions of temperature, shape of finally being shaped under about 370 DEG C of hot conditions 13 seconds obtains grey fluorine-containing
Superoleophobic microporous membrane.In the present embodiment, the effect for adding component C is mainly and avoids directly adding activated carbon micro mist to occur
Viscosity it is too high, mix it is less uniform the problem of.
After testing, 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.
By fluorine-containing superoleophobic microporous membrane and terylene flat fabric (70 grams per square meter), fitting glue point through point-like polyurethane will be thin
Film is combined with cloth, and 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 effectiveness that sealing rod is pasted at thread is good, meets application requirement.Containing activity
The fluorine-containing superoleophobic microporous membrane of charcoal has the ability for removing electrostatic, and other all properties indexs all meet industrial protection garment material
Standard, testing standard is as shown in foregoing table 1.
Comparative example 1 (without special blend is dosed)
The polytetrafluoroethyldispersion dispersion resin powder for being about 2.156 by standard specific gravity (derives from Japan great Jing companies, resin grade
106) with Mobil senior lubricants (trade mark Isopar M) with about 4：1 weight is first pressed into cylinder in advance than mixing after stirring
The paste mixture of shape, then at about 70 DEG C by pushing machine the paste mixture be squeezed into bar-shaped, then it is rolled into
Banding, 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, by this
Dry band about 6 times of longitudinal stretching under about 250 DEG C of hot conditions, then cross directional stretch is about under about 300 DEG C of hot conditions again
12 times, shape of finally being shaped under about 370 DEG C of hot conditions 18 seconds obtains expanding microporous fluorine film.
After testing, 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 the flat fabric of nylon 6 (96 grams per square meter), glue point is fitted by film and cloth through point-like polyurethane
Compound, this composite material, initial water pressure resistance is more than 200kPa, after washing 10 times, and water pressure resistance is less than 10kPa；Film surface oil resistivity
It 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 of air permeable speed about 17~22 seconds；The sealing effectiveness that sealing rod is pasted at thread is bad, it is impossible to which meeting application will
Ask.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, be not added with containing fluoroalkyl) according to CN103158310A
The polytetrafluoroethyldispersion dispersion resin powder for being about 2.156 by standard specific gravity (derives from Japan great Jing companies, resin grade
106) the first polyurethane acrylate prepolymer with obtained by scheme 3A in embodiment 3 and the mixing without fluoroalkyl
Thing, 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, first columned paste mixture is pressed into advance after stirring, then by pushing machine by the paste at about 70 DEG C
Mixture be squeezed into bar-shaped, then rolls and becomes band, 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, most
Shape of being shaped afterwards under about 370 DEG C of hot conditions 11 seconds, that is, obtain fluorine-containing microporous membrane.
After testing, 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 the flat fabric of nylon 6 (96 grams per square meter), through point-like polyurethane fit glue point by film with
Cloth is combined, this composite material, and water pressure resistance is initially less than 150kPa, after washing 10 times, and 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 of air permeable speed about 12~17 seconds；The sealing effectiveness that sealing rod is pasted at thread is bad, it is impossible to which meeting application will
Ask.Such membrane material does not meet waterproof breathable garment fabric standard, and testing standard list is in rear.
Comparative example 3 (is mixed into polymer containing fluoroalkyl, number-average molecular weight according to CN102294181A>
10000)
Method according to CN102294181A embodiments two prepares fluorine-containing microporous membrane and (containing inflammable and explosive solvent, gathered
Compound contains fluoroalkyl, number-average molecular weight>10000), after testing, the milli of thickness about 0.020 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 the flat fabric of nylon 6 (96 grams per square meter), glue point is fitted by film and cloth through point-like polyurethane
Compound, this composite material, water pressure resistance is initially less than 150 kPa, after washing 10 times, and water pressure resistance is less than 50kPa；Film surface oil resistivity
It 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 effectiveness that sealing rod is pasted at thread is bad, it is impossible to meet application requirement.This
The membrane material of sample does not meet waterproof breathable garment fabric standard, and all testing standards are as shown in foregoing table 1.
Summary embodiment and comparative example can be drawn the following conclusions：Fluorine-containing compound using the present invention is raw material system
Standby fluorine-containing superoleophobic microporous barrier, without adding inflammable and explosive lubricating oil, directly can be extruded by pasty state, be pressed into band, unidirectionally or
The more excellent fluorine-containing superoleophobic microporous membrane of safeguard function can be then made in biaxial tension, sizing.Its processing technology is safe, nothing
Three wastes problem, the water proofing property of film product, oil resistivity, water-wash resistance, pollution resistance are higher, and the extraordinary fluorine-containing microporous membrane can be resisted
High hydraulic pressure, and poisonous and harmful liquid intrusion human body is prevented, its air permeable and moisture vapor permeability are excellent, good sealing effect at thread,
The requirement of application needed for meeting.When applied to protective garment is made, penetrated with high anti-hydraulic pressure and anti-poisonous and harmful liquid
Protective function, have light, comfortable, warming, gas permeability concurrently, the fight protection of wearer can be greatly promoted.
For those skilled in the art, technical scheme that can be more than and design, provide various corresponding
Change and deform, and all these change and deform, and should be construed as being included within the protection domain of the claims in the present invention.
Claims (10)
1. a kind of preparation method of fluorine-containing superoleophobic microporous barrier, it is characterised in that comprise the following steps：
S1 uniform stirrings by the way of without shearing by fluorine-containing compound, it is not necessary to add lubricating oil, directly pour into pressure blastostyle bucket
It is interior, embryo is pushed at 20 DEG C~100 DEG C after exhaust, the pasty mixture blastostyle of cylinder is made；
S2 is extruded pasty mixture blastostyle extruding by pushing machine at 20 DEG C~100 DEG C, is then rolled into band；
The band is done uniaxial or biaxial stretching by S3 at 100 DEG C~200 DEG C, finally the thermal finalization at 200 DEG C~390 DEG C,
Produce fluorine-containing superoleophobic microporous barrier；
The fluorine-containing compound includes following component by weight percentage：Component A 50%~90%, B component 3%~25%, C
Component 0%~35%, D components 0%~3%；Wherein, component A includes high molecular weight polytetrafluoroethyldispersions homopolymerization or copolymer is scattered
Resin；B component includes one or more containing fluoroalkyl acrylate monomer；Component C includes one or more without fluorinated monomer；
D components include high temperature radical initiator.
2. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that in step S1, containing
Include in activated carbon powder, graphite, inorganic matter one or more of are added in fluorine compound to add materials, fluorine-containing compound with add
Plus the mixed proportion of material is that weight compares 1:0.1~1.0.
3. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 2, it is characterised in that the inorganic matter is two
Titanium oxide or silica.
4. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that the fluorine-containing compound
By the way that component A, B component, component C and D components are sequentially added into after mixing through being obtained by mixing without shearing.
5. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that the mark of the component A
Quasi- proportion is 2.13~2.18.
6. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that point of the B component
Son amount<3000, fusing point is below 80 DEG C.
7. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that point of the component C
Son amount<8000, fusing point is below 80 DEG C.
8. the preparation method of the fluorine-containing superoleophobic microporous barrier according to claim 1 or 6, it is characterised in that the B component bag
Include perfluoro butyl ethyl propylene acid esters, perfluoro butyl ethylmethyl acrylate, perfluoro hexyl ethyl propylene acid esters, perfluoro hexyl
Ethylmethyl acrylate, perfluorooctylethyl group acrylate, perfluorooctylethyl group methacrylate, N- methyl perfluoro butyl
Sulfanilic acid ethyl propylene acid esters, N- methyl perfluoro butyl sulfonic acid amine ethylmethyl acrylate, N- methyl perfluoro hexyl sulfanilic acids
Ethyl propylene acid esters, N- methyl perfluoro hexyl sulfanilic acids ethylmethyl acrylate, N- methyl perfluoro octyl sulfonic acid amine ethyl third
The one or more of olefin(e) acid ester, N- methyl perfluoro octyl sulfonic acid amine ethylmethyl acrylates.
9. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that the high temperature free radical
Initiator includes cumyl peroxide (CAS：80-43-3), 2,5- dimethyl -2,5- couples-(t-butyl peroxy) hexane (CAS：
78-63-7), di-t-butyl peroxide (CAS：110-05-4), double (tert-butyl peroxide) -3- hexins of 2,5- dimethyl -2,5-
(CAS：1068-27-5), cumyl hydroperoxide (CAS：One or more in 80-15-9).
10. the preparation method of fluorine-containing superoleophobic microporous barrier according to claim 1, it is characterised in that the component C is nothing
Fluoroalkyl, or polyurethane acrylate prepolymer and the mixture without fluoroalkyl.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710470817.9A CN107216431B (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of fluorine-containing superoleophobic microporous barrier |
| 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 |
| 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 |
| 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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| CN201710470817.9A CN107216431B (en) | 2017-06-20 | 2017-06-20 | A kind of preparation method of fluorine-containing superoleophobic microporous barrier |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018233346A1 (en) * | 2017-06-20 | 2018-12-27 | 浙江汉丞科技有限公司 | Fluorine-containing mixture material and fluorine-containing super-oleophobic microporous membrane using same as raw material, and preparation method therefor and use thereof |
| CN112920532A (en) * | 2021-02-07 | 2021-06-08 | 浙江汉丞科技有限公司 | High-moisture-permeability super-breathable microporous film and high-moisture-permeability super-breathable microporous film composite material |
| 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 |
| CN115819912A (en) * | 2022-10-12 | 2023-03-21 | 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018233346A1 (en) * | 2017-06-20 | 2018-12-27 | 浙江汉丞科技有限公司 | Fluorine-containing mixture material and fluorine-containing super-oleophobic microporous membrane using same as raw material, and preparation method therefor and use thereof |
| US11702494B2 (en) | 2017-06-20 | 2023-07-18 | Zhejiang Hyproof Technology Co., Ltd | Fluorine-containing mixture material and fluorine-containing super-oleophobic microporous membrane using same as raw material, and preparation method therefor and use thereof |
| CN112920532A (en) * | 2021-02-07 | 2021-06-08 | 浙江汉丞科技有限公司 | High-moisture-permeability super-breathable microporous film and high-moisture-permeability super-breathable microporous film composite material |
| 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 |
| WO2022166430A1 (en) * | 2021-02-07 | 2022-08-11 | 浙江汉丞科技有限公司 | Preparation method for high-moisture-permeability fluorine-containing super-oleophobic microporous membrane |
| CN115819912A (en) * | 2022-10-12 | 2023-03-21 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretched film and preparation method thereof |
| 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 |
| WO2024046494A1 (en) * | 2022-10-12 | 2024-03-07 | 嘉兴富瑞邦新材料科技有限公司 | Breathable polytetrafluoroethylene stretch film and preparation method therefor |
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