CN117364344A - 一种改性tpu纳米纤维膜及其制备方法 - Google Patents
一种改性tpu纳米纤维膜及其制备方法 Download PDFInfo
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- CN117364344A CN117364344A CN202311285430.8A CN202311285430A CN117364344A CN 117364344 A CN117364344 A CN 117364344A CN 202311285430 A CN202311285430 A CN 202311285430A CN 117364344 A CN117364344 A CN 117364344A
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- nanofiber membrane
- modified tpu
- tpu nanofiber
- modifier
- acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 63
- 239000002121 nanofiber Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003607 modifier Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 21
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
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- 239000002994 raw material Substances 0.000 claims description 12
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- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 claims description 8
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- 238000001914 filtration Methods 0.000 claims description 8
- 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 7
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- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 5
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- 238000001035 drying Methods 0.000 claims description 5
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- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
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- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 2
- ZXDPFAWIADNOFE-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazol-2-one Chemical compound NC1=NN=C(O)S1 ZXDPFAWIADNOFE-UHFFFAOYSA-N 0.000 claims description 2
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
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- 238000004519 manufacturing process Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
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- -1 biphenyl compound Chemical class 0.000 abstract 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 38
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 208000012886 Vertigo Diseases 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000035699 permeability Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000001413 cellular effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QYCPVKMFWNBDPV-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(O)=O QYCPVKMFWNBDPV-UHFFFAOYSA-N 0.000 description 1
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 description 1
- LIHVFFFGWFBSAT-UHFFFAOYSA-N 2,2-difluoropropanedioic acid Chemical compound OC(=O)C(F)(F)C(O)=O LIHVFFFGWFBSAT-UHFFFAOYSA-N 0.000 description 1
- SVHFBAAZRDCASE-UHFFFAOYSA-N 2-(2-methylphenyl)propan-2-amine Chemical compound CC1=CC=CC=C1C(C)(C)N SVHFBAAZRDCASE-UHFFFAOYSA-N 0.000 description 1
- 102100020895 Ammonium transporter Rh type A Human genes 0.000 description 1
- 101100468589 Arabidopsis thaliana RH30 gene Proteins 0.000 description 1
- 101100301844 Arabidopsis thaliana RH50 gene Proteins 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 101150107345 Rhag gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
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- 239000003906 humectant Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- 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 description 1
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Classifications
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—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
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- 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
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
本发明提供了一种改性TPU纳米纤维膜及其制备方法，所述改性TPU纳米纤维膜表面存在大量的含氟联苯结构，所述含氟联苯结构是通过控制湿度条件使得含氟联苯化合物在改性TPU纳米纤维膜表面富集。通过调控含氟联苯化合物的含量与纺丝湿度，实现所述改性TPU纳米纤维膜内部致密化孔结构的形成，最终提高所述改性TPU纳米纤维膜的疏水性，同时不减弱纤维的力学性能，使其具有优秀的定伸应力，降低形变。
Description
技术领域
本发明涉及热塑性聚氨酯纤维膜领域，尤其涉及一种通过湿度调控孔隙结构的改性TPU纳米纤维膜及其制备方法。
背景技术
随着流行性疾病SARS、H1N1等威胁到人们的生命，改善室内空气品质受到人们极大的关注。新风流通仍然是一种有效而经济的方法改善室内空气品质。然而，处理新风的能耗占到空调总能耗的20-40%，在我国南方热湿的夏天，这个能耗甚至还要大很多。为了能够有效地节约能量，数十年来暖通科研工作者们不断寻求一种低能耗的新风热湿回收过程。膜法除湿和膜法热湿回收由于无腐蚀问题，无需阀门切换、无运动部件，系统可靠性高，易维护，能耗小等优点引起了科研工作者的极大兴趣。
全热交换器是新风全热回收的一个关键的技术，这个装置就像在新风通道与室内排风通道之间安装了一个平板式换热器。夏天室外新风往往湿且热，而室内排风干且凉，新风与排风在全热交换器内交换热量与水分后新风能达到接近于室内空气的状态，节约了新风除湿制冷所需负荷；冬天新风干且冷，而室内排风暖且湿润，经过全热交换器后，新风变暖变湿，也达到接近于室内空气的状态，节约加热加湿耗能，同样节约新风负荷，使空调处理新风的能耗节约了70％～80％。与传统的金属换热器的最大优点是：这种膜不仅能够回收显热，而且能够在保证室内排风中的污浊气体不渗透的同时能够有效回收潜热。
专利号为WO03041844的美国专利提出采用蒸汽膜对空气进行除湿，这种蒸汽膜具有很高的选择透过性，当含有水蒸汽的空气流以对流或逆流的方式通过该蒸汽膜时，水蒸汽将会透过该膜，由于存在水蒸汽的部分压力差，水蒸汽将会随着一股清除气流而被排出，该清除气流与进口空气流相比具有较低的水蒸汽部分压力差。专利号为JP11090194的日本专利提出采用聚醚酰亚胺膜对空气进行除湿，该聚醚酰亚胺除湿膜是一种中空纤维膜，该中空纤维膜是由聚醚、酰亚胺-聚醚酰亚胺、酰亚胺混合而成，该膜的内表面最好涂上一层聚乙烯吡咯烷酮或涂一层保湿剂，该膜能够有效地抑制空穴的形成，并且能够提高耐久力。
由于溶质在固体中的扩散系数(<10-8cm2/s)很小，现有膜最大的缺点是难以协调高渗透性与高选择性这对矛盾，制备成本太高。而且现有膜机械强度不高，容易出现掉粉掉渣的情况，这在全热交换器里是十分不利的。
公开号为CN100348304C的中国专利公开了一种复合支撑液膜及其制备方法。其制备的复合支撑液膜具有三层结构的膜，中间为多孔支撑体层，两侧为超薄皮层；多孔支撑体层里面固定了液膜相，液膜相是质量分数为20％～45％的LiCl溶液，具有强吸湿能力和难挥发性；超薄皮层是聚偏氟乙烯膜，是一种疏水性膜，对复合支撑液膜起保护作用。但三层膜结构的缺点是流量较小，且因为膜层较厚，膨胀后液体在膜内停留时间较长，导热性较差，无法满足国际上对全热交换器的最新要求。
发明内容
为了解决上述现有技术中所述全热交换膜存在的缺点，本发明提供了一种改性TPU纳米纤维膜及其制备方法，所述改性TPU纳米纤维膜是通过湿度的调整来控制改性剂含氟联苯在聚酯型TPU纤维上的富集，从而调控最终所得改性TPU纳米纤维膜的致密化孔隙结构，实现力学性能、透湿性能和耐水解性的提升。
第一方面，本发明提供了一种改性TPU纳米纤维膜，按质量百分比计，其包含如下原料：4，4'-二苯基甲烷二异氰酸酯40-45%、1,4-丁二醇32-35%、己二酸19.9-21%和改性剂2-5%。
在本发明的一些实施方式中，所述改性剂的制备过程包含如下步骤：将全氟二元羧酸投入装有有机溶剂1的反应容器中，充入惰性气体，然后在-20~-10℃下向其中滴加缩合剂和促进剂，搅拌1-2h后，再加入2,2-双(4-氨基苯基)六氟丙烷，将反应体系加热至50-70℃进行酰胺化反应，反应3-5h后，将析出晶体过滤洗涤干燥，即得所述改性剂。
在本发明的一些实施方式中，所述全氟二元羧酸为羧酸封端的全氟烷基二酸，且所含碳原子数为3-8。
在本发明的一些实施方式中，所述缩合剂为二环己基碳二亚胺、N,N-二异丙基碳二亚胺和1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺盐酸盐中的至少一种。
在本发明的一些实施方式中，所述促进剂为4-二甲氨基吡啶、4-吡咯烷基吡啶、N-羟基丁二酰亚胺、1-癸基苯并三唑、2-羟基-5-氨基-1,3,4-噻二唑中的至少一种。在本发明的一些实施方式中，所述含氟二元羧酸与2,2-双(4-氨基苯基)六氟丙烷的投加质量比为60-76：67-80。
在本发明的一些实施方式中，所述有机溶剂1选自：二氯甲烷、三氯甲烷、二甲基甲酰胺中的至少一种。
在本发明中，上述改性剂是通过全氟烷基酸与2,2-双(4-氨基苯基)六氟丙烷这一含有苯胺基的含氟物质发生酰胺化反应制备所得，所得改性剂分子中含有大量的氟原子，将其少量加入TPU中，可提高TPU树脂的疏水性，保护TPU树脂分子内酰胺基不轻易被水解。
第二方面，本发明提供一种所述改性TPU纳米纤维膜的制备方法，包含如下步骤：
S1：在装有有机溶剂2的反应器中加入计量的1,4-丁二醇，加热至100-120℃，于真空下脱水1-2h，随后降温至60-75℃，加入计量的4，4'-二苯基甲烷二异氰酸酯和催化剂后升温至80-90℃，保温反应2-3h；
S2：将S1的反应体系降温至60-75℃，加入计量的己二酸和改性剂，快速搅拌，将体系温度升至80-90℃，倒入涂有脱模剂的模具中，于烘箱中熟化脱泡6-8h后，在RH30-80%的条件下，于接收基材上以50-100r/min的纺丝速度制备所述改性TPU纳米纤维膜。
在本发明所提供的制备方法中，通过调整改性剂的添加量及纺丝湿度来实现所述改性TPU纳米纤维膜孔隙结构。在纺丝时，随着溶剂的挥发和蒸汽扩散到纤维膜中，在膜断面形成改性TPU树脂的粘度梯度，纤维膜中发生相分离。溶剂的快速挥发，溶液表面温度会降低，使得蒸汽凝结在溶液表面形成小水滴，随着数量增加、体积增大，表面的水滴在毛细管力的作用下最终形成了蜂窝状的紧密排列。而且，空气湿度越高，进入的水越多，固化速度越慢，最终所述改性TPU纳米纤维膜的细胞状孔隙越小，尤其在膜的内部，孔隙直径比表面的孔隙直径小。另外，由于所述改性剂的含氟疏水结构，随着溶剂向外迁移，所述改性剂也会向表面自富集，会在液膜表面形成一层聚合物皮层，抑制水分向内部迁移的速率，最终所述改性TPU纳米纤维膜在空气侧的表面比内部的结构更疏松，纤维膜的表面具有大量针孔。
若改性剂的用量过大，所述改性TPU纳米纤维膜表面积聚较多的含氟疏水结构，表层形成的孔径会变大，水分易于通过较大的孔隙进入膜的内部，影响内部致密孔隙的结构形成；而且，蒸汽环境的湿度也需严格把控，若湿度太低，所述改性剂无法在膜表面实现理想含量的富集，膜的疏水性得不到提升，若湿度过高，所述改性剂大量向膜表面迁移，内部的孔隙间的连接性变差，无法形成致密化孔结构。综上可知，在纺丝制备所述改性TPU纳米纤维膜时，所述改性剂和环境湿度的控制需在符合条件的范围下。
在本发明的一些实施方式中，所述有机溶剂2可以为但不限于：二甲基甲酰胺（DMF）、二甲基乙酰胺（DMA）、二氧六环、四氢呋喃、甲基异丁酮、二甲基亚矾、甲苯等。
在本发明的一些实施方式中，所述催化剂为叔胺类和有机锡类中的至少一种，具体而言，所述叔胺类包含三乙烯二胺、三乙胺、三甲基苄胺、二甲基乙醇胺等，所述有机锡类包含辛酸亚锡、二月桂酸二丁基锡等，添加量为总反应体系的0.03-0.05wt%。
在本发明的一些实施方式中，所述S2中的纺丝条件为：温度为15-30℃、电压为25-50kV、纺丝混合液的灌注速度为1~5ml/h。
在本发明的一些实施方式中，所述接收基材为无纺布、油光纸、铝箔、金属网中的一种。
有益效果：与现有技术相比，本发明创新性地在TPU树脂中添加含氟疏水结构的改性剂，并通过纺丝阶段的湿度控制，来调控所述改性TPU纳米纤维膜的孔隙结构：
1、溶剂的挥发与蒸汽的进入使得纺丝液中的改性剂逐渐向膜表面富集，最终形成疏水层，提高所述改性TPU纳米纤维膜的疏水性，同时内部的改性剂促使了内部孔隙之间的紧密排列，形成了致密化孔结构，有助于增强所述改性TPU纳米纤维膜的力学性能，降低形变；
2、由于溶剂的流失，TPU树脂在膜断面形成粘度梯度，最终使得所述改性TPU纳米纤维膜在近空气侧的表面结构比接收基质侧的结构更疏松，形成了细胞状孔隙，而内部的孔径比近空气侧的孔径更小，有利于改性TPU纳米纤维膜的透湿性。
具体实施方式
下面结合实例对本发明作进一步详细描述。需要说明的是，下面的实施例及对比例为本发明的示例，仅用来说明本发明，而不用来限制本发明。在不偏离本发明主旨或范围的情况下，可进行本发明构思内的其他组合和各种改良。
以下示例性地说明实施例中所用改性剂的制备过程：
改性剂-1
将12g全氟丙二酸投入装有150ml二氯甲烷的反应容器中，充入氮气，然后在-10℃下向其中滴加0.7g 1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺盐酸盐和0.14g N-羟基丁二酰亚胺，搅拌2h后，再加入14g 2,2-双(4-氨基苯基)六氟丙烷，将反应体系加热至50℃进行酰胺化反应，反应3h后，将析出晶体过滤掉，取过滤液与乙醚混合，再次过滤掉晶体，向过滤液中加入无水硫酸钠干燥后真空去除二氯甲烷，即得所述改性剂-1。
改性剂-2
将14g全氟戊二酸投入装有150ml二氯甲烷的反应容器中，充入氮气，然后在-5℃下向其中滴加0.715g 1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺盐酸盐和0.429g N-羟基丁二酰亚胺，搅拌2h后，再加入16g 2,2-双(4-氨基苯基)六氟丙烷，将反应体系加热至60℃进行酰胺化反应，反应4h后，将析出晶体过滤掉，取过滤液与乙醚混合，再次过滤掉晶体，向过滤液中加入无水硫酸钠干燥后真空去除二氯甲烷，即得所述改性剂-2。
改性剂-3
将22.8g全氟辛二酸投入装有150ml二氯甲烷的反应容器中，充入氮气，然后在-5℃下向其中滴加1.6g 1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺盐酸盐和0.32g N-羟基丁二酰亚胺，搅拌2h后，再加入24g 2,2-双(4-氨基苯基)六氟丙烷，将反应体系加热至70℃进行酰胺化反应，反应5h后，将析出晶体过滤掉，取过滤液与乙醚混合，再次过滤掉晶体，向过滤液中加入无水硫酸钠干燥后真空去除二氯甲烷，即得所述改性剂-3。
实施例1
S1：在装有甲苯的反应器中加入占原料总质量32%的1,4-丁二醇，加热至100℃，于0.67kPa真空下脱水1h，随后降温至60℃，加入占原料总质量45%的4，4'-二苯基甲烷二异氰酸酯和0.03%的三乙胺后升温至80℃，保温反应3h；
S2：将S1的反应体系降温至60℃，加入占原料总质量20.97%的己二酸和2%的改性剂-1，快速搅拌，将体系温度升至80℃，倒入涂有脱模剂的模具中，于50℃烘箱中熟化脱泡6h后，在RH30%的条件下，于无纺布上以50r/min的纺丝速度制备所述改性TPU纳米纤维膜，纺丝温度为15℃，电压25kV，灌注速度为1ml/h。
实施例2
S1：在装有甲苯的反应器中加入占原料总质量35%的1,4-丁二醇，加热至110℃，于0.67kPa真空下脱水1h，随后降温至60℃，加入占原料总质量42%的4，4'-二苯基甲烷二异氰酸酯和0.03%的二月桂酸二丁基锡后升温至80℃，保温反应3h；
S2：将S1的反应体系降温至70℃，加入占原料总质量19.97%的己二酸和3%的改性剂-2，快速搅拌，将体系温度升至80℃，倒入涂有脱模剂的模具中，于50℃烘箱中熟化脱泡7h后，在RH50%的条件下，于油光纸上以80r/min的纺丝速度制备所述改性TPU纳米纤维膜，纺丝温度为20℃，电压35kV，灌注速度为3ml/h。
实施例3
S1：在装有甲苯的反应器中加入占原料总质量32%的1,4-丁二醇，加热至120℃，于0.67kPa真空下脱水2h，随后降温至70℃，加入占原料总质量42%的4，4'-二苯基甲烷二异氰酸酯和0.05%的二月桂酸二丁基锡后升温至90℃，保温反应2h；
S2：将S1的反应体系降温至70℃，加入占原料总质量20.95%的己二酸和5%的改性剂-3，快速搅拌，将体系温度升至80℃，倒入涂有脱模剂的模具中，于50℃烘箱中熟化脱泡8h后，在RH80%的条件下，于铝箔上以100r/min的纺丝速度制备所述改性TPU纳米纤维膜，纺丝温度为30℃，电压50kV，灌注速度为5ml/h。
实施例4
制备过程与实施例3相似，不同之处在于，纺丝湿度为20%。
实施例5
制备过程与实施例3相似，不同之处在于，纺丝湿度为90%。
对比例1
制备过程与实施例3相似，不同之处在于，所述改性剂的添加量为1%。
对比例2
制备过程与实施例3相似，不同之处在于，所述改性剂的添加量为6%。
对比例3
制备过程与实施例3相似，不同之处在于，不添加改性剂。
将上述实施例及对比例中所制备的改性TPU纳米纤维膜进行如下测试：
表面接触角：将膜剪成长条状，用双面胶分别将膜的正反两面粘在载玻片上，用蒸馏水以淌滴法在KRUSS-DSA100型接触角测定仪上测定接触角；
定伸强度：按照GB/T12824-2002标准执行；
拉伸强度：按照GB/T528-1998标准执行，测试条件为室温25℃、拉力机加荷速度50mm/min；
透湿率：按照GB/T 12704.2-2009 《纺织品织物透湿性试验方法第2部分：蒸发法》标准执行。
测试结果见表1：
由表1中的数据可知，实施例1-5中所得改性TPU纳米纤维膜具有优秀的疏水性，其表面与蒸馏水的接触角不低于116°，定伸强度不低于135N的结果说明所述改性TPU纳米纤维膜的耐形变性具有较大的提升（与对比例3的结果相比）；拉伸强度与大于9000 g/（m2•24h）的透湿性的结果说明所述改性TPU纳米纤维树脂的力学性能与透湿性实现了同步提升。
实施例4-5的结果说明，纺丝湿度的变化会影响到所述改性TPU纳米纤维膜表面的疏水性及膜的透湿性，这可能是由于湿度过大或过小影响到了膜内部孔隙结构的形成。
对比例2的结果说明，所述改性剂的添加量也不宜过多，过多的含氟联苯疏水结构的存在虽然也会提高所述改性TPU纳米纤维膜的疏水性，但膜的透湿性却大大降低，这或许是因为膜表面的疏水结构阻挡了蒸汽的进入。
综上可知，本发明所提供的改性TPU纳米纤维膜具有优秀的疏水性、力学性能和透湿性，能够有效避免TPU分子的水解，降低形变，实现高效的全热交换，在TPU纤维膜领域具有可观的应用前景。
Claims (10)
1.一种改性TPU纳米纤维膜，其特征在于，按质量百分比计，包含如下原料：4，4'-二苯基甲烷二异氰酸酯40-45%、1,4-丁二醇32-35%、己二酸19.9-21%和改性剂2-5%。
2.根据权利要求1所述改性TPU纳米纤维膜，其特征在于，所述改性剂的制备过程包含如下步骤：将全氟二元羧酸投入装有有机溶剂1的反应容器中，充入惰性气体，然后在-20~-10℃下向其中滴加缩合剂和促进剂，搅拌1-2h后，再加入2,2-双(4-氨基苯基)六氟丙烷，将反应体系加热至50-70℃进行酰胺化反应，反应3-5h后，将析出晶体过滤，取过滤液干燥后真空去除溶剂，即得所述改性剂。
3.根据权利要求2所述改性TPU纳米纤维膜，其特征在于，所述全氟二元羧酸为羧酸封端的全氟烷基二酸，且所含碳原子数为3-8。
4.根据权利要求2所述改性TPU纳米纤维膜，其特征在于，所述缩合剂为二环己基碳二亚胺、N,N-二异丙基碳二亚胺和1-(3-二甲基氨基丙基)-3-乙基碳化二亚胺盐酸盐中的至少一种，添加量为反应体系质量的0.5-1%。
5.根据权利要求2所述改性TPU纳米纤维膜，其特征在于，所述促进剂为4-二甲氨基吡啶、4-吡咯烷基吡啶、N-羟基丁二酰亚胺、1-癸基苯并三唑、2-羟基-5-氨基-1,3,4-噻二唑中的至少一种，添加量为反应体系总质量的0.1-0.3%。
6.根据权利要求2所述改性TPU纳米纤维膜，其特征在于，所述催化剂为盐酸或98%的硫酸。
7.根据权利要求2所述改性TPU纳米纤维膜，其特征在于，所述含氟二元羧酸与2,2-双(4-氨基苯基)六氟丙烷的投加质量比为60-76：67-80。
8.根据权利要求1-7任意一项所述改性TPU纳米纤维膜的制备方法，其特征在于，包含如下步骤：
S1：在装有有机溶剂2的反应器中加入计量的1,4-丁二醇，加热至100-120℃，于真空下脱水1-2h，随后降温至60-75℃，加入计量的4，4'-二苯基甲烷二异氰酸酯和催化剂后升温至80-90℃，保温反应2-3h；
S2：将S1的反应体系降温至60-75℃，加入计量的己二酸和改性剂，快速搅拌，将体系温度升至80-90℃，倒入涂有脱模剂的模具中，于烘箱中熟化脱泡6-8h后，在RH30-80%的条件下，于接收基材上以50-100r/min的纺丝速度制备所述改性TPU纳米纤维膜。
9.根据权利要求8所述制备方法，其特征在于，所述S2中的纺丝条件为：温度为15-30℃、电压为25-50kV、纺丝混合液的灌注速度为1~5ml/h。
10.根据权利要求8所述制备方法，其特征在于，所述接收基材为无纺布、油光纸、铝箔、金属网中的一种。
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