CN117385554A - Polyurethane nanofiber membrane, preparation system and preparation method - Google Patents
Polyurethane nanofiber membrane, preparation system and preparation method Download PDFInfo
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- CN117385554A CN117385554A CN202311671333.2A CN202311671333A CN117385554A CN 117385554 A CN117385554 A CN 117385554A CN 202311671333 A CN202311671333 A CN 202311671333A CN 117385554 A CN117385554 A CN 117385554A
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- nanofiber membrane
- polyurethane nanofiber
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 66
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 66
- 239000002121 nanofiber Substances 0.000 title claims abstract description 63
- 239000012528 membrane Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 116
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 238000009987 spinning Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 239000013538 functional additive Substances 0.000 claims abstract description 18
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 150000003077 polyols Chemical class 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002216 antistatic agent Substances 0.000 claims abstract description 5
- 239000003063 flame retardant Substances 0.000 claims abstract description 5
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 5
- 239000000080 wetting agent Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- 238000009826 distribution Methods 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- -1 zinc carboxylate Chemical class 0.000 claims description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- VFAAJFFHAACWTI-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-propylazanium;octadecanamide;nitrate Chemical compound [O-][N+]([O-])=O.CCC[N+](C)(C)CCO.CCCCCCCCCCCCCCCCCC(N)=O VFAAJFFHAACWTI-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- ITFGZZGYXVHOOU-UHFFFAOYSA-N n,n-dimethylmethanamine;methyl hydrogen sulfate Chemical compound C[NH+](C)C.COS([O-])(=O)=O ITFGZZGYXVHOOU-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- 235000010215 titanium dioxide Nutrition 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 229940113125 polyethylene glycol 3000 Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- 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
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
- D04H1/4358—Polyurethanes
-
- 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
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43838—Ultrafine fibres, e.g. microfibres
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a polyurethane nanofiber membrane, a preparation system and a preparation method, and belongs to the technical field of nanofiber membranes. The preparation method comprises the following steps of S1, reacting isocyanate with polyol A to obtain a component A; -NCO/-OH ratio greater than 2.5; mixing the polyol B, a chain extender, a catalyst and a functional additive to obtain a component B; the functional additive is one or more selected from flame retardant, anti-wetting agent, anti-static agent and reinforcing agent; s2, conveying the component A and the component B of the S1 to a micro-channel mixing reactor through a capillary liquid supply pipe for reaction to obtain a mixed liquid; and S3, spinning and solidifying the mixed solution of the step S2 to obtain the polyurethane nanofiber membrane. The preparation method of the invention obtains uniform and viscosity-controllable spinning solution and realizes the production of the solvent-free polyurethane nanofiber which is truly environment-friendly.
Description
Technical Field
The invention belongs to the technical field of nanofiber membranes, and particularly relates to a polyurethane nanofiber membrane, a preparation system and a preparation method.
Background
The polyurethane nanofiber membrane prepared by electrostatic spinning or high-speed turbulence assisted spinning has wide application prospect in the field of separation filtration and protection, the filtration and protection efficiency is mainly determined by the thickness of fibers, and generally, the filtration and protection efficiency is higher when the fiber size is reduced. The solution to be spun to obtain ultra-fine fibers requires a certain viscosity, generally the lower the viscosity the finer the fibers, but too low a viscosity may not result in continuous fibers or poor mechanical strength of the fibers. The traditional preparation method of the polyurethane nanofiber membrane comprises a solvent method and a hot melting method. The hot melt method is difficult to achieve high filtration or protection efficiency in the micron scale because of too high viscosity and the fibers prepared by electrospinning are relatively coarse. The solvent method utilizes an organic solvent to dissolve polyurethane, can reduce the solution viscosity by adjusting the concentration of the solvent to prepare fibers of tens to hundreds of nanometers, has high filtration and protection effects, but has the risks of flammability, explosiveness and environmental pollution.
Spinning using solvent-free polyols and isocyanates and additives by direct reaction or by semi-prepolymerization followed by reaction is a method which overcomes the need to avoid the use of solvents for spinning. At present, no report of directly mixing polyol, isocyanate and additives for mixed spinning is available, mainly because the system has rapid reaction process and great difficulty in viscosity regulation. In order to overcome the problem of high viscosity, CN 104532367A discloses a method for preparing polyurethane micro-nano fibers by solvent-free electrostatic spinning, which is characterized in that the ratio of-NCO/-OH is set to be 1.1-2.1 in the semi-prepolymerization degradation reaction, and then the semi-prepolymerization degradation reaction is carried out with a chain extender and the like, and the viscosity is reduced by taking the chain extender as a diluent to carry out electrostatic spinning, but the fiber obtained by the method is thick in size and can only reach micron-sized and the fiber is very uneven. One reason is that the viscosity of the reaction system increases slowly and then rapidly, and the viscosity of the system increases extremely rapidly after the system reaches a certain viscosity and begins spinning; the second reason is that the viscosity of the solution, which is subsequently reacted but not consumed, is higher and higher, since the consumption rate of the electrospinning solution is very slow (less than 10 g/min), the resulting fibers are coarse and heterogeneous.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the risks of solvent fire explosion and environmental pollution existing in the spinning based on an organic solvent system in the prior art; and the literature reports that solvent-free system spinning based on semi-prepolymerization reaction has the problems of large and uneven fiber size, uncontrollable viscosity and the like.
In order to solve the technical problems, the invention provides a polyurethane nanofiber membrane, a preparation system and a preparation method.
The first object of the invention is to provide a preparation method of a polyurethane nanofiber membrane, which comprises the following steps:
s1, reacting isocyanate with polyol A to obtain a component A; -NCO/-OH ratio greater than 2.5; the component A comprises 100 parts of isocyanate and 20-55 parts of polyol A;
mixing the polyol B, a chain extender, a catalyst and a functional additive to obtain a component B; the functional additive is one or more selected from flame retardant, anti-wetting agent, anti-static agent and reinforcing agent;
s2, conveying the component A and the component B which are described in the step S1 to a micro-channel mixing reactor through a capillary liquid supply pipe for reaction to obtain mixed liquid; the inner diameter of the capillary liquid supply pipe is 0.5mm-3mm; the inner diameter of the micro-channel is 0.5mm-3mm, and the total length is 8cm-20cm;
and S3, spinning and solidifying the mixed solution in the step S2 to obtain the polyurethane nanofiber membrane.
In one embodiment of the present invention, in S1, the component B comprises 20 to 60 parts by mass of polyol B, 5 to 15 parts by mass of chain extender, 0.05 to 1 part by mass of catalyst and 0.5 to 5 parts by mass of functional additive.
In one embodiment of the present invention, in S1, the isocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the polyol A is selected from polytetrahydrofuran ether glycol and/or polycaprolactone glycol.
In one embodiment of the present invention, in S1, the flame retardant is selected from one or more of isopropyl triphenyl phosphate, aluminum oxide, cresyl diphenyl phosphate, ammonium polyphosphate, and aluminum hydroxide; the anti-wetting agent is one or more selected from fluorinated acrylic ester, fluorinated polyurethane, silicone oil modified acrylic ester, silicone oil modified polyurethane, polydimethylsiloxane and aerosil; the antistatic agent is selected from one or more of trimethyl ammonium methyl sulfate salt, conductive carbon black, stearic acid amide propyl dimethyl hydroxyethyl ammonium nitrate and graphene; the reinforcing agent is selected from one or more of carbon nano tube, carbon black and titanium white.
In one embodiment of the invention, in S1, the polyol B is selected from polyethylene glycol and/or polypropylene glycol; the chain extender is selected from one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol and triethylene glycol; the catalyst is selected from dibutyl tin dilaurate, zinc carboxylate or stannous octoate.
Further, the molecular weight of the polyethylene glycol is 1000-3000; the molecular weight of polypropylene glycol is 1000-3000.
In one embodiment of the invention, in S2, the feed rate ratio of component a to component B is 1-3:1.
in one embodiment of the invention, in S2, the configuration of the microchannels of the microchannel mixing reactor is S-shaped.
The second object of the invention is to provide a polyurethane nanofiber membrane prepared by the preparation method.
In one embodiment of the invention, the polyurethane nanofiber membrane has a fiber diameter of 50nm to 1000nm.
A third object of the present invention is to provide a system for preparing a polyurethane nanofiber membrane, which prepares a polyurethane nanofiber membrane by using the preparation method of the polyurethane nanofiber membrane, the preparation system comprising:
the first stirring tank is used for preparing the component A, an outlet of the first stirring tank is communicated with an inlet of a first liquid distribution pipe, the component A is conveyed to a plurality of first capillary liquid supply pipes through the first liquid distribution pipe, and the component A is conveyed into the microchannel mixing reactor through the first capillary liquid supply pipes;
the outlet of the second stirring tank is communicated with the inlet of the second liquid distribution pipe, the second liquid distribution pipe is used for conveying the component B to a plurality of second capillary liquid supply pipes, and the component B is conveyed into the microchannel mixing reactor;
the component A and the component B react in the micro-channel mixing reactor, and the mixture from the micro-channel mixing reactor enters a spinning nozzle for spinning.
Compared with the prior art, the technical scheme of the invention has the following advantages:
according to the preparation method disclosed by the invention, the system viscosity is diluted and regulated by adopting isocyanate and polyalcohol with the proportion of-NCO/-OH being greater than 2.5, the mixture of semi-prepolymer containing isocyanate groups and isocyanate monomers is obtained after prepolymerization, and the excessive isocyanate monomers can be used as an organic solvent, so that the system viscosity is reduced. And then the component A and the component B are respectively sent into a micro-channel mixing reactor through capillary liquid supply pipes, micro liquid supply is carried out by utilizing the capillary liquid supply pipes, the rapid mixing and full mixing of the AB two reaction systems are promoted by utilizing the fold line structure of the micro-channel mixing reactor, and the AB two reaction systems are instantly fed into a spinning nozzle in a short range under proper viscosity, so that superfine fibers can be obtained through full stretching and thinning, meanwhile, the ultra-short range and ultra-micro mixing and liquid supply scheme ensures that the micro solution which is already mixed and reacted is rapidly consumed, and the high-viscosity and non-uniform solution cannot exist due to the retention of the solution, so that uniform and viscosity-controllable spinning solution is obtained, and the production of the polyurethane nanofiber without solvent is truly environment-friendly.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic diagram of a system for preparing a polyurethane nanofiber membrane of the present invention;
FIG. 2 is an electron microscopic view of the polyurethane nanofiber membrane prepared in example 1 of the present invention;
FIG. 3 is an electron microscopic view of the polyurethane nanofiber membrane prepared in example 2 of the present invention;
FIG. 4 is an electron microscopic view of the polyurethane nanofiber membrane prepared in example 3 of the present invention;
FIG. 5 is an electron microscopic view of the polyurethane nanofiber membrane prepared in example 4 of the present invention;
FIG. 6 is an electron microscopic view of the polyurethane nanofiber membrane prepared in comparative example 1 of the present invention;
FIG. 7 is an electron microscopic view of the polyurethane nanofiber membrane prepared in comparative example 2 of the present invention;
FIG. 8 is an electron microscopic view of the polyurethane nanofiber membrane prepared in comparative example 3 of the present invention;
FIG. 9 is an electron microscopic view of the polyurethane nanofiber membrane prepared in comparative example 4 of the present invention;
reference numerals illustrate: 1-first raw material tank, 2-second raw material tank, 3-third raw material tank, 4-fourth raw material tank, 5-measuring pump, 61-first agitator tank, 62-second agitator tank, 7-first liquid distribution pipe, 8-second liquid distribution pipe, 91-first capillary liquid supply pipe, 92-second capillary liquid supply pipe, 10-microchannel mixing reactor, 11-spinning nozzle, 12-stainless steel heating belt, and 13-light wave radiation pipe.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
In the present invention, a schematic diagram of a preparation system of a polyurethane nanofiber membrane is shown in fig. 1, including: a first stirring tank 61 for preparing the component A, wherein isocyanate is sent from a first raw material tank 1 and polyol A from a second raw material tank 2 to the first stirring tank 61 through a metering pump 5, an outlet of the first stirring tank 61 is communicated with an inlet of a first liquid distribution pipe 7, and is sent to a plurality of first capillary liquid supply pipes 91 and second capillary liquid supply pipes 921 through the first liquid distribution pipe 7, and the component A of the first liquid supply pipes 91 and the second capillary liquid supply pipes 921 is sent to the micro-channel mixing reactor 10;
a second stirring tank 62 for preparing a component B, wherein the polyol B is sent from a third raw material tank 3 and a chain extender/catalyst/functional additive to the second stirring tank 62 through a metering pump 5 from a fourth raw material tank 4, the outlet of the second stirring tank 62 is communicated with the inlet of a second liquid distribution pipe 8, and is sent to a plurality of first capillary liquid supply pipes 91 and second capillary liquid supply pipes 92 through the second liquid distribution pipe 8, and the component B of the component B is sent to the micro-channel mixing reactor 10 through the first capillary liquid supply pipes 91 and the second capillary liquid supply pipes 922; the component A and the component B react in a micro-channel mixing reactor 10, the mixture coming out of the micro-channel mixing reactor 10 enters a spinning nozzle 11 for spinning, a stainless steel heating belt 12 is taken as a receiving device, and the mixture is solidified under the action of a light wave radiant tube 12, so that the polyurethane nanofiber membrane is obtained.
In the present invention, the functional additive used in examples and comparative examples was alumina unless otherwise specified.
Example 1
The invention relates to a polyurethane nanofiber membrane and a preparation method thereof, which specifically comprise the following steps:
s1, delivering isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (52 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 2.6:1;
polyethylene glycol 2000 (40 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the components B after micro-channel mixing (the configuration of the micro-channel is S-shaped, the inner diameter of the micro-channel is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, solidifying the fibers under the action of a light wave radiation pipe 12, and obtaining the polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 200nm-500nm (figure 2), and the filtering efficiency of sodium chloride particles of 0.3 mu m is 99.13%.
Example 2
The invention relates to a polyurethane nanofiber membrane and a preparation method thereof, which specifically comprise the following steps:
s1, delivering isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (52 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 2.6:1;
polyethylene glycol 2000 (20 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the components B after micro-channel mixing (the configuration of the micro-channel is S-shaped, the inner diameter of the micro-channel is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, solidifying the fibers under the action of a light wave radiation pipe 12, and obtaining the polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 100nm-400nm (figure 3), and the filtering efficiency of sodium chloride particles of 0.3 mu m is 99.53%.
Example 3
The invention relates to a polyurethane nanofiber membrane and a preparation method thereof, which specifically comprise the following steps:
s1, feeding isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (20 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the proportion of-NCO/-OH is about 6.8:1, a step of;
polyethylene glycol 3000 (30 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the component B after micro-channel mixing (the configuration of the micro-channel is S-shaped, the inner diameter of the micro-channel is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, and solidifying the fiber under the action of a light wave radiation pipe 12 to obtain the polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 200nm-800nm (figure 4).
Example 4
The invention relates to a polyurethane nanofiber membrane and a preparation method thereof, which specifically comprise the following steps:
s1, feeding isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (20 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the proportion of-NCO/-OH is about 6.8:1, a step of;
polyethylene glycol 2000 (20 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/zinc carboxylate (0.4 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the component B after micro-channel mixing (the configuration of the micro-channel is S-shaped, the inner diameter of the micro-channel is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, and solidifying the fiber under the action of a light wave radiation pipe 12 to obtain the polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 300nm-700nm (figure 5).
Comparative example 1
S1, delivering isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (52 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 2.6:1;
polyethylene glycol 2000 (40 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, respectively, mixing the components A and the component B through micro-channels, rapidly reacting (the configuration of the micro-channels is S-shaped, the inner diameter of the micro-channels is 5mm, and the total length is 10 cm), then entering a spinning needle 11 for spinning, and solidifying the fibers under the action of a light wave radiation pipe 12 to obtain a polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 300nm-3000nm (figure 6), and the micro-channel has larger inner diameter, faster flow speed and uneven reaction; the filtration efficiency for 0.3 μm sodium chloride particles was 51.25%.
Comparative example 2
S1, delivering isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (20 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 6.8:1;
polyethylene glycol 2000 (40 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, respectively, quickly reacting the components A and the component B after mixing the micro-channels (the configuration of the micro-channels is S-shaped, the inner diameter of the micro-channels is 0.5mm and the total length is 50 cm), then entering a spinning needle 11 for spinning, and solidifying the fibers under the action of a light wave radiation pipe 12 to obtain the polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 800nm-5000nm (figure 7), and the total length of the micro-channels is too long, the reaction is complete, the molecular weight is higher, and the fibers are thicker; the filtration efficiency for 0.3 μm sodium chloride particles was 51.66%.
Comparative example 3
S1, delivering isophorone diisocyanate (100 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (20 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 for stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 6.8:1;
polyethylene glycol 2000 (40 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively feeding the component A and the component B into a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (the liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively feeding the components A and the component B into a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the components B after mixing the micro-channels (the configuration of the micro-channels is S-shaped, the inner diameter of the micro-channels is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, and solidifying the fibers under the action of a light wave radiation pipe 12 to obtain a polyurethane nanofiber membrane, wherein the fiber diameter of the polyurethane nanofiber membrane is about 300nm-4000nm (figure 8), and the reaction is uneven due to the fact that the inner diameter of the capillary liquid supply pipe is too large, the capillary resistance is too fast, and the gravity flow speed is too fast; the filtration efficiency for 0.3 μm sodium chloride particles was 56.37%.
Comparative example 4
S1, transferring isophorone diisocyanate (70 parts by mass) from a first raw material tank 1 and polytetrahydrofuran ether glycol (52 parts by mass) from a second raw material tank 2 to a first stirring tank 61 through a metering pump 5 to carry out stirring reaction to obtain a component A, wherein the ratio of-NCO/-OH is about 1.8:1.
Polyethylene glycol 2000 (20 parts by weight) was fed from the third raw material tank 3, 1, 4-butanediol chain extender (8 parts by weight)/dibutyltin dilaurate (0.8 parts by weight)/functional additive (1 part by weight) from the fourth raw material tank 4 to the second stirring tank 62 through the metering pump 5 to be mixed to obtain component B.
S2, respectively delivering the component A and the component B to a first liquid distribution pipe 7 and a second liquid distribution pipe 8, indirectly controlling the liquid supply speed (liquid supply speed ratio is 1:1) of the first liquid distribution pipe 7 and the second liquid distribution pipe 8 through metering pumps, respectively delivering the components A and the component B to a micro-channel mixing reactor 10 (the inner diameter of the capillary liquid supply pipe is 0.5 mm) through a first capillary liquid supply pipe 91 and a second capillary liquid supply pipe 92, quickly reacting the components A and the components B after mixing the micro-channels (the configuration of the micro-channels is S-shaped, the inner diameter of the micro-channels is 0.5mm and the total length is 10 cm), then entering a spinning needle 11 for spinning, solidifying the fiber under the action of a light wave radiation pipe 12, and basically obtaining the micro-ball with the diameter of 5-20 micrometers (figure 9) due to the small proportion of-NCO/-OH and the large solution viscosity, and the filtering efficiency of 0.3 mu m sodium chloride particles is 70.5%.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The preparation method of the polyurethane nanofiber membrane is characterized by comprising the following steps of:
s1, reacting isocyanate with polyol A to obtain a component A; -NCO/-OH ratio greater than 2.5; the component A comprises 100 parts of isocyanate and 20-55 parts of polyol A;
mixing the polyol B, a chain extender, a catalyst and a functional additive to obtain a component B; the functional additive is one or more selected from flame retardant, anti-wetting agent, anti-static agent and reinforcing agent;
s2, conveying the component A and the component B which are described in the step S1 to a micro-channel mixing reactor through a capillary liquid supply pipe for reaction to obtain mixed liquid; the inner diameter of the capillary liquid supply pipe is 0.5mm-3mm; the inner diameter of the micro-channel is 0.5mm-3mm, and the total length is 8cm-20cm;
and S3, spinning and solidifying the mixed solution in the step S2 to obtain the polyurethane nanofiber membrane.
2. The method for preparing a polyurethane nanofiber membrane according to claim 1, wherein in S1, the component B comprises 20-60 parts by mass of polyol B, 5-15 parts by mass of chain extender, 0.05-1 part by mass of catalyst and 0.5-5 parts by mass of functional additive.
3. The method for preparing a polyurethane nanofiber membrane according to claim 1, wherein in S1, the isocyanate is selected from one or more of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenylmethane diisocyanate; the polyol A is selected from polytetrahydrofuran ether glycol and/or polycaprolactone glycol.
4. The method of producing a polyurethane nanofiber membrane according to claim 1, wherein in S1, the polyol B is selected from polyethylene glycol and/or polypropylene glycol; the chain extender is selected from one or more of ethylene glycol, diethylene glycol, 1, 4-butanediol, neopentyl glycol and triethylene glycol; the catalyst is selected from dibutyl tin dilaurate, zinc carboxylate or stannous octoate.
5. The method of producing a polyurethane nanofiber membrane according to claim 1, wherein in S1, the flame retardant is selected from one or more of isopropyl triphenyl phosphate, aluminum oxide, toluene diphenyl phosphate, ammonium polyphosphate and aluminum hydroxide; the anti-wetting agent is one or more selected from fluorinated acrylic ester, fluorinated polyurethane, silicone oil modified acrylic ester, silicone oil modified polyurethane, polydimethylsiloxane and aerosil; the antistatic agent is selected from one or more of trimethyl ammonium methyl sulfate salt, conductive carbon black, stearic acid amide propyl dimethyl hydroxyethyl ammonium nitrate and graphene; the reinforcing agent is selected from one or more of carbon nano tube, carbon black and titanium white.
6. The method for producing a polyurethane nanofiber membrane according to claim 1, wherein in S2, the liquid feed rate ratio of component a to component B is 1 to 3:1.
7. the method of preparing a polyurethane nanofiber membrane according to claim 1, wherein in S2, the configuration of the micro channel mixing reactor is S-shaped.
8. A polyurethane nanofiber membrane prepared by the preparation method of any one of claims 1-7.
9. The polyurethane nanofiber membrane according to claim 8, wherein the fiber diameter of the polyurethane nanofiber membrane is 50nm-1000nm.
10. A system for preparing a polyurethane nanofiber membrane, wherein the polyurethane nanofiber membrane is prepared by the preparation method of the polyurethane nanofiber membrane according to any one of claims 1 to 7, the preparation system comprising:
the first stirring tank is used for preparing the component A, an outlet of the first stirring tank is communicated with an inlet of a first liquid distribution pipe, the component A is conveyed to a plurality of first capillary liquid supply pipes through the first liquid distribution pipe, and the component A is conveyed into the microchannel mixing reactor through the first capillary liquid supply pipes;
the outlet of the second stirring tank is communicated with the inlet of the second liquid distribution pipe, the second liquid distribution pipe is used for conveying the component B to a plurality of second capillary liquid supply pipes, and the component B is conveyed into the microchannel mixing reactor;
the component A and the component B react in the micro-channel mixing reactor, and the mixture from the micro-channel mixing reactor enters a spinning nozzle for spinning.
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