CN106012303B - A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method - Google Patents
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method Download PDFInfo
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- CN106012303B CN106012303B CN201610325975.0A CN201610325975A CN106012303B CN 106012303 B CN106012303 B CN 106012303B CN 201610325975 A CN201610325975 A CN 201610325975A CN 106012303 B CN106012303 B CN 106012303B
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
Abstract
The present invention provides a kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation methods, which is characterized in that including：Diisocyanate and oligomer dihydric alcohol are dissolved in solvent, reacted under nitrogen protection, the reaction system containing performed polymer is obtained；At least one of Fluorinated dihydric alcohol and end hydroxypropyl based polysiloxane are dissolved in solvent, is added in reaction system and is reacted, obtain the reactive hydrophobic polyurethane solution with terminal isocyanate groups；Using above-mentioned reactive hydrophobic polyurethane electrostatic spinning is carried out as raw material, the temperature for controlling spinning environment is 20 35 DEG C, relative humidity is 70 95%, make in solution jet fiber forming process, reactive hydrophobic polyurethane with terminal isocyanate groups is crosslinked with the hydrone in air to react, and obtains fiber base waterproof humidity-permeant film.The present invention effectively improves the mechanical performance of membrane material, and processing technology is simple and convenient to operate and reaction condition is mild, easily controllable.
Description
Technical field
The invention belongs to electrostatic spinning field, it is related to a kind of electrostatic spinning of high strength fiber Wiki waterproof humidity-permeant film/wet solid
Change preparation method, is a kind of reactive hydrophobic polyurethane with terminal isocyanate groups of synthesis, and using it as raw material specifically
Electrostatic spinning is carried out, is reacted using being crosslinked with the hydrone in air in spinning solution jet stream fiber forming process, makes polymer
Strand rapid growth and improve fiber bodies intensity, while formed between fiber it is a large amount of mutually bond structures and prevent to slide,
To obtain that there is the tunica fibrosa of very good mechanical properties and waterproofing and moisture-penetration performances.
Background technology
Moisture permeable laminated fabric is the novel fabric using waterproof humidity-permeant film as core, can not only meet severe cold, sleet, big
Protection of the people when carrying out outdoor activities needs under the bad weather circumstances such as wind, while being also applied for people in daily life
The requirement of comfortable features of clothing, thus there is vast potential for future development.Existing waterproof humidity-permeant film includes mainly hydrophilic non-porous film and dredges
Water microporous barrier, wherein hydrophilic non-porous film is usually molded through melting extrusion as raw material using thermoplastic polyurethane and is made, processing technology
Relatively simple and water resistance is good, but the film rely primarily on " adsorption -diffusion-desorption " between hydrone and hydrophilic radical act on into
Row wet steam transmits, and penetrability is poor, causes corresponding waterproof moisture permeating fabric comfort and protective poor；In dewatering microporous film
The a large amount of hydrophobicity connected pore channels in portion can prevent the infiltration of liquid water, the mainstream product such as U.S. while allowing water vapor diffusion
Gore companies utilize microporous teflon membran prepared by biaxial tension method, compared with hydrophilic non-porous film, have preferably anti-
Water water vapour permeability, but its production technology is complicated, technology and equipment requirement are high, valuable product, and membrane material prepared by this method
Pore passage structure inside material is difficult to control, thus is difficult to further increase its waterproofing and moisture-penetration performances, meanwhile, it is difficult after the product abandonment
With degradation, there is certain environmental hazard, thus seriously limit its extensive use in Waterproof Breathable field.In addition, existing
Hydrophilic non-porous film and dewatering microporous film generally face the deficiency of bad mechanical property, and machinability and useful life longevity still need
It improves.
Electrostatic spinning technique is simple for process, manufacturing cost is cheap, can be quickly obtained distribution of fiber diameters from several nanometers to several
The superfine fibre of micron, tunica fibrosa prepared by this method have many advantages, such as that fibre diameter is small, fiber membrane aperture is small, porosity is high,
It is very suitable for the application demand of waterproof humidity-permeant film, by the regulation and control to tunica fibrosa pore passage structure and hydrophobic performance, is expected to realize
The Synchronous lifting of water proofing property and penetrability has huge application potential in waterproof humidity-permeant film manufacture field.It is presently disclosed quiet
The technology of electrospinning fibre base waterproof humidity-permeant film includes：A kind of electrospinning process of the fiber base waterproof humidity-permeant film of high moisture-inhibiting flux
And its device (CN104452109A), a kind of Waterproof Breathable composite membrane and preparation method thereof (CN103963393A), a kind of waterproof
The multi-functional composite micro/nano fabric of moisture-inhibiting and preparation method thereof (CN103388265A), a kind of waterproof humidity-permeant film, preparation method
And waterproof moisture permeating fabric, preparation method (CN104207390A), the preparation method of waterproof humidity-permeant film, waterproof moisture permeating fabric and its
The electrospinning process and its device of the fiber base waterproof humidity-permeant film of preparation method (CN103437072A), a kind of super abrasive
(CN104480639A), a kind of Static Spinning aeroge composite nano-fiber membrane and preparation method thereof (CN104911901A), one kind
Waterproof moisture-permeable composite fabric and preparation method thereof (CN104911901A, a kind of system of permeable watertight polyurethane nanofiber film
Preparation Method (CN102517794A), a kind of High-efficiency waterproof moisture-permeable shell fabric and preparation method thereof (CN102632648A) etc., however, on
State in the tunica fibrosa of patented technology preparation that adhesion degree is low, porosity is low, aperture is big between fiber, cause the mechanical strength difference of film and
Waterproofing and moisture-penetration performances are difficult to be promoted, its practical application is made to be restricted.It is raw material using reactive polymer, by post-processing side
It is a kind of method effectively improving material mechanical performance that method, which makes polymer crosslink reaction, and existing the relevant technologies are using instead at present
The cross-linking reaction of answering property polymer improves the mechanical property of tunica fibrosa, such as：One kind has cross-linked structure polyimide nano fine
It ties up film and prepares (CN102766270A), a kind of enhanced bi-component nano fiber porous film and preparation method
(CN104480639A), a kind of reinforced nanofiber porous membrane and preparation method thereof (CN102140762A) etc., above-mentioned patent
Technology can improve the mechanical property of tunica fibrosa to a certain extent, however, the crosslinking of its reactive materials needs complicated post-processing
Process, such as the alkali cleaning of polyamic acid tunica fibrosa, washing, drying, heating, cooling procedure, for another example reactive polyurethane high humidity environment is warm
Processing etc., treatment process is cumbersome, cross-linking reaction condition requires that harsh, processing cost is excessively high, and crosslinked polymer degree with
Degree is mutually glued between fiber to be difficult to control, and the mechanical property of tunica fibrosa is promoted limited.
Invention content
The object of the present invention is to provide a kind of electrostatic spinning of high strength fiber Wiki waterproof humidity-permeant film/moisturecuring preparation sides
Method can solve existing waterproof humidity-permeant film water pressure resistance and the low deficiency of vapor transfer rate and the mechanical performance for effectively improving tunica fibrosa.
In order to achieve the above object, the present invention provides a kind of electrostatic spinning/moisturecuring systems of fiber base waterproof humidity-permeant film
Preparation Method, which is characterized in that including：
The first step：Diisocyanate and oligomer dihydric alcohol are dissolved in solvent, solution A, the diisocyanate are obtained
Ester is reacted under nitrogen protection with oligomer dihydric alcohol, obtains the reaction system containing performed polymer；
Second step：At least one of Fluorinated dihydric alcohol and end hydroxypropyl based polysiloxane are dissolved in solvent, solution is obtained
Solution B is added in the reaction system obtained by the first step and reacts by B, obtains having the reactivity of terminal isocyanate groups to dredge
Water polyurethane solutions；
Third walks：The reactive hydrophobic polyurethane solution with terminal isocyanate groups of second step is subjected to electrostatic spinning,
Control spinning environment temperature be 20-35 DEG C, relative humidity 70-95%, make in solution jet fiber forming process, have isocyanide
The reactive hydrophobic polyurethane of acid esters end group is crosslinked with the hydrone in air to react, and obtains fiber base waterproof humidity-permeant film.
Further, the tensile strength of the fiber base waterproof humidity-permeant film is reachable up to 50MPa or more, water pressure resistance
100kPa or more, vapor transfer rate are up to 15000g/m2/ d or more.
Further, the diisocyanate in the first step is that methyl diphenylene diisocyanate (MDI), toluene two are different
Cyanate (TDI), 1, hexamethylene-diisocyanate (HDI), isoflurane chalcone diisocyanate, dicyclohexyl methyl hydride diisocyanate,
Benzene dimethylene diisocyanate, paraphenylene diisocyanate, dimethyl diphenyl diisocyanate, xyxylene isocyanates,
Liquefied mdi, TDI dimers and one kind in HDI dimers or arbitrary several combination.
Further, the solvent in the first step is tetrahydrofuran, dimethylformamide, dimethylacetylamide, methyl
One kind in pyrrolidones, toluene, ethyl acetate, butyl acetate, methylisobutylketone, diethylene glycol ether, butanone and acetone or
Arbitrary several combination.
Further, the oligomer dihydric alcohol in the first step is line style dihydric alcohol, relative molecular mass 400-
4000。
Further, the oligomer dihydric alcohol in the first step is polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether two
Alcohol, tetrahydrofuran-propylene oxide copolymerization dihydric alcohol, polyethylene glycol adipate dihydric alcohol, polypropylene glycol adipate dihydric alcohol,
Poly adipate succinic acid ester dihydric alcohol, polydiethylene glycol adipate dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, poly- ε-
Caprolactone diol, polycarbonate glycol, polyolefin dihydric alcohol and one kind or arbitrary several in polyacrylate dihydric alcohol
Combination.
Further, the molar ratio of the oligomer dihydric alcohol in the first step and diisocyanate is 1: 4-8, solution A
The mass fraction of middle solute is 40-60%.
Further, the first step, reaction condition be：Mixing speed is 100-300rpm, reaction temperature 40-60
DEG C, reaction time 0.5-3h.
Further, contained at least one of the Fluorinated dihydric alcohol in the second step and end hydroxypropyl based polysiloxane
The molar ratio of remaining isocyanate groups is 1: 2-4 in reaction system obtained by some hydroxyl groups and the first step, solution
Total mass fraction is 50-70%.
Further, the second step, reaction condition be：Mixing speed is 200-300rpm, reaction temperature 60-80
DEG C, reaction time 0.5-3h.
Further, the molecular formula of the Fluorinated dihydric alcohol in the second step is HOCH2(CF2)nCH2OH, wherein n 2-
Integer between 10.
Further, the molecular formula of the end hydroxypropyl based polysiloxane is HO (CH2)3[Si(CH3)2O]mSi(CH3)2
(CH2)3OH, m are integer.
Further, the relative molecular mass of the end hydroxypropyl based polysiloxane is 400-3000.
Further, the feed postition of the solution B in the second step is to be added dropwise, and rate of addition is 20-30 drops/min.
Further, when the concentration of isocyanate groups in reaction system is reduced to 0.5-3mol/L, stop reaction, obtain
To the reactive hydrophobic polyurethane solution with terminal isocyanate groups.
Further, the electrospinning conditions in the third step are：Voltage is 10-100kV, reception distance is 10-
30cm, liquid supply speed 0.1-10mL/h.
Further, the reception base material of the electrostatic spinning in third step be copper mesh, aluminium foil, parchamyn paper, non-woven fabrics or
Thin polymer film.
A kind of electrostatic spinning/moisturecuring preparation method of fiber base waterproof humidity-permeant film of the present invention, it is reactive in of the invention
The synthetic route chart of hydrophobic polyurethane is as shown in Figure 1, using the reactive hydrophobic polyurethane independently synthesized as raw material, using Static Spinning
Silk/moisturecuring one-step shaping method prepares polyurethane nanofiber film, by controlling the ring in polymer solution jet stream fiber forming process
Border humiture makes reactive hydrophobic polyurethane quickly be crosslinked with the hydrone in air and reacts, post-processed without complexity
Journey can be obtained the polymer with high molecular weight and the nano fibrous membrane with mutual bonding structure, and preparation is simple,
And the mutual viscous degree in film between fiber is easy to regulate and control, and can effectively promote the properties of fiber base waterproof humidity-permeant film.Meanwhile this
The polymer solution spinning of higher concentration can be used in invention, effectively increases manufacture efficiency, and simple production process, is very suitable for
In industrial demand.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) a kind of method preparing reactive hydrophobic polyurethane disclosed by the invention, during regulation and control electrostatic spinning
Ambient temperature and humidity, so that reactive hydrophobic polyurethane is quickly crosslinked with the hydrone in air and react, with obtain have point
It is anti-to realize high strength fiber Wiki to effectively improve the mechanical performance of membrane material for son amount and the nano fibrous membrane for mutually bonding structure
Prepared by the electrostatic spinning of water moisture permeable membrane/moisturecuring one-step method, processing technology is simple and convenient to operate and reaction condition is mild, is easy to
Control.
(2) polyurethane synthesized in the present invention contains a large amount of silicon/fluorin radical, has good hydrophobicity, and fiber base is anti-
Water moisture permeable membrane have the characteristics that aperture is small, porosity is high, it can be achieved that waterproofing and moisture-penetration performances effective promotion；Meanwhile in tunica fibrosa
There are a large amount of mutually bonding structures between polymer molecular weight height and fiber, thus with excellent mechanical performance.
(3) heretofore described method is using the hydrophobic polyurethane solution with reactive terminal group as raw material, spinning solution
Content it is high, so as to which the efficiency of electrostatic spinning process, and the use of less solvent is substantially improved, it is saturating to be suitable for high performance water proof
The industrialization clean manufacturing of wet film.
(4) electrostatic spinning/moisturecuring method of the invention is of low cost, simple for process, using the polymerization of higher concentration
Object solution carries out spinning, effectively increases manufacture efficiency, meanwhile, prepared fiber base waterproof humidity-permeant film has both excellent machinery
Performance and waterproofing and moisture-penetration performances have broad application prospects in fields such as protective clothes.
Description of the drawings
Fig. 1 is the synthetic route chart of reactive hydrophobic polyurethane in the present invention.Wherein, n and m is arbitrary integer.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
The content of isocyanate groups is measured by di-n-butylamine titration method in following embodiment.
Embodiment 1
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.15mol polyethylene glycol (relative molecular mass 2000), 1mol methyl diphenylene diisocyanates
It is added in four-hole bottle with solvent dimethylformamide 400mL, stirring makes it fully dissolve, and obtains solution A, wherein solute
Total mass fraction is 59%, reacts 1h under nitrogen protection, and reaction temperature is 40 DEG C, and mixing speed 150rpm is contained
The reaction system of performed polymer, remaining isocyanate groups are 1.7mol in reaction system；
Second step：By the ends 0.3mol hydroxypropyl based polysiloxane, (molecular formula is HO (CH2)3[Si(CH3)2O]mSi(CH3)2
(CH2)3OH, relative molecular mass 2000) it is dissolved in solvents tetrahydrofurane 250mL, solution B is obtained, solution B is added drop-wise to
It is reacted in reaction system obtained by one step, rate of addition is 20 drops/min, and the total mass fraction of solute is in reaction process
66%, mixing speed 300rpm, reaction temperature are 60 DEG C, 1h are reacted under nitrogen protection, when isocyanates in reaction system
When the concentration of group is reduced to 1.2mol/L, stops reaction, obtain having the reactive hydrophobic polyurethane of terminal isocyanate groups molten
Liquid；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 24 when controlling spinning
DEG C, relative humidity 80%, voltage 30kV, it is 15cm to receive distance, and liquid supply speed 3mL/h, reception base material is copper mesh, is spun
The silk time is 2h, is made in solution jet fiber forming process, in reactive hydrophobic polyurethane and air with terminal isocyanate groups
Hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 60MPa, and water pressure resistance is
105kPa, vapor transfer rate 16000g/m2/d。
Embodiment 2
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：0.075mol polytetrahydrofuran ether glycol (relative molecular mass 1000) and 0.5mol toluene two is different
Cyanate and solvent dimethylacetylamide 200mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A, wherein
The total mass fraction of solute is 46%, reacts 1h under nitrogen protection, and reaction temperature is 50 DEG C, and mixing speed 150rpm is obtained
To the reaction system containing performed polymer, remaining isocyanate groups are 0.85mol in reaction system；
Second step：By the ends 0.15mol hydroxypropyl based polysiloxane, (molecular formula is HO (CH2)3[Si(CH3)2O]mSi(CH3)2
(CH2)3OH, relative molecular mass 2000) it is dissolved in solvents tetrahydrofurane 200mL, solution B is obtained, solution B is added drop-wise to
It is reacted in reaction system obtained by one step, rate of addition is 25 drops/min, and the total mass fraction of solute is in reaction process
56%, mixing speed 300rpm, reaction temperature are 60 DEG C, 1h are reacted under nitrogen protection, when isocyanates in reaction system
When the concentration of group is reduced to 0.9mol/L, stops reaction, obtain having the reactive hydrophobic polyurethane of terminal isocyanate groups molten
Liquid；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 28 when controlling spinning
DEG C, relative humidity 80%, voltage 40kV, it is 15cm to receive distance, and liquid supply speed 2mL/h, reception base material is aluminium foil, is spun
The silk time is 3h, is made in solution jet fiber forming process, in reactive hydrophobic polyurethane and air with terminal isocyanate groups
Hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 65MPa, and water pressure resistance is
120kPa, vapor transfer rate 15000g/m2/d。
Embodiment 3
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.45mol polyethylene glycol (relative molecular mass 2000) and 3mol toluene di-isocyanate(TDI)s and molten
Agent dimethylformamide 1050mL is added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A, wherein total matter of solute
It is 59% to measure score, reacts 2h under nitrogen protection, and reaction temperature is 60 DEG C, and mixing speed 150rpm is obtained containing pre-polymerization
The reaction system of body, remaining isocyanate groups are 5.1mol in reaction system；
Second step：By 1.2mol hexafluoros pentanediol (molecular formula HOCH2(CF2)3CH2OH) it is dissolved in solvent dimethyl formyl
In amine 100mL, obtain solution B, solution B be added drop-wise in the reaction system of the first step and reacted, rate of addition be 30 drop/
Min, the total mass fraction of solute is 61% in reaction process, mixing speed 200rpm, and reaction temperature is 75 DEG C, is protected in nitrogen
Shield is lower to react 1.5h, when the concentration of isocyanate groups in reaction system is reduced to 1.8mol/L, stops reaction, is had
The reactive hydrophobic polyurethane solution of terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 22 when controlling spinning
DEG C, relative humidity 90%, voltage 60kV, it is 20cm to receive distance, and liquid supply speed 6mL/h, reception base material is aluminium foil, is spun
The silk time is 1h, is made in solution jet fiber forming process, in reactive hydrophobic polyurethane and air with terminal isocyanate groups
Hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 75MPa, and water pressure resistance is
110kPa, vapor transfer rate 17000g/m2/d。
Embodiment 4
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.3mol poly adipate succinic acid esters dihydric alcohol (relative molecular mass 1000) and the different fluorine thats of 2mol
Ketone diisocyanate and solvent dimethylacetylamide 550mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A,
Wherein, the total mass fraction of solute is 59%, reacts 1h under nitrogen protection, and reaction temperature is 55 DEG C, and mixing speed is
200rpm obtains the reaction system containing performed polymer, and remaining isocyanate groups are 3.4mol in reaction system；
Second step：By 0.8mol octafluoros -1,6 hexylene glycol (molecular formula HOCH2(CF2)4CH2OH) it is dissolved in solvent dimethyl
In acetamide 100mL, solution B is obtained, solution B is added drop-wise in the reaction system of the first step and is reacted, rate of addition 30
Drop/min, the total mass fraction of solute is 61% in reaction process, and mixing speed 300rpm, reaction temperature is 80 DEG C, in nitrogen
1.5h is reacted under gas shielded, when the concentration of isocyanate groups in reaction system is reduced to 2.5mol/L, stops reaction, obtains
Reactive hydrophobic polyurethane solution with terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 24 when controlling spinning
DEG C, relative humidity 75%, voltage 90kV, it is 30cm to receive distance, and liquid supply speed 5mL/h, reception base material is parchamyn paper,
The spinning time is 1.2h, is made in solution jet fiber forming process, the reactive hydrophobic polyurethane with terminal isocyanate groups and sky
Hydrone in gas crosslinks reaction, obtains fiber base waterproof humidity-permeant film, and gained fiber film-strength is 55MPa, and water pressure resistance is
116kPa, vapor transfer rate 15000g/m2/d。
Embodiment 5
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By oneself two isocyanides of 0.3mol polytetrahydrofuran ether glycol (relative molecular mass 1000) and 2mol1,6-
Acid esters and solvent dimethylformamide 500mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A, wherein molten
The total mass fraction of matter is 58%, reacts 1h under nitrogen protection, and reaction temperature is 50 DEG C, and mixing speed 200rpm is obtained
Reaction system containing performed polymer, remaining isocyanate groups are 3.4mol in reaction system；
Second step：By 0.8mol octafluoros -1,6 hexylene glycol (molecular formula HOCH2(CF2)4CH2OH) it is dissolved in solvent dimethyl
In formamide 50mL, solution B is obtained, solution B is added drop-wise in the reaction system of the first step and is reacted, rate of addition 20
Drop/min, the total mass fraction of solute is 62% in reaction process, and mixing speed 300rpm, reaction temperature is 75 DEG C, in nitrogen
1h is reacted under gas shielded, when the concentration of isocyanate groups in reaction system is reduced to 3mol/L, stops reaction, is had
The reactive hydrophobic polyurethane solution of terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 27 when controlling spinning
DEG C, relative humidity 78%, voltage 55kV, it is 15cm to receive distance, and liquid supply speed 4mL/h, reception base material is aluminium foil, is spun
The silk time is 1.5h, is made in solution jet fiber forming process, reactive hydrophobic polyurethane and air with terminal isocyanate groups
In hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 70MPa, and water pressure resistance is
108kPa, vapor transfer rate 17000g/m2/d。
Embodiment 6
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.45mol poly adipate succinic acid esters dihydric alcohol (relative molecular mass 1000) and 3mol dimethyl
It being added in four-hole bottle in biphenyl diisocyanate and solvent ethyl acetate 923mL, stirring makes it fully dissolve, and obtains solution A,
Wherein, the total mass fraction of solute is 60%, reacts 1h under nitrogen protection, and reaction temperature is 50 DEG C, and mixing speed is
200rpm obtains the reaction system containing performed polymer, and remaining isocyanate groups are 5.1mol in reaction system；
Second step：By 1.2mol tetrafluoros butanediol (molecular formula HOCH2(CF2)2CH2OH) it is dissolved in solvent methyl pyrrolidines
In ketone 50mL, obtain solution B, solution B be added drop-wise in the reaction system of the first step and reacted, rate of addition be 25 drop/
Min, the total mass fraction of solute is 62% in reaction process, mixing speed 300rpm, and reaction temperature is 65 DEG C, is protected in nitrogen
Shield is lower to react 1h, when the concentration of isocyanate groups in reaction system is reduced to 1.5mol/L, stops reaction, obtains having different
The reactive hydrophobic polyurethane solution of cyanic acid ester terminal；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 30 when controlling spinning
DEG C, relative humidity 75%, voltage 65kV, it is 18cm to receive distance, and liquid supply speed 8mL/h, reception base material is parchamyn paper,
The spinning time is 0.8h, is made in solution jet fiber forming process, the reactive hydrophobic polyurethane with terminal isocyanate groups and sky
Hydrone in gas crosslinks reaction, obtains fiber base waterproof humidity-permeant film, and gained fiber film-strength is 62MPa, and water pressure resistance is
125kPa, vapor transfer rate 16000g/m2/d。
Embodiment 7
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.15mol polytetrahydrofuran ether glycol (relative molecular mass 2000) and 1mol dimethyl diphenyls
Diisocyanate and solvent ethyl acetate 450mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A, wherein
The total mass fraction of solute is 58%, reacts 0.5h under nitrogen protection, and reaction temperature is 55 DEG C, mixing speed 150rpm,
The reaction system containing performed polymer is obtained, remaining isocyanate groups are 1.7mol in reaction system；
Second step：By 0.4mol tetrafluoros butanediol (molecular formula HOCH2(CF2)2CH2OH) it is dissolved in solvent methyl pyrrolidines
In ketone 100mL, solution B is obtained, solution B is added drop-wise in the reaction system of the first step, rate of addition is 25 drops/min, is reacted
Solute total mass fraction is 55% in journey, and mixing speed 300rpm, reaction temperature is 75 DEG C, reacts 1h under nitrogen protection,
When the concentration of isocyanate groups in reaction system is reduced to 1mol/L, stops reaction, obtain that there are terminal isocyanate groups
Reactive hydrophobic polyurethane solution；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 30 when controlling spinning
DEG C, relative humidity 80%, voltage 100kV, it is 28cm to receive distance, and liquid supply speed 2mL/h, reception base material is copper mesh,
The spinning time is 3h, is made in solution jet fiber forming process, reactive hydrophobic polyurethane and air with terminal isocyanate groups
In hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 74MPa, and water pressure resistance is
130kPa, vapor transfer rate 18000g/m2/d。
Embodiment 8
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.15mol polyethylene glycol (relative molecular mass 2000) the xyxylene isocyanates between 1mol
It is added in four-hole bottle with solvent methyl pyrrolidones 300mL, stirring makes it fully dissolve, and obtains solution A, wherein solute
Total mass fraction is 60%, reacts 3h under nitrogen protection, and reaction temperature is 60 DEG C, and mixing speed 300rpm is contained
The reaction system of performed polymer, remaining isocyanate groups are 1.7mol in reaction system；
Second step：By 0.4mol1H, 1H, 8H, 12 fluoro- 1,8- ethohexadiols (molecular formula HOCH of 8H-2(CF2)6CH2OH)
It is dissolved in solvent dimethylformamide 100mL, obtains solution B, solution B is added drop-wise in the reaction system of the first step, speed is added dropwise
Degree is 30 drops/min, is remained in the reaction system in the hydroxyl group and the first step contained by Fluorinated dihydric alcohol being added in second step
The molar ratio of remaining isocyanate groups is 1: 2, and solute total mass fraction is 60% in reaction process, and mixing speed is
200rpm, reaction temperature are 70 DEG C, 3h are reacted under nitrogen protection, when the concentration of isocyanate groups in reaction system is reduced to
When 2mol/L, stops reaction, obtain the reactive hydrophobic polyurethane solution with terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 25 when controlling spinning
DEG C, relative humidity 90%, voltage 40kV, it is 26cm, liquid supply speed 10mL/h to receive distance, and it is glossy to receive base material
Paper, the spinning time be 0.6h, make in solution jet fiber forming process, with terminal isocyanate groups reactive hydrophobic polyurethane with
Hydrone in air crosslinks reaction, obtains fiber base waterproof humidity-permeant film, and gained fiber film-strength is 78MPa, water pressure resistance
For 145kPa, vapor transfer rate 20000g/m2/d。
Embodiment 9
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.3mol polypropylene glycols (relative molecular mass 1000) and 2mol dicyclohexyl methyl hydride diisocyanates
Ester and solvent methyl pyrrolidones 600mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A, wherein solute
Total mass fraction be 57%, react 2h under nitrogen protection, reaction temperature is 45 DEG C, and mixing speed 300rpm is contained
There is a reaction system of performed polymer, remaining isocyanate groups are 3.4mol in reaction system；
Second step：By 0.6mol1H, 1H, 10H, 10H- perfluors -1,10- decanediol (molecular formula HOCH2(CF2)8CH2OH it) is dissolved in solvent dimethylacetylamide 200mL, obtains solution B, solution B is added drop-wise in the reaction system of the first step,
Rate of addition is 30 drops/min, and solute total mass fraction is 58% in reaction process, mixing speed 300rpm, and reaction temperature is
70 DEG C, 1.5h is reacted under nitrogen protection, when the concentration of isocyanate groups in reaction system is reduced to 2.3mol/L, is stopped
Reaction, obtains the reactive hydrophobic polyurethane solution with terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 32 when controlling spinning
DEG C, relative humidity 95%, voltage 75kV, it is 23cm to receive distance, and liquid supply speed 7.5mL/h, reception base material is nonwoven
Cloth, the spinning time be 0.8h, make in solution jet fiber forming process, with terminal isocyanate groups reactive hydrophobic polyurethane with
Hydrone in air crosslinks reaction, obtains fiber base waterproof humidity-permeant film, and gained fiber film-strength is 75MPa, water pressure resistance
For 132kPa, vapor transfer rate 15000g/m2/d。
Embodiment 10
A kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, the specific steps are：
The first step：By 0.24mol polytetrahydrofuran ether glycol (relative molecular mass 1000) and 1.5mol isophorones
Diisocyanate and solvent dimethylformamide 400mL are added in four-hole bottle, and stirring makes it fully dissolve, and obtains solution A,
In, the total mass fraction of solute is 60%, reacts 1h under nitrogen protection, and reaction temperature is 40 DEG C, mixing speed 200rpm,
The reaction system containing performed polymer is obtained, remaining isocyanate groups are 2.52mol in reaction system；
Second step：By 0.5mol1H, 1H, 9H, 9H- perfluor -1,9- nonane glycol (molecular formula HOCH2(CF2)7CH2OH)
It is dissolved in solvent dimethylformamide 100mL, obtains solution B, solution B is added drop-wise in the reaction system of the first step, speed is added dropwise
It is 20 drops/min to spend, and solute total mass fraction is 62% in reaction process, mixing speed 300rpm, and reaction temperature is 80 DEG C,
2h is reacted under nitrogen protection, when the concentration of isocyanate groups in reaction system is reduced to 2.5mol/L, is stopped reaction, is obtained
To the reactive hydrophobic polyurethane solution with terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution of second step is subjected to electrostatic spinning, temperature is 35 when controlling spinning
DEG C, relative humidity 70%, voltage 60kV, it is 24cm to receive distance, and liquid supply speed 5mL/h, reception base material is aluminium foil, is spun
The silk time is 1.2h, is made in solution jet fiber forming process, reactive hydrophobic polyurethane and air with terminal isocyanate groups
In hydrone crosslink reaction, obtain fiber base waterproof humidity-permeant film, gained fiber film-strength is 65MPa, and water pressure resistance is
140kPa, vapor transfer rate 18000g/m2/d。
Claims (10)
1. a kind of electrostatic spinning of fiber base waterproof humidity-permeant film/moisturecuring preparation method, which is characterized in that including：
The first step：Diisocyanate and oligomer dihydric alcohol are dissolved in solvent, obtain solution A, the diisocyanate with
Oligomer dihydric alcohol is reacted under nitrogen protection, obtains the reaction system containing performed polymer；
Second step：Fluorinated dihydric alcohol is dissolved in solvent, either end hydroxypropyl based polysiloxane is dissolved in solvent or by fluorine-containing two
First alcohol and end hydroxypropyl based polysiloxane are dissolved in solvent, obtain solution B, solution B is added to the reaction system obtained by the first step
In reacted, obtain the reactive hydrophobic polyurethane solution with terminal isocyanate groups；
Third walks：The reactive hydrophobic polyurethane solution with terminal isocyanate groups of second step is subjected to electrostatic spinning, control
The temperature of spinning environment is 20-35 DEG C, relative humidity 70-95%, is made in solution jet fiber forming process, has isocyanates
The reactive hydrophobic polyurethane of end group is crosslinked with the hydrone in air to react, and obtains fiber base waterproof humidity-permeant film.
2. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
The tensile strength of the fiber base waterproof humidity-permeant film is reached up to 50MPa or more, water pressure resistance up to 100kPa or more, vapor transfer rate
15000g/m2/ d or more.
3. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
Diisocyanate in the first step is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), the own diisocyanates of 1,6-
Ester, isoflurane chalcone diisocyanate, dicyclohexyl methyl hydride diisocyanate, benzene dimethylene diisocyanate, to two isocyanide of benzene
In acid esters, dimethyl diphenyl diisocyanate, xyxylene isocyanates, liquefied mdi, TDI dimers and HDI dimers
A kind of or arbitrary several combination.
4. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
Oligomer dihydric alcohol in the first step is polyethylene glycol, polypropylene glycol, polytetramethylene ether diol, tetrahydrofuran-oxidation
Propylene is copolymerized dihydric alcohol, polyethylene glycol adipate dihydric alcohol, polypropylene glycol adipate dihydric alcohol, poly adipate succinic acid ester
Dihydric alcohol, polydiethylene glycol adipate dihydric alcohol, polyneopentyl glycol adipate dihydric alcohol, poly-epsilon-caprolactone glycol, poly- carbon
Acid esters dihydric alcohol, polyolefin dihydric alcohol and one kind in polyacrylate dihydric alcohol or arbitrary several combination.
5. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
The molar ratio of oligomer dihydric alcohol and diisocyanate in the first step is 1：4-8, the mass fraction of solute is in solution A
40-60%。
6. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
The reaction condition of the first step is：Mixing speed is 100-300rpm, and reaction temperature is 40-60 DEG C, reaction time 0.5-
3h。
7. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
Institute in Fluorinated dihydric alcohol, end hydroxypropyl based polysiloxane or Fluorinated dihydric alcohol and end hydroxypropyl based polysiloxane in the second step
The molar ratio of remaining isocyanate groups is 1 in the reaction system obtained by hydroxyl group and the first step contained：2-4, solution
Total mass fraction be 50-70%.
8. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
The reaction condition of the second step is：Mixing speed is 200-300rpm, and reaction temperature is 60-80 DEG C, reaction time 0.5-
3h。
9. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
The feed postition of solution B in the second step is to be added dropwise, and rate of addition is 20-30 drops/min.
10. the electrostatic spinning of fiber base waterproof humidity-permeant film as described in claim 1/moisturecuring preparation method, which is characterized in that
Electrospinning conditions in third step are：Voltage is 10-100kV, reception distance is 10-30cm, liquid supply speed 0.1-
10mL/h。
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| CN107587268B (en) * | 2017-08-24 | 2020-08-11 | 东华大学 | Preparation method of environment-friendly solvent type electrostatic spinning waterproof moisture-permeable film |
| 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 |
| CN111455474B (en) * | 2020-03-23 | 2022-04-08 | 东华大学 | Wool-like crimped electrostatic spinning nanofiber and preparation method thereof |
| CN111850835B (en) * | 2020-06-17 | 2021-08-06 | 吉祥三宝高科纺织有限公司 | Processing method of heat-humidity comfortable nanofiber waterproof moisture-permeable film |
| CN114703600B (en) * | 2022-04-11 | 2023-02-07 | 江苏伊贝实业股份有限公司 | Preparation method of waterproof breathable polyurethane bootie lining film |
| CN115262089A (en) * | 2022-08-06 | 2022-11-01 | 安徽东锦服饰有限公司 | Production process of waterproof and moisture permeable composite fabric |
| CN116497602A (en) * | 2023-04-28 | 2023-07-28 | 江苏鸿鹏服饰有限公司 | Moisture-permeable and easily-dried sleeping bag fabric and preparation method thereof |
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