CN103981633A - Preparation method of porous nanofiber non-woven fabric - Google Patents
Preparation method of porous nanofiber non-woven fabric Download PDFInfo
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- CN103981633A CN103981633A CN201410195207.9A CN201410195207A CN103981633A CN 103981633 A CN103981633 A CN 103981633A CN 201410195207 A CN201410195207 A CN 201410195207A CN 103981633 A CN103981633 A CN 103981633A
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- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 67
- 239000002121 nanofiber Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 239000012749 thinning agent Substances 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000007664 blowing Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000009987 spinning Methods 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 10
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 carrene Chemical compound 0.000 claims description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
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- 239000007789 gas Substances 0.000 claims description 7
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002912 waste gas Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical class OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000002485 combustion reaction Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 150000002194 fatty esters Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Chemical class OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 150000005677 organic carbonates Chemical class 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical class [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Chemical class 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 17
- 239000003085 diluting agent Substances 0.000 description 13
- 238000005191 phase separation Methods 0.000 description 12
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000006184 cosolvent Substances 0.000 description 10
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 8
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- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GXCLVBGFBYZDAG-UHFFFAOYSA-N N-[2-(1H-indol-3-yl)ethyl]-N-methylprop-2-en-1-amine Chemical compound CN(CCC1=CNC2=C1C=CC=C2)CC=C GXCLVBGFBYZDAG-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to a preparation method of porous nanofiber non-woven fabric, and aims to provide a method capable of realizing large-scale preparation for porous nanofiber non-woven fabric. According to the technical scheme, the preparation method of the porous nanofiber non-woven fabric comprises the following steps in sequence: (1) stirring and dissolving polymers and a combined thinning agent uniformly in a reaction kettle at the temperature of 25-150 DEG C to prepare a polymer solution with the percent concentration of 10-60%, wherein the combined thinning agent is a mixture of a good solvent and a bad solvent, the mass ratio of the good solvent to the bad solvent is between 9: 1 and 1: 9, and the boiling point of the good solvent is lower than that of the bad solvent; (2) producing the polymer solution in the first step with melting blowing equipment to obtain primary non-woven fabric; (3) extracting and removing the combined thinning agent in the primary non-woven fabric in the second step and forming pores on fibers of the primary non-woven fabric, and drying to obtain the porous nanofiber non-woven fabric.
Description
Technical field
The invention belongs to nanometer field of new, be specifically related to a kind of the solvent evaporates pore-forming technology that is separated is combined with melt blown technology and prepares the method for porous nano-fibre nonwoven fabric, the nonwoven fabric making can be applicable to high-accuracy gas filtration and water treatment field.
Background technology
Superfine fibre nonwoven cloth, the nano fiber non-woven fabric of fibre diameter below 1000nm particularly, have that specific area is large, grammes per square metre is little, permeability is good, porosity is high, the little and advantage such as pore space structure connects mutually, solute diffusional resistance is little of hole between fiber, be the fiber product of a kind of high-performance, high added value.Nano fiber non-woven fabric is widely used in fields such as sewage disposal, air cleaning, warming heat insulation, health care, acoustic material, battery diaphragms, and the whole world is in explosive growth period to its consumption and demand.The sharpest edges of porous structure material are to be issued to more excellent result of use at more economical material usage.If introduce loose structure on nanofiber surface or inside, just can further increase specific area, improving product application performance, compare feltwork, porous fibre surface hydrophilic and hydrophobic more easily regulates, filter interdiction capability stronger, adsorption capacity and adsorptive selectivity are higher, as sensing material response and sensitivity more excellent.The feature of therefore comprehensive nano fiber non-woven fabric and loose structure, porous nano-fibre nonwoven fabric is expected to be applied to fine, ultraprecise, high efficiency separated adsorption filtration field, and separation as affine in protein, haze PM2.5 particulate filter, ultra-clean water are prepared etc.
At present, still there is no ripe technology realizing aspect nano fiber non-woven fabric production in enormous quantities, more promising manufacturing technique mainly contains two kinds of electrostatic spinning and melt blown technologies.But electrostatic spinning needs several kilovolts of volt high direct voltages even up to ten thousand, high to solution conductivity requirement, existing electrostatic spinning pilot plant can only be carried out normal temperature spinning, and this has limited its commercial application greatly.Melt blown technology is the manufacture method that has realized commercialization, superfine fibre nonwoven cloth on the largest scale, and it relies at a high speed, high temperature gas flow (often approaching melting point polymer) winding-up polymer melt is stretched rapidly it and a step prepares nonwoven fabric.Yet existing meltblown fibers diameter is many between 2～4 μ m, on nano-scale fiber, still there is certain difficulty preparing, this be mainly because: pure melt viscosity is large, and jet stretchings/whip is moving difficult; Experiment is observed and is found that jet temperature temperature range of decrease when leaving die head 2cm surpasses 200 ℃, and jet solidifies rapidly.Adopt melt-blowing equipment to carry out polymer solution jet spinning, can obtain Nano grade fabric nonwoven cloth, but fiber is smooth, there is no pore space structure.The introducing of loose structure can, by add inconsistent inorganic nano-particle or polymer in meltblown polymer master batch, then carry out selective removal pore-forming by the method for dissolution with solvents or calcining; But the method can cause fibre machinery performance greatly to decline and exist dissolving incomplete problem, and fibre diameter is also at micron order.Bibliographical information receives the mode of spinning jet and prepares porous fibre by bathing with non-solvent, but fibre diameter is even thicker between 3～5 μ m; If this is that solvent evaporates speed is too fast because fibre diameter reaches Nano grade, that cannot realize that solvent-nonsolvent exchange causes is separated and can only obtains feltwork.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned background technology, provide a kind of the solvent evaporates pore-forming technology that is separated is combined with melt blown technology, realize the method for the extensive preparation of porous nano-fibre nonwoven fabric.
The technical solution adopted in the present invention is: a kind of preparation method of porous nano-fibre nonwoven fabric, carries out successively according to following steps:
(1) by polymer and composite thinning agent at 25～150 ℃ of temperature in reactor stirring and dissolving even, make mass percent concentration and be 10～60% polymer solution; Described composite thinning agent is the mixture of good solvent and poor solvent, and the mass ratio of good solvent and poor solvent is between 9:1～1:9, and described good solvent boiling point is lower than poor solvent boiling point;
(2) polymer solution in step 1 is produced and obtained nascent nonwoven fabric with melt-blowing equipment;
(3) pore-forming on composite thinning agent in the nascent nonwoven fabric of step 2 fiber in nascent nonwoven fabric is removed in extraction, obtains porous nano-fibre nonwoven fabric after dry.
Polymer used in the present invention requires fibre-forming performance more excellent, can be dissolved in good solvent at normal temperatures, be at least one in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, ethylene-vinyl alcohol copolymer, polyether sulfone, polyacrylonitrile, polysulfones, polyester, polystyrene, polyurethane, polyamide, polyether-ether-ketone, polyvinyl alcohol, polyimides, polymethyl methacrylate, polyvinyl butyral, cellulose acetate, polyvinyl chloride.In the present invention, the initial mass percent concentration of polymer in mixture is 10～60%: excessive concentration, there is gelation phase process, and cannot pore-forming; Concentration is too low, and fibrous fracture in spray silk process, cannot form fiber and pile up nonwoven fabric construct, and be that pearl fiber or granule are piled up form.
Good solvent used in the present invention has the solvent of fine solubility at normal temperatures to described polymer, a kind of in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, acetone, triethyl phosphate, sulfolane, carrene, formic acid, chloroform, trifluoroacetic acid, ethyl acetate, oxolane, dimethylbenzene, or the mixing of two or more arbitrary proportions.
The poor solvent using in composite thinning agent in the present invention for boiling point above and can not dissolve the liquid or solid of described polymer at normal temperatures at 180 ℃, be specially polyethylene glycol and (be mainly Macrogol 200, PEG400 and Macrogol 600), higher alcohols, polyalcohols, glycol, phthalate, monoglyceride class, benzoates, organic carbonate class, citric acid ester type, high-grade fatty ester class, butyrolactone, butyl acetate, maleic anhydride, benzophenone, polymine, benzophenone, calcium stearate, mineral oil, tetramethyl sulfone, methyl iso-butyl ketone (MIBK), glycol monoethyl ether acetate, solid paraffin, dimethyl sulfone, crude vegetal, higher alkane, higher fatty acids, high fatty amine, cyclohexanone, isopropylamine alcohol, aromatic hydrocarbon, diphenyl sulphone (DPS), diphenyl ether, a kind of in benzaldehyde, or the mixing of two or more arbitrary proportions.Poor solvent further can be subdivided into again two kinds of non-solvent and cosolvents, and wherein non-solvent at high temperature also can not dissolve polymer, and cosolvent at high temperature can dissolve polymer but separated out under room temperature.According to the difference of the difference of type of polymer used and dissolution with solvents ability, above-mentioned poor solvent can be called respectively non-solvent or cosolvent, as the higher alcohol tetradecanol non-solvent that is polyacrylonitrile, and is polyacrylic cosolvent.
The mass ratio of described good solvent and poor solvent is preferably between 9:1～1:5.
Melt-blowing equipment used in the present invention is conventional whole complete production unit, spinning technology parameter is slit shower nozzle, spinning nozzle diameter 0.2～0.85mm, 30 °～60 ° of air drain angles, slit width 0.35～0.65mm, 25～160 ℃ of die temperature, 25～180 ℃ of hot air temperatures, gas pressure 0.05～0.5Mpa, receiving range 8～30cm, spinning speed 25～150kg/h, can select technological parameter according to actual conditions.
Thereby pore-forming on the fiber with the diluent in the nascent nonwoven fabric of extractant removal in this nonwoven fabric, extraction process adopts conventional impregnation technology to realize, and also can for example, according to the described method of related documents (Chinese patent 200810172232.X, Chinese patent 201010150961.2, Chinese patent 201320634857.X, Chinese patent 200610113814.1), realize.After extraction bone dry (conventional heating drying process), obtain porous nano-fibre nonwoven fabric, wherein nonwoven fabric fabric width is 0.6～3.2m, and grammes per square metre scope is 20～100g/m
2, average fibre diameter is 100nm～900nm, and nonwoven fabric porosity is 50%～80%, and single fiber porosity is 20%～80%, and the distribution of sizes scope of fiber mesopore is 20nm～500nm.
Extractant used in the present invention is for dissolving the liquid that composite thinning agent can not dissolve polymer, be specially a kind of in water, ethanol, isopropyl alcohol, ethylene glycol, glycerine, n-hexane, acetone, butanone, butanols, methyl alcohol, benzinum or the mixing of two or more arbitrary proportions.
For the waste gas that melts and sprays production and extraction process generation, the present invention absorbs by spray column or waste gas absorption-combustion system is processed, and realizes safety, green production.
The porous nano-fibre nonwoven fabric preparation method who the present invention relates to, also may be used on going in electrostatic spinning technique, by normal temperature or high temperature electrospinning, can in laboratory scope, prepare a small amount of porous nano-fibre nonwoven fabric sample.
The porous nano-fibre nonwoven fabric preparation method who the present invention relates to, also can change the shower nozzle in complete melt-blowing equipment into internal diameter 0.1～0.4mm, the coaxial shower nozzle of external diameter 0.24～0.85mm, shower nozzle inside is logical high-speed air also, the high speed rotary-drum that is 1000～2500rpm using rotating speed is as gathering-device, just can prepare internal diameter 50nm～800nm, the Hollow nanofibre film of external diameter 100nm～900nm.Compare with the hollow-fibre membrane of existing diameter more than 100 μ m, can greatly improve wastewater treatment efficiency.
Key of the present invention is to have used the mixed diluent being comprised of good solvent and higher boiling poor solvent, and wherein the boiling point of poor solvent, only can a small amount of volatilization or volatilization hardly in jet motion process more than 180 ℃.Adding of composite thinning agent greatly reduces polymer malt viscosity, and jet stretching whip is moving to be strengthened, and makes meltblown fibers variation in diameter.In jet, vying each other between phase separation speed and solvent evaporates speed depended in the formation of loose structure, so a small amount of volatilization of poor solvent has guaranteed the generation of phase separation and the formation of loose structure in jet.In addition, adding of good solvent, greatly reduces polymer dissolution temperature and phase separation temperature, improved the stability of polymer solution, the moving time of jet stability whip extends greatly, and a large amount of volatilizations of good solvent are further refinement fiber, makes fibre diameter be down to nanoscale.
The invention has the beneficial effects as follows:
1) diluent is also the plasticizer in polymer processing, adding of Macrodilution agent can make polymer malt viscosity greatly reduce, be beneficial to and extrude and reduce meltblown fibers diameter, also can greatly reduce die head and the hot air temperature in production process, energy consumption is little and slow down depolymerization;
2) use of the mixed diluent that good solvent and higher boiling poor solvent form, greatly reduce polymer dissolution temperature and phase separation temperature, improved the stability of polymer solution, guaranteed in jet, phase separation to occur when good solvent volatilizees, the moving time of jet stability whip extends greatly, is successfully prepared nanometer porous fabric nonwoven cloth.
3) in porous nano-fibre nonwoven fabric, single fiber porosity is the highest can be 80%, and nonwoven fabric grammes per square metre is only original 20%, can greatly reduce consumption of raw materials amount.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph on Kynoar porous nano-fibre surface prepared in embodiment 1.
Fig. 2 is the scanning electron microscope (SEM) photograph on Kynoar porous nano-fibre surface prepared in embodiment 2.
Fig. 3 is the scanning electron microscope (SEM) photograph of polyvinylidene fluoride nanometer doughnut section prepared in embodiment 4.
The specific embodiment
The solvent evaporates pore-forming technology that is separated comprises thermic solvent evaporates (the thermally assisted evaporation phase separation that is separated, be called for short TAEPS) and two kinds of dry method solvent evaporates inversion of phases (dry phase inversion or air-cast), researcher's extensive concern caused in recent years.The basic principle of TAEPS is as follows: by polymer dissolution, in the mixed diluent being comprised of good solvent and cosolvent, (polymer good solvent system at normal temperatures can stable existence, polymer cosolvent system is at high temperature dissolved phase-splitting under low temperature), good solvent boiling point is lower than cosolvent, therefore along with the volatilization of mixed diluent, cosolvent and polymer content increase, cause phase separation temperature to raise bringing out thermic liquid-liquid (L-L) or solid-liquid (S-L) is separated, then with extractant, remove residual diluent, mixture Central Plains diluent takes up space and becomes hole.The basic principle of Air-cast is as follows: by polymer dissolution in the mixed diluent being formed by good solvent and non-solvent, good solvent boiling point is lower than non-solvent, therefore along with the volatilization of mixed diluent, non-solvent and polymer content increase, cause solution system generation phase separation (non-solvent induced phase separation, be called for short NIPS), then with extractant, remove residual diluent, mixture Central Plains diluent takes up space and becomes hole.By the solvent evaporates loose structure that pore-forming technology obtains that is separated, have porosity high, be difficult for forming the features such as defect, good mechanical property, pore-size distribution and porosity be controlled.
The present invention combines the solvent evaporates pore-forming technology that is separated and prepares porous nano-fibre nonwoven fabric with melt blown technology, polymer, good solvent, poor solvent, the solvent selection of applicable the method are all quite extensive, the permutation and combination of different polymer/composite thinning agent/extractants can obtain very many process conditions, but basic principle is constant, can obtain the porous nano-fibre nonwoven fabric of different type of polymer, fabric width and grammes per square metre, fibre diameter, fiber porosity, fiber pore-size distribution.Can be applicable to fine, ultraprecise, high efficiency separated adsorption filtration field, separation as affine in protein, haze PM2.5 particulate filter, ultra-clean water are prepared etc.
The whole technological process of production of the present invention is very simple, mainly comprises that polymer/diluent dissolves-melt and spray production-extraction diluent-dry.Below in conjunction with Figure of description, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1 Kynoar/dimethylacetylamide/n-butyl phthalate thermic solvent evaporates phase-separated system
Polymer raw material is that Su Wei produces Kynoar 6010, and the good solvent in composite thinning agent is dimethylacetylamide, and cosolvent is n-butyl phthalate, and extractant is ethanol.Kynoar mass percent concentration is 20%, and dimethylacetylamide mass percent concentration is 64%, and n-butyl phthalate mass percent concentration is 16%; At 85 ℃ of temperature, in reactor, stirring and dissolving is made homogeneous solution completely, and this solution at room temperature can stable existence.Homogeneous solution is melted and sprayed to production, technological parameter is slit shower nozzle, spinning nozzle diameter 0.25mm, 30 ° of air drain angles, slit width 0.42mm, 40 ℃ of die temperature, 50 ℃ of hot air temperatures, gas pressure 0.09Mpa, receiving range 25cm, spinning speed 100kg/h, nascent nonwoven fabric grammes per square metre is 100g/m
2, fabric width is 1.6m.In jet motion process, good solvent dimethylacetylamide volatilizees in a large number, and Kynoar and n-butyl phthalate content are increased, and phase separation temperature improves, and the inner generation of jet thermic solid-liquid phase is separated.Nascent nonwoven fabric is by conventional impregnating production-line equipment, use the ethanol continuous impregnating extraction residual dimethylacetylamide of part and a large amount of residual n-butyl phthalate, make the fiber pore-forming in this nonwoven fabric, the dry Kynoar porous nano-fibre nonwoven fabric that obtains, use sem observation surface topography, as shown in Figure 1.Porous nano-fibre nonwoven fabric grammes per square metre is 45g/m
2, average fibre diameter is 120nm, and nonwoven fabric porosity is 80%, and single fiber porosity is 55%, and the diameter distribution of fiber mesopore is 20nm～80nm.
Embodiment 2 Kynoar/dimethylacetylamide/n-butyl phthalate thermic solvent evaporates phase-separated system
Polymer raw material is that Su Wei produces Kynoar 1010, and the good solvent in composite thinning agent is dimethylacetylamide, and cosolvent is n-butyl phthalate, and extractant is n-hexane.Kynoar mass percent concentration is 20%, and dimethylacetylamide mass percent concentration is 25%, and n-butyl phthalate mass percent concentration is 55%.At 120 ℃ of temperature, in reactor, stirring and dissolving is made homogeneous solution completely, this solution can only be at 100 ℃ stable existence.Homogeneous solution is melted and sprayed to production, technological parameter is slit shower nozzle, spinning nozzle diameter 0.35mm, 40 ° of air drain angles, slit width 0.55mm, 110 ℃ of die temperature, 120 ℃ of hot air temperatures, gas pressure 0.2Mpa, receiving range 30cm, spinning speed 80kg/h, nascent nonwoven fabric grammes per square metre is 60g/m
2, fabric width is 2.4m.In jet motion process, the volatilization of good solvent dimethylacetylamide, phase separation temperature improves, and jet temperature is also reducing simultaneously, and it is separated to there is rapidly thermic solid-liquid phase in jet inside.Nascent nonwoven fabric is by conventional impregnating production-line equipment, use the n-hexane continuous impregnating extraction residual dimethylacetylamide of part and a large amount of residual n-butyl phthalate, make the fiber pore-forming in this nonwoven fabric, the dry Kynoar porous nano-fibre nonwoven fabric that obtains, use sem observation surface topography, as shown in Figure 2.Porous nano-fibre nonwoven fabric grammes per square metre is 15g/m
2, average fibre diameter is 800nm, and nonwoven fabric porosity is 70%, and single fiber porosity is 75%, and the diameter distribution of fiber mesopore is 100nm～300nm.
Embodiment 3 polyacrylonitrile/dimethyl formamide/tetradecanol dry method solvent evaporates inversion of phases system
Polymer raw material is the polyacrylonitrile of number-average molecular weight 160,000, and the good solvent in composite thinning agent is dimethyl formamide, and non-solvent is tetradecanol, and extractant is acetone.Polyacrylonitrile mass percent concentration is 15%, and dimethyl formamide mass percent concentration is 65%, and tetradecanol mass percent concentration is 20%.At 60 ℃ of temperature, in reactor, stirring and dissolving is made homogeneous solution completely, and this solution at room temperature can stable existence.Homogeneous solution is melted and sprayed to production, technological parameter is slit shower nozzle, spinning nozzle diameter 0.42mm, 30 ° of air drain angles, slit width 0.55mm, 25 ℃ of die temperature, 30 ℃ of hot air temperatures, gas pressure 0.15Mpa, receiving range 15cm, spinning speed 120kg/h, nascent nonwoven fabric grammes per square metre is 60g/m
2, fabric width is 3.2m.In jet motion process, good solvent dimethyl formamide volatilizees in a large number, and polyacrylonitrile and tetradecanol content are increased, and the inner non-solvent that occurs of jet causes liquid-liquid phase separation.The nascent nonwoven fabric of collecting floods 2h, 1h and 30min successively in 3 acetone grooves, for extraction (extraction of batch (-type) dipping) the residual dimethyl formamide of part and a large amount of residual tetradecanol, make the fiber pore-forming in this nonwoven fabric, the dry polyacrylonitrile porous nano-fibre nonwoven fabric that obtains.Porous nano-fibre nonwoven fabric grammes per square metre is 18g/m
2, average fibre diameter is 350nm, and nonwoven fabric porosity is 65%, and single fiber porosity is 65%, and the diameter distribution of fiber mesopore is 80nm～150nm.
Embodiment 4 Kynoar/dimethylacetylamide/n-butyl phthalate thermic solvent evaporates phase-separated system
Basic technology parameter and embodiment 2 are same, and melt-blowing equipment is used coaxial shower nozzle instead, and spinning nozzle internal diameter is 0.25mm, and external diameter is 0.35mm, and the high speed rotary-drum that is 1200rpm with rotating speed is as gathering-device.Under liquid nitrogen, quench disconnected, with scanning electron microscopic observation Hollow nanofibre film cross-section morphology, as shown in Figure 3, preparing internal diameter is 700nm, the Hollow nanofibre film that external diameter is 800nm, and all the other character and embodiment 2 are same.
Above-described embodiment is only explanation technical conceive of the present invention and feature, its objective is to allow to be familiar with these those skilled in the art and can to understand content of the present invention enforcement according to this, can not limit the scope of the invention with this.Any those skilled in the art are not departing within the scope of technical solution of the present invention; when can utilizing the technology contents of above-mentioned announcement to make a little change or being modified to the equivalent embodiment of equivalent variations; in every case be the content that does not depart from technical solution of the present invention; any simple modification, equivalent variations and the modification above embodiment done according to technical spirit of the present invention, within all should being encompassed in protection scope of the present invention.
Claims (9)
1. a preparation method for porous nano-fibre nonwoven fabric, carries out successively according to following steps:
(1) by polymer and composite thinning agent at 25～150 ℃ of temperature in reactor stirring and dissolving even, make mass percent concentration and be 10～60% polymer solution; Described composite thinning agent is the mixture of polymer good solvent and poor solvent, and the mass ratio of good solvent and poor solvent is between 9:1～1:9, and described good solvent boiling point is lower than poor solvent boiling point;
(2) polymer solution in step 1 is produced and obtained nascent nonwoven fabric with melt-blowing equipment;
(3) pore-forming on composite thinning agent in the nascent nonwoven fabric of step 2 fiber in nascent nonwoven fabric is removed in extraction, obtains porous nano-fibre nonwoven fabric after dry.
2. the preparation method of porous nano-fibre nonwoven fabric according to claim 1, is characterized in that described polymer is at least one in Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, ethylene-vinyl alcohol copolymer, polyether sulfone, polyacrylonitrile, polysulfones, polyester, polystyrene, polyurethane, polyamide, polyether-ether-ketone, polyvinyl alcohol, polyimides, polymethyl methacrylate, polyvinyl butyral, cellulose acetate, polyvinyl chloride.
3. the preparation method of porous nano-fibre nonwoven fabric according to claim 1, it is characterized in that described polymer good solvent is a kind of in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, acetone, triethyl phosphate, sulfolane, carrene, formic acid, chloroform, trifluoroacetic acid, ethyl acetate, oxolane, dimethylbenzene, or the mixing of two or more arbitrary proportions.
4. the preparation method of porous nano-fibre nonwoven fabric according to claim 1, it is characterized in that described poor solvent boiling point is more than 180 ℃, for polyethylene glycol, higher alcohols, polyalcohols, glycol, phthalate, monoglyceride class, benzoates, organic carbonate class, citric acid ester type, high-grade fatty ester class, butyrolactone, butyl acetate, maleic anhydride, benzophenone, polymine, benzophenone, calcium stearate, mineral oil, tetramethyl sulfone, methyl iso-butyl ketone (MIBK), glycol monoethyl ether acetate, solid paraffin, dimethyl sulfone, crude vegetal, higher alkane, higher fatty acids, high fatty amine, cyclohexanone, isopropylamine alcohol, aromatic hydrocarbon, diphenyl sulphone (DPS), diphenyl ether, a kind of in benzaldehyde, or the mixing of two or more arbitrary proportions.
5. the preparation method of porous nano-fibre nonwoven fabric according to claim 1, it is characterized in that described extractant is a kind of of water, ethanol, isopropyl alcohol, ethylene glycol, glycerine, n-hexane, acetone, butanone, butanols, methyl alcohol, benzinum, or the mixing of two or more arbitrary proportions.
6. the preparation method of porous nano-fibre nonwoven fabric according to claim 1, is characterized in that the mass ratio of described good solvent and poor solvent is between 9:1～1:5.
7. according to the preparation method of the porous nano-fibre nonwoven fabric described in claim 2 or 3 or 4 or 5 or 6, it is characterized in that the shower nozzle in described melt-blowing equipment is slit shower nozzle, spinning nozzle diameter 0.2～0.85mm, 30 °～60 ° of air drain angles, slit width 0.35～0.65mm, 25～160 ℃ of die temperature, 25～180 ℃ of hot air temperatures, gas pressure 0.05～0.5Mpa, receiving range 8～30cm, spinning speed 25～150kg/h.
8. the preparation method of porous nano-fibre nonwoven fabric according to claim 7, is characterized in that melting and spraying the composite thinning agent waste gas that production process produces, and by spray column, absorbs or waste gas absorption-combustion system is processed.
9. the preparation method of porous nano-fibre nonwoven fabric according to claim 8, it is characterized in that the shower nozzle employing internal diameter in described melt-blowing equipment is 0.1～0.4mm, external diameter is the coaxial shower nozzle of 0.24～0.85mm, shower nozzle inside is logical high-speed air also, rotating speed is that the high speed rotary-drum of 1000～2500rpm is as gathering-device, take and prepare internal diameter as 50nm～800nm, the Hollow nanofibre film that external diameter is 100nm～900nm.
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| CN115467170A (en) * | 2022-08-26 | 2022-12-13 | 东华大学 | A kind of sheath-core structure yarn with porous surface and preparation method thereof |
| CN115404701A (en) * | 2022-08-26 | 2022-11-29 | 东华大学 | A kind of porous yarn with temperature regulating function and its preparation method |
| CN115404701B (en) * | 2022-08-26 | 2023-08-29 | 东华大学 | A kind of porous yarn with temperature regulating function and its preparation method |
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Application publication date: 20140813 |