CN103386261A - Super hydrophobic polytetrafluoroethylene hollow fiber membrane preparation method - Google Patents
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- CN103386261A CN103386261A CN2013102754494A CN201310275449A CN103386261A CN 103386261 A CN103386261 A CN 103386261A CN 2013102754494 A CN2013102754494 A CN 2013102754494A CN 201310275449 A CN201310275449 A CN 201310275449A CN 103386261 A CN103386261 A CN 103386261A
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 66
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 66
- 239000012528 membrane Substances 0.000 title claims abstract description 47
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 44
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 40
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000004809 Teflon Substances 0.000 claims description 20
- 229920006362 Teflon® Polymers 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 3
- VIFIHLXNOOCGLJ-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl VIFIHLXNOOCGLJ-UHFFFAOYSA-N 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 239000002352 surface water Substances 0.000 abstract description 7
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000010612 desalination reaction Methods 0.000 abstract 1
- 238000009998 heat setting Methods 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 230000035515 penetration Effects 0.000 abstract 1
- 238000003825 pressing Methods 0.000 abstract 1
- 239000013535 sea water Substances 0.000 abstract 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 abstract 1
- 239000011148 porous material Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a super hydrophobic polytetrafluoroethylene hollow fiber membrane preparation method. The method comprises the steps of mixing polytetrafluoroethylene dispersion resin powder with an extruding-aid agent, pressing a blank, extruding the blank into a polytetrafluoroethylene hollow tube through an extruder, then processing modification to the polytetrafluoroethylene hollow tube through silica sol, and then performing vertical stretching, sintering and heat setting in a baking oven, finally performing penetration processing by using perfluorosilane to obtain the super hydrophobic polytetrafluoroethylene hollow fiber membrane. The processed super hydrophobic polytetrafluoroethylene hollow fiber membrane has an average aperture on external layer of between 0.10-1.0 micrometer and an average aperture on internal layer of between 5.0-20 micrometer, and a surface water contact angle of 152-160 degree. The membrane is mainly used in membrane distillation and separation process, and can be used for seawater desalination, industrial waste water processing and in foodstuff and biological product cryoconcentration.
Description
Technical field
The present invention relates to the preparation method of hollow-fibre membrane, be specifically related to a kind of preparation method of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
Background technology
Film distillation technology is a kind of take the poor isolation technics of new membrane as the mass transfer driving force of hydrophobic microporous membrane both sides steam pressure.Due to film distillation technology have can repel involatile substance in solution (as ion, large molecule and solid particle etc.), operating pressure simple lower than counter-infiltration, equipment, to raw water quality require low, only have steam to see through fenestra, produce water water quality purity advantages of higher, can be used for all many-sides such as concentrated and crystallization of the degree of depth Treatment for Reuse of desalinization, industrial wastewater and food, biological products.
In the film distillation, the selection of hydrophobic micropore membrane material is crucial.Polytetrafluoroethylene (PTFE) is a kind of hydrophobic film material that acid, alkali, organic solvent and hot environment etc. is had well tolerable property, is the ideal material of film distillation.Adopt the hollow-fibre membrane of polytetrafluoroethylmaterial material preparation because its film silk intensity is high, the advantages such as pliability good, porosity is high, loading density is high, floor space is little, easy cleaning, extensive use in the film separation processes such as ultra filtration, film distillation, film absorption and membrane bioreactor.Patent CN102284251A prepares polytetrafluoroethylhollow hollow fiber membrane by the method for continuous looping polytetrafluoroethylene film on polyester (PET) fiber braided tube supporter, but this method adopts the poor PET fiber braided tube of hydrophobicity as supporter, in long-time high temperature distillation process, the PET fiber braided tube, easily by water-wet, descends greatly thereby cause the film distillation to produce water quality.Patent CN102941025A mixes polytetrafluoroethyldispersion dispersion resin the blank of compacting and extrudes and form the polytetrafluoroethylene (PTFE) hollow tube by the pushing machine with extrusion aid, the polytetrafluoroethylene (PTFE) hollow tube is carried out longitudinal stretching and sintering thermal finalization obtains polytetrafluoroethylhollow hollow fiber membrane in baking oven, adopt the surface water contact angle of the polytetrafluoroethylhollow hollow fiber membrane that this method obtains between 120～130 degree.
Due to the super-hydrophobic phenomenon of the self-cleaning embodiment of occurring in nature lotus leaf surface, super hydrophobic material starts to cause people's extensive concern.Super hydrophobic material refers generally to the material of surface of solids water contact angle greater than 150 degree, and its excellent waterproof, grease proofing, anti-pollution and self-cleaning performance, make super hydrophobic material have broad application prospects in industrial and agricultural production He in daily life.Because needing microporous membrane material, film distillation technology possesses good hydrophobicity, therefore use super hydrophobic material can make microporous barrier long-term hydrophobicity that keeps in operating process in the film distillation, can be not processed feed liquid pollute and wetting, can not cause that the film distillation produces water quality decline.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane, the method is by the polytetrafluoroethyldispersion dispersion resin powder is mixed with extrusion aid, and pressed compact, extrude the polytetrafluoroethylene (PTFE) hollow tube with blank by the pushing machine.Again the polytetrafluoroethylene (PTFE) hollow tube is immersed in Ludox, obtains the modified Teflon hollow tube.Then the modified Teflon hollow tube is carried out in baking oven longitudinal stretching and sintering thermal finalization, use finally the perfluor silane treatment, be prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane, be mainly used in film separated process.
The step of the technical solution used in the present invention is as follows:
A) batch mixing: select the polytetrafluoroethyldispersion dispersion resin powder, the polytetrafluoroethyldispersion dispersion resin powder is mixed 1:0.22～0.40 in mass ratio with extrusion aid, under 20～40 ° of C standing 60～80 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with extrusion aid, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 100～200 ° of C, extruded velocity is 100～300 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 1～5:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 1～10:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 60～120 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 1～5 hour, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 200～320 ° of C, draw ratio is 0.5～3 times, then sintering thermal finalization under 320～400 ° of C, sintering time is 20～80 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluor silane after solvent dilution 1～10 hour, takes out, 40～100 ° of C oven dry 10～60 seconds, be prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
In described a) step, the molecular weight of polytetrafluoroethyldispersion dispersion resin powder is 200～1,000 ten thousand, and described extrusion aid is liquid paraffin, benzinum or kerosene.
Described f) in step, perfluor silane is perfluoro capryl trichlorosilane, perfluor decyltrichlorosilane, perfluoro capryl triethoxysilane, perfluoro capryl trimethoxy silane, perfluor decyl trimethoxy silane or perfluor decyl triethoxysilane.
Described f) in step, solvent is n-hexane, ethyl acetate, butanone, acetone, cyclohexane, isopropyl alcohol, n-butanol, carrene or chloroform.
Compare with background technology, the beneficial effect that the present invention has is:
(1) compared with prior art, this law adopts silica sol modified processing and high temperature sintering, forms the micro-nano classification coarse structure of silica on the polytetrafluoroethylhollow hollow fiber membrane surface, then uses low-surface-energy material perfluor silane treatment, forms super hydrophobic surface.The polytetrafluoroethylhollow hollow fiber membrane surface water contact angle for preparing is greater than 150 degree, and it can keep hydrophobicity for a long time in the film still-process, can processed feed liquid pollution and wetting.
(2) this law, based on preparation technology and the equipment of existing polytetrafluoroethylhollow hollow fiber membrane, need not added extras, and of the present invention method is simple, and cost is lower, has great practical value.
The present invention is mainly used in film separated process, can be used for the fields such as the low temperature of desalinization, Industrial Wastewater Treatment and food and biological products is concentrated.
The specific embodiment
Embodiment 1:
A) batch mixing: the selection molecular weight is 2,000,000 polytetrafluoroethyldispersion dispersion resin powder, with polytetrafluoroethyldispersion dispersion resin powder and liquid paraffin in mass ratio 1:0.22 mix, under 20 ° of C standing 60 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with liquid paraffin, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 100 ° of C, extruded velocity is 100 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 1:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 1:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 60 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 5 hours, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 200 ° of C, draw ratio is 0.5 times, then sintering thermal finalization under 320 ° of C, sintering time is 80 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluoro capryl trichlorosilane after n-hexane dilution 10 hours, takes out, under 100 ° of C, oven dry is 10 seconds, is prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
The outer average pore size of the super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane of processing is 0.10 micron, and the internal layer average pore size is 5.0 microns, and wall thickness is 0.1 millimeter, and the surface water contact angle is 152 degree.
Embodiment 2:
A) batch mixing: the selection molecular weight is 1,000 ten thousand polytetrafluoroethyldispersion dispersion resin powder, with polytetrafluoroethyldispersion dispersion resin powder and benzinum in mass ratio 1:0.40 mix, under 40 ° of C standing 80 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with benzinum, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 200 ° of C, extruded velocity is 300 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 5:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 10:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 120 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 1 hour, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 320 ° of C, draw ratio is 3 times, then sintering thermal finalization under 400 ° of C, and sintering time is 20 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluor decyltrichlorosilane after butanone dilution 1 hour, takes out, under 40 ° of C, oven dry is 60 seconds, is prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
The outer average pore size of the super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane of processing is 1.0 microns, and the internal layer average pore size is 20 microns, and the surface water contact angle is 160 degree.
Embodiment 3:
A) batch mixing: the selection molecular weight is 5,000,000 polytetrafluoroethyldispersion dispersion resin powder, with polytetrafluoroethyldispersion dispersion resin powder and kerosene in mass ratio 1:0.30 mix, under 25 ° of C standing 70 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with kerosene, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 145 ° of C, extruded velocity is 150 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 3:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 4:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 80 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 2 hours, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 260 ° of C, draw ratio is 1.5 times, then sintering thermal finalization under 360 ° of C, sintering time is 50 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluoro capryl triethoxysilane after isopropanol 3 hours, takes out, under 60 ° of C, oven dry is 40 seconds, is prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
The outer average pore size of the super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane of processing is 0.25 micron, and the internal layer average pore size is 10 microns, and the surface water contact angle is 155 degree.
Embodiment 4:
A) batch mixing: the selection molecular weight is 8,000,000 polytetrafluoroethyldispersion dispersion resin powder, with polytetrafluoroethyldispersion dispersion resin powder and benzinum in mass ratio 1:0.36 mix, under 35 ° of C standing 65 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with benzinum, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 160 ° of C, extruded velocity is 200 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 4:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 8:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 100 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 2 hours, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 220 ° of C, draw ratio is 2 times, then sintering thermal finalization under 380 ° of C, and sintering time is 40 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluor decyl trimethoxy silane after carrene dilution 8 hours, takes out, under 80 ° of C, oven dry is 20 seconds, is prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
The outer average pore size of the super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane of processing is 0.5 micron, and the internal layer average pore size is 15 microns, and the surface water contact angle is 158 degree.
Claims (4)
1. the preparation method of a super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane, is characterized in that, comprises the following steps:
A) batch mixing: select the polytetrafluoroethyldispersion dispersion resin powder, the polytetrafluoroethyldispersion dispersion resin powder is mixed 1:0.22～0.40 in mass ratio with extrusion aid, under 20～40 ° of C standing 60～80 hours, the polytetrafluoroethyldispersion dispersion resin powder is fully mixed with extrusion aid, form the polytetrafluoroethylene (PTFE) material;
B) pressed compact with extrude: described polytetrafluoroethylene (PTFE) material is pressed into cylindrical blank on harder, cylindrical blank, by the pushing machine, is extruded formation polytetrafluoroethylene (PTFE) hollow tube under 100～200 ° of C, extruded velocity is 100～300 cm per minute;
C) preparation of Ludox: with mass fraction be 30% ammoniacal liquor and absolute ethyl alcohol by volume 1～5:50 mix, stirred 20 minutes under 40 ° of C, form the ammoniacal liquor alcohol mixeding liquid, then 1～10:50 drips ethyl orthosilicate in the ammoniacal liquor alcohol mixeding liquid by volume, stirred 60～120 minutes under 60 ° of C, form Ludox;
D) preparation of modified Teflon hollow tube: the polytetrafluoroethylene (PTFE) hollow tube is immersed in described Ludox 1～5 hour, takes out, be prepared into the modified Teflon hollow tube;
E) longitudinal stretching and sintering thermal finalization: described modified Teflon hollow tube is carried out longitudinal stretching under 200～320 ° of C, draw ratio is 0.5～3 times, then sintering thermal finalization under 320～400 ° of C, sintering time is 20～80 seconds, is prepared into polytetrafluoroethylhollow hollow fiber membrane;
F) polytetrafluoroethylhollow hollow fiber membrane is immersed in perfluor silane after solvent dilution 1～10 hour, takes out, 40～100 ° of C oven dry 10～60 seconds, be prepared into super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane.
2. the preparation method of a kind of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane according to claim 1, it is characterized in that: in described a) step, the molecular weight of polytetrafluoroethyldispersion dispersion resin powder is 200～1,000 ten thousand, and described extrusion aid is liquid paraffin, benzinum or kerosene.
3. the preparation method of a kind of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane according to claim 1, it is characterized in that: described f) in step, perfluor silane is perfluoro capryl trichlorosilane, perfluor decyltrichlorosilane, perfluoro capryl triethoxysilane, perfluoro capryl trimethoxy silane, perfluor decyl trimethoxy silane or perfluor decyl triethoxysilane.
4. the preparation method of a kind of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane according to claim 1, it is characterized in that: described f) in step, solvent is n-hexane, ethyl acetate, butanone, acetone, cyclohexane, isopropyl alcohol, n-butanol, carrene or chloroform.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104843852A (en) * | 2015-04-23 | 2015-08-19 | 四川和鼎环保工程有限责任公司 | Treatment tank conducive to interactive interface area increasing |
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| CN106012525A (en) * | 2016-06-22 | 2016-10-12 | 华东理工大学 | Super-hydrophobic modification method for polytetrafluoroethylene (PTTE) fibers applied to oily sewage treatment |
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| CN107158953A (en) * | 2017-07-18 | 2017-09-15 | 中国科学院生态环境研究中心 | A kind of preparation method of membrane distillation nano wire hydrophobic membrane |
| CN111330453A (en) * | 2020-03-06 | 2020-06-26 | 自然资源部天津海水淡化与综合利用研究所 | Polytetrafluoroethylene hollow fiber composite membrane and preparation method thereof |
| CN111534030A (en) * | 2020-06-03 | 2020-08-14 | 河北澳科中意环保科技有限公司 | Polytetrafluoroethylene fiber membrane and sealing system containing same |
| CN112795996A (en) * | 2021-01-27 | 2021-05-14 | 浙江格尔泰斯环保特材科技股份有限公司 | Super-hydrophobic polytetrafluoroethylene fiber filament and preparation method thereof |
| CN113731199A (en) * | 2021-07-20 | 2021-12-03 | 东华大学 | Super-amphiphobic membrane and preparation method and application thereof |
| CN114011253A (en) * | 2021-11-17 | 2022-02-08 | 中核同辐（长春）辐射技术有限公司 | PTFE microporous membrane surface modification method and application thereof |
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| CN104073896B (en) * | 2014-07-18 | 2016-03-30 | 上海灵氟隆新材料科技有限公司 | The preparation method of the polytetrafluoroethylfilament filament of base cloth is strengthened for water thorn filtrate |
| CN104073896A (en) * | 2014-07-18 | 2014-10-01 | 上海灵氟隆新材料科技有限公司 | Method for preparing polytetrafluoroethylene filament for spunlace filter material reinforcing base cloth |
| CN104843852A (en) * | 2015-04-23 | 2015-08-19 | 四川和鼎环保工程有限责任公司 | Treatment tank conducive to interactive interface area increasing |
| CN105289327B (en) * | 2015-12-01 | 2018-01-30 | 天津工业大学 | A kind of preparation method for the Na20-B203-Si02 glass hollow-fibre membrane that homogeneity is modified |
| CN105289327A (en) * | 2015-12-01 | 2016-02-03 | 天津工业大学 | Preparation method of homogeneous modified sodium borosilicate glass hollow fiber membrane |
| CN106012525A (en) * | 2016-06-22 | 2016-10-12 | 华东理工大学 | Super-hydrophobic modification method for polytetrafluoroethylene (PTTE) fibers applied to oily sewage treatment |
| CN106862040A (en) * | 2017-03-29 | 2017-06-20 | 武汉理工大学 | A kind of method that wire cutting prepares the orderly micro-nano super-drainage structure in metal surface |
| CN107158953A (en) * | 2017-07-18 | 2017-09-15 | 中国科学院生态环境研究中心 | A kind of preparation method of membrane distillation nano wire hydrophobic membrane |
| CN107158953B (en) * | 2017-07-18 | 2020-05-19 | 中国科学院生态环境研究中心 | Preparation method of nanowire hydrophobic membrane for membrane distillation |
| CN111330453A (en) * | 2020-03-06 | 2020-06-26 | 自然资源部天津海水淡化与综合利用研究所 | Polytetrafluoroethylene hollow fiber composite membrane and preparation method thereof |
| CN111330453B (en) * | 2020-03-06 | 2022-04-19 | 自然资源部天津海水淡化与综合利用研究所 | Polytetrafluoroethylene hollow fiber composite membrane and preparation method thereof |
| CN111534030A (en) * | 2020-06-03 | 2020-08-14 | 河北澳科中意环保科技有限公司 | Polytetrafluoroethylene fiber membrane and sealing system containing same |
| CN112795996A (en) * | 2021-01-27 | 2021-05-14 | 浙江格尔泰斯环保特材科技股份有限公司 | Super-hydrophobic polytetrafluoroethylene fiber filament and preparation method thereof |
| CN113731199A (en) * | 2021-07-20 | 2021-12-03 | 东华大学 | Super-amphiphobic membrane and preparation method and application thereof |
| CN114011253A (en) * | 2021-11-17 | 2022-02-08 | 中核同辐（长春）辐射技术有限公司 | PTFE microporous membrane surface modification method and application thereof |
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