CN104788712B - A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof - Google Patents
A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof Download PDFInfo
- Publication number
- CN104788712B CN104788712B CN201510131019.4A CN201510131019A CN104788712B CN 104788712 B CN104788712 B CN 104788712B CN 201510131019 A CN201510131019 A CN 201510131019A CN 104788712 B CN104788712 B CN 104788712B
- Authority
- CN
- China
- Prior art keywords
- filling perforation
- polyurethane
- polymerization
- basement membrane
- moisture permeable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a kind of filling perforation polyurethane water-proof moisture permeable membrane, including basement membrane and filling perforation material, the quality of filling perforation material is the 5% ~ 85% of basement membrane and filling perforation material gross mass, and filling perforation material is that hydrophilic monomer and hydrophobic monomer are respectively through the in-situ cross-linked weight/mass percentage composition for polymerizeing hydrophilic monomer, hydrophobic monomer and crosslinking agent in the copolymerising hydrophilic macromolecule formed, described filling perforation material in the presence of crosslinking agent：Hydrophilic monomer：20%~90%；Crosslinking agent：1%~9%；Hydrophobic monomer：Surplus.The present invention discloses its preparation method.Filling perforation material of the present invention is greatly enhanced to the absorption of moisture and through ability；Adhesion between the filling perforation material and basement membrane is significantly improved；The structure of composite membrane has good comprehensive mechanical property.And the preparation process of waterproof humidity-permeant film, the process that especially filling perforation material is introduced into the micropore of basement membrane is quickly, simply, effectively.
Description
Technical field
The present invention relates to a kind of membrane material and preparation method thereof, more particularly to a kind of filling perforation polyurethane water-proof moisture permeable membrane and its
Preparation method and preparation method thereof, belongs to materialogy technical field.
Background technology
Waterproof moisture permeable fabric, is also Water-proof breathable fabric and " can breathe fabric ", is collection waterproof, moisture-inhibiting, windproof and warming
Performance, in the functional fabric of one, is one of high value added product for developing successively in recent years.Water-proof function requires fabric one
It is not spontaneously wet out by water or permeates under fixed hydraulic pressure, so as to resists infringement of the bad weathers such as sleet to human body.Moisture-inhibiting function is then
It is required that the sweat steam that human body is distributed can be spread by fabric or be transmitted to the external world, condensation is gathered not between body surface and fabric,
So as to prevent from wearing the phenomenon of stuffy and clammy sense, it is ensured that comfort.Waterproof moisture permeable fabric is produced as a kind of high added value fabric
Product, can be used as anorak, anorak, gym suit, immersion suit, industry cloth etc., quickly grow in recent years.
Waterproof moisture permeable fabric mainly includes following three kinds in the market：High density fabric, coated fabric and laminated fabric.
High density fabric utilizes the capillary suction of the gap hole produced during warp and weft interweaving and fiber to act on human body in work
Produced sweat gas is diffused out in vitro when dynamic, realizes waterproofing and moisture-penetration performances.Present highly dense type waterproof moisture permeating fabric is mostly ultra-fine
Polyester or nylon fabric.Ventile fabrics and the Sorela of Di Ren companies are exactly the Typical Representative of this kind fabric.It is highly dense to knit
Thing cost is of a relatively high, and process is also complex.
Compared with high density fabric, coated fabric and laminated fabric are the main product types of waterproof moisture permeable fabric.Coating is knitted
The essence of thing and laminated fabric is by macromolecule membrane and fabric side with Waterproof Breathable ability by coating and lamination
Material is compound, reaches Waterproof Breathable function.Waterproof Breathable macromolecule membrane is the core composition of this two classes product.It is saturating according to its waterproof
Moor reason mainly has two classes：Pore type film and dense form film.A large amount of diameters are distributed with above pore type film should be 2
Micropore between~20 microns.Due to surface tension effects, so small micropore can prevent the drop of water from passing through, and but allow water
Molecule in individual molecule form by (water vapour), it is achieved thereby that waterproof (liquid) moisture-inhibiting (gas) function.Its Typical Representative
Second generation Gore-tex products of such as Gore companies and the Thintech brands of Minnesota Mining and Manufacturing Company's production.Dense form film by
Hydrophilic macromolecule is constituted, and vapor is by adsorbing the physical actions such as a diffusion one desorption with hydrophilic radical effect through thin
Film, makes fabric have penetrability.Sympatex laminated fabrics, the U.S. Bao Litai of Typical Representative such as AkzoNobel companies of Holland
Qualitex multifunctional water-proofing moisture permeable fabricses of Internaional, Inc etc..
In the 1960s, high speed development and application and development with polyurethane industrial, people utilize polyurethane（PU）Tree
Fat is coated on various base materials, has prepared the imitative leather product of excellent performance.Synthetic Leather not only has and base material is bonded
Excellent performance, wear-resistant, the excellent mechanical performance such as flex endurant and cold resistance are good, easy to process, the advantages of cheap, are
Ideal natural leather substitute, is widely used in the fields such as clothes, shoemaking, automobile cushion.But polyurethane resin institute
The coating of formation it is naturally occurring the defect of permeability difference, this will greatly hinder the transmission of gas and vapor, reduction synthesis
The snugness of fit and sanitation performance of leather.In recent years, people improve the gas permeability of polyurethane material by various means, gradually shape
Into the polyurethane water-proof moisture-permeable shell fabric product for having waterproof and breathable function concurrently.
Waterproof ventilated membrane based on polyurethane can equally be divided into two major classes:Pore type film and dense form film.Shut out in the U.S.
Company of nation by it is molten cause phase in version (NIPS) process exploitation go out microporous polyurethane membrane material, its surface apertures in 0.5 microns,
Reach Waterproof Breathable function.Using the Entrant of the typical brand such as Dong Li companies of Japan of such product.Breast can also be passed through
Salt solution condensing method formation microporous polyurethane film, such as the Permutex of Britain Stahi (ICI)/NL companies.It is hydrophilic poly-
Urethane nonporous film is then main to be completed by the way that hydrophilic component is blended in polyurethane or hydrophilic segment etc. is introduced by copolymerization,
Also the more rapid aqueous polyurethane technology of latest developments is included.The typical products such as X-Liner of Britain Baxenden companies,
Bion II that Japanese east is spun etc., Excepor-U of Mitsubishi's chemical conversion etc..In addition, the DiaPlex products of Mitsubishi heavy industry are by shape
Shape memory polyurethane is made, its penetrability can variation with temperature and change.
The most critical issue that waterproof humidity-permeant film is realized is the unification of water proofing property and penetrability.And in the prior art, pore type
The greatest problem of macromolecule member material is that micropore can over time increase and block, and is remarkably decreased its penetrability.And dense form
The penetrability of macromolecule member material relies on its hydrophily.But there is problem in the application in the high high polymer material of hydrophily.It is first
First, the high macromolecule of hydrophily is generally polar molecule, and its glass transition temperature is high, and rigidity, fragility is easily presented, and is led in the application such as fabric
Domain can bring processing difficulties and reduction snugness of fit.Secondly, hydrophilic macromolecule is swelled after absorbing water, and mechanical property is
It is remarkably decreased, is easily caused structure destruction.Finally, it is hydrophilic to improve and be swelled after hydrophilic, it is meant that the decline of water proofing property.In order to
Ensure gas permeability, the thickness of usual dense form macromolecule member material can not be too big.This further reduces water proofing property and structure
Stability.
Concrete analysis is by taking polyurethane as an example, by the way that the hydrophily side that hydrophilic component improves polyurethane is blended in polyurethane
The problem of method is present is mainly hydrophilic component and the compatibility of polyurethane matrix:I.e. hydrophilic component can not be very well in polyurethane
In disperse；By the method for the copolymerization hydrophilic unit in polyurethane segment, then cost is high, complex process.Either copolymerization and altogether
It is mixed, material basic structure can be all had influence on, so as to influence film-forming process.Why polyurethane material has higher mechanical property
Can, its Microphase Separation structure is major reason.Introduce after copolymerization and blending unit, this Microphase Separation structure is affected and broken
It is bad, so as to significantly reduce the mechanical property of film forming.
The content of the invention
For solve the deficiencies in the prior art, the present invention provide one kind in the case where not influenceing polyurethane body structure, it is simultaneous
Has filling perforation polyurethane water-proof moisture permeable membrane of high moisture-inhibiting and strong mechanical performance and preparation method thereof.
The technical solution adopted in the present invention is：
A kind of filling perforation polyurethane water-proof moisture permeable membrane, it is characterised in that：Including basement membrane and filling perforation material, described filling perforation material
Quality be the 5% ~ 85% of basement membrane and filling perforation material gross mass, and described filling perforation material is hydrophilic monomer and hydrophobic monomer
Hydrophily list in the copolymerising hydrophilic macromolecule formed in the presence of crosslinking agent through in-situ cross-linked polymerization, described filling perforation material
The weight/mass percentage composition of body, hydrophobic monomer and crosslinking agent is respectively：
Hydrophilic monomer：20%~90%；
Crosslinking agent：1%~9%；
Hydrophobic monomer：Surplus.
Further, above-mentioned basement membrane is the microporous polyurethane film with dissymmetrical structure, and described microporous polyurethane film
In polyurethane material any of for EU, PAUR and aqueous polyurethane, and described poly- ammonia
The porosity of ester microporous barrier is then 10% ~ 80%, and average pore size is 100 nanometers ~ 100 microns.
And above-mentioned hydrophilic monomer be acrylic acid, methacrylic acid, acrylamide, vinyl amine, vinylbenzenesulfonic acid,
At least one of hydroxy-ethyl acrylate, vinyl ammonium salt and its derivative.
And described hydrophobic monomer is then at least one of methyl methacrylate, Styrene and its derivatives.
In addition, described crosslinking agent be divinylbenzene, DAAM, N, N'- methylene diacrylamides and its
At least one of derivative.
Further, the preparation method of above-mentioned basement membrane is immersion precipitation phase conversion method.
Described immersion precipitation phase conversion method is concretely comprised the following steps：
1) polyurethane material is dissolved in organic solvent, is made into poly- ammonia in polyurethane solutions, described polyurethane solutions
The weight/mass percentage composition of ester material is 20% ~ 80%；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to be run along fixed-direction to scratch film forming, and avoid producing in knifing process
Bubble；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred to standing in coagulating bath
6h, in vacuum drying oven, dries 24h at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is treated after cleaning-drying
With.
8th, a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 7, it is characterised in that：Step 1）Described
Organic solvent is：At least one of DMF, toluene, acetone, ethyl acetate, and step 4）Described coagulating bath is that water or DMF are molten
Liquid.
A kind of preparation method of above-mentioned filling perforation polyurethane water-proof moisture permeable membrane, it is characterised in that comprise the following steps：
（1）Prepare basement membrane：Turned using foaming, pore-foaming agent method, the freeze-dried method of emulsion, phase separation method, immersion precipitation phase
Any of change method method prepares basement membrane；
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：Filling perforation material and radical initiator are dissolved in organic solvent
In, prepare polymerization and prepare liquid, the addition quality of described radical initiator is that filling perforation material and radical initiator are total
The 0.5% ~ 5% of quality, and it is 30% ~ 80% that described polymerization, which prepares the solid content of liquid,；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares
In liquid, taken out after infiltration 10-30min, basement membrane is then put into culture dish, inserts and 40 is heated in baking ovenoC~80oC triggers poly-
Close, polymerization time is 2h ~ 10h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent is removed and free radical triggers
Agent, obtains the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
Further：Step（2）Described in organic solvent be DMF solution, in toluene, acetone, ethyl acetate, water, ethanol
At least one, and step（2）Described in radical initiator be BP, dilauroyl peroxide, the isobutyl of azo two
Any of nitrile, ABVN, peroxidating two acyl, persulfate, hydrogen peroxide, ferrous sulfate, sulphite.
The beneficial effects of the present invention are：The present invention is improved and optimized by the formula to filling perforation material so that filled out
Adhesion between Porous materials and basement membrane can be effectively improved, while so that filling perforation material is big to the absorption of moisture and through ability
Big enhancing, and with excellent mechanical property；And the improvement and optimization of the preparation method by device to hole polyurethane water-proof moisture permeable membrane, make
During the preparation for obtaining hole polyurethane water-proof moisture permeable membrane, the process that especially filling perforation material is introduced into the micropore of basement membrane is fast
It is fast, simple, effective.
Brief description of the drawings：
Fig. 1 is the phase-separation model figure of basement membrane in immersion precipitation phase conversion method of the present invention；
Fig. 2 is the unidirectional wellability schematic diagram of filling perforation polyurethane water-proof moisture permeable membrane of the present invention；
Fig. 3 is the filling perforation process schematic of filling perforation material.
Embodiment：
Specific introduction is done to the present invention below in conjunction with the accompanying drawings.
Embodiment 1：
The preparation process of filling perforation polyurethane water-proof moisture permeable membrane is as follows：
（1）Prepare basement membrane：
First, basement membrane is microporous polyurethane film, in the present embodiment, the polyurethane material in described microporous polyurethane film
It is 40%, 1.3 microns of average pore size for the porosity of EU, and microporous polyurethane film；
Secondly, the preparation method of basement membrane is：Immersion precipitation phase conversion method, is concretely comprised the following steps：
1) polyurethane material is dissolved in organic solvent DMF, is made into polyurethane solutions, described polyurethane solutions and gathers
The weight/mass percentage composition of urethane material is 40%；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to be run along fixed-direction to scratch film forming, and avoid producing in knifing process
Bubble；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred to standing in coagulating bath
6h, described coagulating bath is water.In vacuum drying oven, 24h is dried at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is treated after cleaning-drying
With.
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：By filling perforation material（Hydrophilic monomer acrylic acid, hydrophobic monomer
Methyl methacrylate and crosslinking agent B IS（N, N'- methylene diacrylamide）With radical initiator AIBN（The isobutyl of azo two
Nitrile）In organic solvent, described organic solvent is ethanol and the mixture of toluene, and the volume ratio of ethanol and toluene for dissolving
For：1:2, prepare polymerization and prepare liquid, wherein, described filling perforation material is hydrophilic monomer and hydrophobic monomer in crosslinking agent
In the presence of the copolymerising hydrophilic macromolecule that is formed through in-situ cross-linked polymerization, and the addition quality of described radical initiator is
Polymerization prepares the 0.5% of liquid gross mass, and described polymerization prepares in liquid, and the weight/mass percentage composition of acrylic acid is 20%, acrylic acid
The weight/mass percentage composition of methyl esters is 10%, and crosslinking agent B IS weight/mass percentage composition is 2%；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares
In liquid, wherein, the mass ratio of filling perforation material is in basement membrane and polymerization preparation liquid：1：Taken out after 5, infiltration 15min, then by basement membrane
Culture dish is put into, inserts and 70 is heated in baking ovenoC triggers polymerization, and polymerization time is 3h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent is removed and free radical triggers
Agent, obtains the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
After tested, the vapor transfer rate for the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation that embodiment 1 is prepared is
4023g/(m224h), ASTM E96-1995 BW；The mmH of resistance to hydrostatic pressure 6572O/m2, GB/T 4744-1997；Fracture strength
35.3MPa, ASTM D-412.
Embodiment 2：
First, basement membrane is microporous polyurethane film, in the present embodiment, the polyurethane material in described microporous polyurethane film
It is that porosity is then 30% for the porosity of PAUR, and microporous polyurethane film, average pore size is 0.5 micron；
Secondly, the preparation method of basement membrane is：Immersion precipitation phase conversion method, is concretely comprised the following steps：
1) polyurethane material is dissolved in organic solvent-acetone, is made into polyurethane solutions, described polyurethane solutions and gathers
The weight/mass percentage composition of urethane material is 70%；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to be run along fixed-direction to scratch film forming, and avoid producing in knifing process
Bubble；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred to standing in coagulating bath
6h, described coagulating bath is water.In vacuum drying oven, 24h is dried at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is treated after cleaning-drying
With.
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：By filling perforation material（Hydrophilic monomer acrylic acid acrylamide, dredge
Aqueous monomers styrene and cross-linker divinylbenzene and radical initiator benzoyl peroxide dissolve in organic solvent, institute
The organic solvent stated is the mixture of water and acetone, and the volume ratio of water and acetone is：1:4, prepare polymerization and prepare liquid, its
In, described filling perforation material is that hydrophilic monomer and hydrophobic monomer polymerize what is formed in the presence of crosslinking agent through in-situ cross-linked
Copolymerising hydrophilic macromolecule, and the addition quality of described radical initiator prepares the 2% of liquid gross mass for polymerization, and it is described
Polymerization prepare in liquid, the weight/mass percentage composition of acrylamide is 40%, and the weight/mass percentage composition of styrene is 5%, crosslinking agent two
The weight/mass percentage composition of vinyl benzene is 5%；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares
In liquid, wherein, the mass ratio of filling perforation material is in basement membrane and polymerization preparation liquid：1：Taken out after 5, infiltration 10min, then by basement membrane
Culture dish is put into, inserts in baking oven and is heated to 80 DEG C of initiation polymerizations, polymerization time is 6h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent is removed and free radical triggers
Agent, obtains the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
After tested, the vapor transfer rate for the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation that embodiment 2 is prepared is
3223g/(m224h), ASTM E96-1995 BW；The mmH of resistance to hydrostatic pressure 9812O/m2, GB/T 4744-1997；Fracture strength
43.6MPa, ASTM D-412.
Embodiment 3：
First, basement membrane is microporous polyurethane film, in the present embodiment, the polyurethane material in described microporous polyurethane film
It is that porosity is then 70% for the porosity of aqueous polyurethane, and microporous polyurethane film, average pore size is 7.8 microns；
Secondly, the preparation method of basement membrane is：Immersion precipitation phase conversion method, is concretely comprised the following steps：
1) polyurethane material is dissolved in the mixed solvent (volume ratio 1 of toluene and acetone：1) in, polyurethane solutions are made into,
The weight/mass percentage composition of polyurethane material is 60% in described polyurethane solutions；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to be run along fixed-direction to scratch film forming, and avoid producing in knifing process
Bubble；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred to standing in coagulating bath
6h, described coagulating bath is water.In vacuum drying oven, 24h is dried at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is treated after cleaning-drying
With.
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：By filling perforation material（Hydrophilic monomer is vinylbenzenesulfonic acid, third
Olefin(e) acid hydroxyl ethyl ester, hydrophobic monomer methyl methacrylate and crosslinking agent DAAM and radical initiator persulfuric acid
In a solvent, described solvent is for water and the mixture of acetone, and the volume ratio of water and acetone for sodium and ferrous sulfate dissolving：1:
2, prepare polymerization and prepare liquid, wherein, described filling perforation material is the work of hydrophilic monomer and hydrophobic monomer in crosslinking agent
With lower through the in-situ cross-linked copolymerising hydrophilic macromolecule for polymerizeing formation, and the addition quality of described radical initiator is polymerization
Prepare the 4% of liquid gross mass, and described polymerization prepares in liquid, the weight/mass percentage composition of vinylbenzenesulfonic acid is 15%, acrylic acid
The weight/mass percentage composition of hydroxyl ethyl ester is 15%, and the weight/mass percentage composition of methyl methacrylate is 5%, crosslinking agent diacetone acrylamide acyl
The weight/mass percentage composition of amine is 7%；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares
In liquid, wherein, the mass ratio of filling perforation material is in basement membrane and polymerization preparation liquid：1：Taken out after 5, infiltration 30min, then by basement membrane
Culture dish is put into, inserts in baking oven and is heated to 40 DEG C of initiation polymerizations, polymerization time is 8h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent is removed and free radical triggers
Agent, obtains the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
After tested, the vapor transfer rate for the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation that embodiment 3 is prepared is
3423g/(m224h), ASTM E96-1995 BW；Resistance to hydrostatic pressure 768mmH2O/m2, GB/T 4744-1997；Fracture strength
23.4MPa, ASTM D-412.
Embodiment 4：
First, basement membrane is microporous polyurethane film, in the present embodiment, the polyurethane material in described microporous polyurethane film
It is 20% for the porosity of EU, and microporous polyurethane film, average pore size is 0.8 micron；
Secondly, the preparation method of basement membrane is：Immersion precipitation phase conversion method, is concretely comprised the following steps：
1) polyurethane material is dissolved in the mixed solvent of organic solvent DMF and ethyl acetate（Volume ratio 1:1）In, it is made into
The weight/mass percentage composition of polyurethane material is 50% in polyurethane solutions, described polyurethane solutions；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to be run along fixed-direction to scratch film forming, and avoid producing in knifing process
Bubble；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred to standing in coagulating bath
6h, described coagulating bath is water.In vacuum drying oven, 24h is dried at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is treated after cleaning-drying
With.
In addition, the preparation method of basement membrane can also select foaming, pore-foaming agent method, the freeze-dried method of emulsion, phase separation method,
The above method is common method, therefore is no longer discussed in detail.
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：By filling perforation material（Hydrophilic monomer vinyl amine and vinyl ammonium
Sodium salt, hydrophobic monomer methyl methacrylate and cross-linker divinylbenzene and the dissolving of radical initiator azodiisobutyronitrile
In organic solvent, described organic solvent is for DMF and the mixture of ethanol, and the volume ratio of DMF and ethanol：2:1, prepare
Obtain polymerization and prepare liquid, wherein, described filling perforation material is that hydrophilic monomer and hydrophobic monomer are passed through in the presence of crosslinking agent
The copolymerising hydrophilic macromolecule that in-situ cross-linked polymerization is formed, and the addition quality of described radical initiator prepares liquid for polymerization
The 1% of gross mass, and described polymerization prepares in liquid, the weight/mass percentage composition of vinyl amine is 20%, the matter of vinyl ammonium sodium salt
It is 20% to measure percentage composition, and the weight/mass percentage composition of methyl methacrylate is 10%, the quality percentage of cross-linker divinylbenzene
Content is 2%；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares
In liquid, wherein, the mass ratio of filling perforation material is in basement membrane and polymerization preparation liquid：1：Taken out after 5, infiltration 15min, then by basement membrane
Culture dish is put into, inserts and 60 is heated in baking ovenoC triggers polymerization, and polymerization time is 10h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent is removed and free radical triggers
Agent, obtains the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
After tested, the vapor transfer rate for the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation that embodiment 1 is prepared is
3122g/(m224h), ASTM E96-1995 BW；Resistance to hydrostatic pressure 572mmH2O/m2, GB/T 4744-1997；Fracture strength
35.3MPa, ASTM D-412.
Fig. 1 is the phase-separation model figure of basement membrane in immersion precipitation phase conversion method of the present invention；Fig. 2 is of the present invention
Filling perforation polyurethane water-proof moisture permeable membrane unidirectional wellability schematic diagram.
As depicted in figs. 1 and 2：Basement membrane used in the present embodiment has dissymmetrical structure, according to the difference of split-phase mechanism, its
Membrane pore structure according to depth difference and be divided into sphaerulitic, cellular small structure and finger-like macroporous structure, its aperture from
Cortex starts, and gradually increases with depth increase.No matter use which kind of filling perforation mode, its filling perforation be all since macropore side, by
In the limitation of surface tension, small boring ratio macropore is more difficult to enter, and therefore, passes through the filling perforation polyurethane water-proof moisture-inhibiting described in the present embodiment
Effective control of the preparation process of film, can be achieved uneven distribution of the filling perforation material on basement membrane cross section, that is, concentrates on macropore
Side, its result is to constitute unidirectional wellability, and hydrophily is presented because there is the concentration of hydrophilic gel in macropore side,
Cortex side then still retains the original hydrophobic character of basement membrane simultaneously.Unidirectional application of the wellability to garment material field has
Special Significance, can make fabric have higher absorbing sweat performance in the side towards body surface, while in the side towards external environment
Retain good water resistance.
Above-mentioned filling perforation material is only distributed across in hole, does not penetrate into microporous polyurethane membrane structure, therefore microporous polyurethane
The phase separation structure of film is unaffected.So as to keep its original mechanical characteristic；And due to there is basement membrane to support, filling perforation material
Material only need to consider hydrophilic and hydrophobic, and its mechanical property then mustn't excessively be considered.
Fig. 3 is the filling perforation process schematic of filling perforation material.
As shown in Figure 3：The filling perforation method of basement membrane described in the present embodiment is situ aggregation method, for example above-mentioned step of detailed process
It is described.During above-mentioned filling perforation, pore structure, size and its connection situation of basement membrane influence the difficulty or ease and filling perforation caudacoria of filling process
Hydrone pass through passage, e.g., dead end hole cuts little ice in water penetration；And polymerize and prepare hydrophobic monomer in liquid and contain
Amount must be moderate, and too high levels can reduce the absorption and diffusivity to moisture content, and content is too low, reduces the filling polymerization of formation
The compatibility of thing and matrix, easily causes filling defect, damages water proofing property, and initiator is then generally selected in elicitation procedure without gas
Body or few gas generator, to prevent forming bubble, and should select to trigger active higher initiator.
Described above is only the preferred embodiment of patent of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of patent principle of the present invention is not departed from, some improvements and modifications can also be made, these improve and
Retouching also should be regarded as the protection domain of patent of the present invention.
Claims (10)
1. a kind of filling perforation polyurethane water-proof moisture permeable membrane, it is characterised in that：Including basement membrane and filling perforation material, described filling perforation material
Quality is the 5% ~ 85% of basement membrane and filling perforation material gross mass, and described filling perforation material is that hydrophilic monomer and hydrophobic monomer exist
Hydrophily list in the copolymerising hydrophilic macromolecule formed in the presence of crosslinking agent through in-situ cross-linked polymerization, described filling perforation material
The weight/mass percentage composition of body, hydrophobic monomer and crosslinking agent is respectively：
Hydrophilic monomer：20%~90%；
Crosslinking agent：1%~9%；
Hydrophobic monomer：Surplus.
2. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 1, it is characterised in that：Described basement membrane be with
Polyurethane material in the microporous polyurethane film of dissymmetrical structure, and described microporous polyurethane film is EU, poly-
Any of ester type polyurethane and aqueous polyurethane, and the porosity of described microporous polyurethane film is 10% ~ 80%, average hole
Footpath is 100 nanometers ~ 100 microns.
3. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 1, it is characterised in that：Described hydrophilic monomer
For acrylic acid, methacrylic acid, acrylamide, vinyl amine, vinylbenzenesulfonic acid, hydroxy-ethyl acrylate, vinyl ammonium salt and
At least one of its derivative.
4. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 1, it is characterised in that：Described hydrophobic monomer
For at least one of methyl methacrylate, Styrene and its derivatives.
5. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 1, it is characterised in that：Described crosslinking agent is two
Vinyl benzene, DAAM, N, at least one of N'- methylene diacrylamides and its derivative.
6. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 1, it is characterised in that：The preparation of described basement membrane
Method is immersion precipitation phase conversion method.
7. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 6, it is characterised in that：Described immersion precipitation phase
Method for transformation is concretely comprised the following steps：
1) polyurethane material is dissolved in organic solvent, is made into polyurethane material in polyurethane solutions, described polyurethane solutions
The weight/mass percentage composition of material is 20% ~ 80%；
2) polyurethane solutions are poured on horizontal glass plate；
3) it is careful smoothly to promote scraper to run to scratch film forming along fixed-direction, and avoid producing bubble in knifing process；
4) after the polyurethane film coated will be scraped together with glass plate in atmosphere horizontal 5min, it is transferred in coagulating bath and stands 6h,
In vacuum drying oven, 24h is dried at 60 DEG C；
5) fully dry polyurethane film carefully is torn off from glass plate, sealed storage is stand-by after cleaning-drying.
8. a kind of filling perforation polyurethane water-proof moisture permeable membrane according to claim 7, it is characterised in that：Step 1）Described is organic
Solvent is：At least one of DMF, toluene, acetone, ethyl acetate, and step 4）Described coagulating bath is water or DMF solution.
9. the preparation method of the filling perforation polyurethane water-proof moisture permeable membrane described in a kind of claim 1, it is characterised in that including following step
Suddenly：
（1）Prepare basement membrane：Utilize foaming, pore-foaming agent method, the freeze-dried method of emulsion, phase separation method, immersion precipitation inversion of phases side
Any of method method prepares basement membrane；
（2）Polymerization, which is prepared, using filling perforation material prepares liquid：By filling perforation material and radical initiator dissolving in organic solvent, system
Standby to obtain polymerization preparation liquid, the addition quality of described radical initiator is filling perforation material and radical initiator gross mass
0.5% ~ 5%, and it is 30% ~ 80% that described polymerization, which prepares the solid content of liquid,；
（3）Infiltration, polymerization filling perforation：By step（1）The basement membrane immersion step prepared（2）The polymerization prepared prepares liquid
In, taken out after infiltration 10-30min, basement membrane is then put into culture dish, inserts and 40 is heated in baking ovenoC~80oC triggers polymerization,
Polymerization time is 2h ~ 10h；
（4）Post-processing：After the completion of polymerization, oven temperature is raised, 24h is dried, residual solvent and radical initiator is removed, obtains
To the polyurethane-base waterproof humidity-permeant film being combined based on filling perforation.
10. a kind of preparation method of filling perforation polyurethane water-proof moisture permeable membrane according to claim 9, it is characterised in that：Step
（2）Described in organic solvent be DMF solution, at least one of toluene, acetone, ethyl acetate, water, ethanol, and step（2）
Described in radical initiator be BP, dilauroyl peroxide, azodiisobutyronitrile, ABVN, peroxide
Change any of two acyls, persulfate, hydrogen peroxide, ferrous sulfate, sulphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510131019.4A CN104788712B (en) | 2015-03-25 | 2015-03-25 | A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510131019.4A CN104788712B (en) | 2015-03-25 | 2015-03-25 | A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104788712A CN104788712A (en) | 2015-07-22 |
| CN104788712B true CN104788712B (en) | 2017-10-31 |
Family
ID=53553927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510131019.4A Active CN104788712B (en) | 2015-03-25 | 2015-03-25 | A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104788712B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106751719A (en) * | 2016-12-01 | 2017-05-31 | 江苏宏远新材料科技有限公司 | Temperature-sensitive waterproof moisture-permeable film |
| GB201810160D0 (en) * | 2018-06-20 | 2018-08-08 | Royal College Of Art | Wearable artificial gill |
| JP2021532287A (en) * | 2018-07-31 | 2021-11-25 | ダブリュ.エル.ゴア アンド アソシエイツ, インコーポレイティドW.L. Gore & Associates, Incorporated | Polyethylene film |
| CN109957346B (en) * | 2019-03-26 | 2021-06-18 | 东莞奥得时精密电子有限公司 | Antifogging adhesive film and its material and technology |
| CN111019332B (en) * | 2019-12-10 | 2021-09-03 | 浙江华峰合成树脂有限公司 | Polyurethane waterproof moisture-permeable film and preparation method thereof |
| CN110992874B (en) | 2019-12-30 | 2022-10-04 | 武汉天马微电子有限公司 | Display panel, driving method thereof and display device |
| CN111036091B (en) * | 2020-01-17 | 2022-03-25 | 湖南科技大学 | Preparation method of hydrophobic composite membrane |
| CN114232327A (en) * | 2021-12-18 | 2022-03-25 | 吴江市巨龙纺织品有限公司 | Preparation method of moisture-absorbing spandex filament, moisture-absorbing yarn and waterproof moisture-absorbing fabric |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803116A (en) * | 1985-10-31 | 1989-02-07 | Toray Industries Incorporated | Waterproof fabric having high moisture permeability and method of making same |
| CN101011645A (en) * | 2006-12-27 | 2007-08-08 | 南京工业大学 | Method for hydrophilic modification of polypropylene porous membrane surface by using amphipathic molecule |
| CN102423642A (en) * | 2011-12-13 | 2012-04-25 | 北京碧水源科技股份有限公司 | Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same |
| CN103483618A (en) * | 2013-10-11 | 2014-01-01 | 苏州汇龙膜技术发展有限公司 | Hydrophilic modification method of polytetrafluoroethylene porous membrane |
| CN103910969A (en) * | 2014-04-18 | 2014-07-09 | 昆山金有利新材料科技有限公司 | Water-resistant air-permeable polyurethane film and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004315817A (en) * | 2003-04-03 | 2004-11-11 | Seiren Co Ltd | Polyurethane film and method for producing the same |
-
2015
- 2015-03-25 CN CN201510131019.4A patent/CN104788712B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4803116A (en) * | 1985-10-31 | 1989-02-07 | Toray Industries Incorporated | Waterproof fabric having high moisture permeability and method of making same |
| CN101011645A (en) * | 2006-12-27 | 2007-08-08 | 南京工业大学 | Method for hydrophilic modification of polypropylene porous membrane surface by using amphipathic molecule |
| CN102423642A (en) * | 2011-12-13 | 2012-04-25 | 北京碧水源科技股份有限公司 | Permanent hydrophilic modification method for surface of porous membrane and porous membrane obtained by same |
| CN103483618A (en) * | 2013-10-11 | 2014-01-01 | 苏州汇龙膜技术发展有限公司 | Hydrophilic modification method of polytetrafluoroethylene porous membrane |
| CN103910969A (en) * | 2014-04-18 | 2014-07-09 | 昆山金有利新材料科技有限公司 | Water-resistant air-permeable polyurethane film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "Pore-filling type polymer electrolyte membranes for a direct methanol fuel cell";Takeo Yamaguchi, et al.;《Journal of Membrane Science》;20030110;第214卷;第283-292页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104788712A (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104788712B (en) | A kind of filling perforation polyurethane water-proof moisture permeable membrane and preparation method thereof | |
| CN102533186B (en) | Adhesive for alkali resistant acrylate glass fiber mesh cloth shaping, and preparation method thereof | |
| CN101956331B (en) | Method for preparing waterproof moisture-penetrating coated fabric | |
| US20180178144A1 (en) | Material used for rapid separation of oil and water and preparation method and application thereof | |
| CN102173154B (en) | Polyurethane windproof air-permeable coat compounded textile fabric and preparation method thereof | |
| CN102744940A (en) | Method for producing waterproof moisture permeability fabric based on water foaming system | |
| CN107551832B (en) | A kind of preparation method of the cross-linking modified nanofiltration membrane of regenerated cellulose base | |
| CN109177370A (en) | Three layers of composite water-proof breathable fabric of one kind and preparation method thereof | |
| CN102425069A (en) | Method for producing aqueous polyurethane synthetic leather for costume by using physically-foamed pore forming coating technology | |
| CN103962113A (en) | Difunctional cellulose based microsphere adsorbent and preparation method thereof | |
| CN103172785A (en) | Super-absorbent self-crosslinking epoxy acrylate copolymer as well as preparation and application thereof | |
| CN109349709A (en) | A kind of seamless down-filling feather dress fabric and its production method | |
| CN102041687A (en) | Waterproof ventilated synthetic leather and preparation method thereof | |
| CN107043437A (en) | A kind of water-fast high-elastic expandable pure-acrylic emulsion and the expanded material based on its preparation | |
| CN102977269A (en) | Chitosan acrylate graft latex and cotton fiber processing solution containing chitosan acrylate graft latex | |
| CN101994258A (en) | Porous material textile with ventilation and adsorption and preparation method thereof | |
| CN102650103B (en) | Preparation method for polyurethane synthetic leather with water repellent performance | |
| CN108978249B (en) | Air-suction moisture-permeable leather for shoe lining and preparation method thereof | |
| CN106747102B (en) | Mandruka concrete and its preparation process | |
| CN106925238A (en) | A kind of sponge support type organic solvent absorbent and preparation method thereof | |
| CN112709005A (en) | Preparation method of high-oil-absorption melt-blown non-woven fabric | |
| CN102504089B (en) | Preparation method of water-resistant acrylic ester core-shell emulsion | |
| CN107369802A (en) | A kind of cellulose coating lithium ion battery diaphragm and preparation method thereof | |
| CN109208343B (en) | Dry-method microporous coating manufacturing process and microporous coating fabric production process | |
| CN106867017A (en) | Controllable micro-porous film in a kind of aperture and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |