CN110433662A - A kind of preparation method of membrane distillation super-amphiphobic PS membrane - Google Patents
A kind of preparation method of membrane distillation super-amphiphobic PS membrane Download PDFInfo
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- CN110433662A CN110433662A CN201910798844.8A CN201910798844A CN110433662A CN 110433662 A CN110433662 A CN 110433662A CN 201910798844 A CN201910798844 A CN 201910798844A CN 110433662 A CN110433662 A CN 110433662A
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- 239000012528 membrane Substances 0.000 title claims abstract description 107
- 238000004821 distillation Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 10
- 210000004379 membrane Anatomy 0.000 claims description 97
- 239000007788 liquid Substances 0.000 claims description 57
- 239000011259 mixed solution Substances 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 31
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 31
- 238000005266 casting Methods 0.000 claims description 21
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- 239000000908 ammonium hydroxide Substances 0.000 claims description 20
- 150000003384 small molecules Chemical class 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011521 glass Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 210000002469 basement membrane Anatomy 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 238000006482 condensation reaction Methods 0.000 claims description 11
- 238000007711 solidification Methods 0.000 claims description 11
- 230000008023 solidification Effects 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- NYTYVZFFEIBDBZ-UHFFFAOYSA-N CO[SiH](OC)OC.[Ru].[F] Chemical compound CO[SiH](OC)OC.[Ru].[F] NYTYVZFFEIBDBZ-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QRPMCZNLJXJVSG-UHFFFAOYSA-N trichloro(1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl)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)C(F)(F)C(F)(F)[Si](Cl)(Cl)Cl QRPMCZNLJXJVSG-UHFFFAOYSA-N 0.000 claims description 4
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 4
- SWFWDIAODYABMV-UHFFFAOYSA-N C(CCCCCCC)[Si](Cl)(Cl)Cl.[F] Chemical compound C(CCCCCCC)[Si](Cl)(Cl)Cl.[F] SWFWDIAODYABMV-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 229960004756 ethanol Drugs 0.000 claims description 2
- 238000001879 gelation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 230000015271 coagulation Effects 0.000 claims 1
- 238000005345 coagulation Methods 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 19
- 230000009977 dual effect Effects 0.000 abstract description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007788 roughening Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 14
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003075 superhydrophobic effect Effects 0.000 description 9
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 229940051250 hexylene glycol Drugs 0.000 description 7
- -1 salt ion Chemical class 0.000 description 7
- 238000010041 electrostatic spinning Methods 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- YESRULSVSWLZLT-UHFFFAOYSA-N C(C)O[SiH](OCC)OCC.[Ru].[F] Chemical class C(C)O[SiH](OCC)OCC.[Ru].[F] YESRULSVSWLZLT-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VYQRBKCKQCRYEE-UHFFFAOYSA-N ctk1a7239 Chemical compound C12=CC=CC=C2N2CC=CC3=NC=CC1=C32 VYQRBKCKQCRYEE-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000000608 laser ablation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Abstract
The invention discloses a kind of methods of preparation super-amphiphobic PS membrane being simple and efficient, and are related to UF membrane field.The present invention has the PS membrane of interpenetrating networks pore structure using traditional solvent-induced phase inversion preparation first, which forms " reentrant features " in film surface.Then pass through substep sol-gel method equally distributed nano SiO 2 particle of in-situ preparation on interpenetrating networks hole wall, certain nanoscale rough structure is provided for PS membrane.A layered low-surface energy fluorosilane compounds film finally is coated in roughening polysulfones film surface, super-amphiphobic PS membrane is obtained, realizes the dual anti-wellability to water droplet and organic drop, water droplet contact angle is up to 150 ° or more, and n-hexane contact angle is up to 65 ° or more.When the super-amphiphobic PS membrane of preparation is applied with membrane distillation process, salt-stopping rate and stronger resist wet stability with 99.5% or more.
Description
Technical field
The present invention relates to a kind of preparation methods of seperation film for membrane distillation process, and in particular to a kind of super-amphiphobic film
Preparation method.
Background technique
Currently, China's water resource is poorer, per mu less per capita, especially Northern Coastal Provinces and Islands ' Water Resource are short
Problem becomes increasingly conspicuous.To alleviate water resources crisis, while water-saving energetically, active development utilizes the unconventional water such as seawater in China
Resource.Sea water desalination gradually becomes the important supplement and strategic reserves of water resource as stable water resource increment technique.Product
Sea water desalination industry is developed in pole, to alleviation China coast water-deficient area and Islands ' Water Resource shortage problem, reasonably optimizing water knot
Structure pushes sustainable utilization of water resource to have extremely important meaning.
Reverse osmosis is the film desalting technology for being now widely used for sea water desalination, however, reverse osmosis is not the high salinity of processing
The ideal chose of waste water, it faces huge challenge in terms of handling haline water, because overcoming required for haline water osmotic pressure
Operating pressure is considerably beyond the limit of reverse osmosis membrane, and the salinity of waste water is also considerably beyond the limit of reverse osmosis operation.Film steams
It evaporates due to its unique advantage, including resisting high-concentration salt water and low operating pressure, is developed as to substitute reverse osmosis most promising
Method.Membrane distillation be it is a kind of the seawater of heating is evaporated by porous membrane, the steam evaporated is in the other side of film
The process of condensation, hydrophobic membrane play the role of interface between liquid and steam.Aperture ratio hydrone, the salt ion of distillation film are big
Much, up to several microns, hydrone and salt ion can be made to be separated from each other under temperature difference driving.
In recent years, more and more extensive about the research of film distillation technology, originally, face one of membrane distillation process is important to be asked
Topic is not exclusively for the film of membrane distillation preparation, and the structure and material physical property of the film generally used is difficult to meet the need of distillation process
It wants.Later, it is contemplated that this critical issue of film wetability, it is believed that the hydrophobicity of the film for distillation process is of great significance,
Therefore many scholars start to consider for hydrophobic surface even super hydrophobic surface to be applied in membrane distillation.Many of nature is planted
The surface of object and animal has superhydrophobic characteristic and self-cleaning function.It is inspired by it, different sides has been proposed in many scholars
Method comes constructing super-drainage surface, and has summed up the necessary condition for preparing super hydrophobic surface.When preparing super hydrophobic surface, structure
Building rough surface and being modified using low-surface energy substance is indispensable two conditions.It is commonly used to prepare the method for super-hydrophobic film
There are method of electrostatic spinning, coating, phase inversion and plasma technique etc..With the expansion of membrane distillation application field, separation group
Dividing no longer is simple saline solution, usually contains some organic solvents, so while super-hydrophobic film has excellent hydrophobicity
Can, but most of super hydrophobic surfaces are easy to be soaked by organic liquid, including oil, alkane and alcohol etc..When super hydrophobic surface is exposed to
When in the environment of organic pollutant, their anti-wettability may be subjected to damage, eventually lead to the forfeiture of self-cleaning ability, produce
Raw serious dirt.So develop a kind of pair of water droplet and the organic drop of low surface tension while having the film of anti-wellability (super double
Dredge film) become the direction that many researchers are studied.Only by the general coarse structure of building and use low-surface-energy object
Matter modifies ultra-amphosphobic difficult to realize, and the building of reentrant features is wherein playing important role.But reentrant features are upper width
Under narrow special construction, it is larger to obtain difficulty, and the methods of template reported in the literature, laser ablation can construct re-entrant angle knot
Structure, but matters are not used for surface of separating film of polymer.Application No. is 201710958054.2 Chinese invention patents to disclose one
Kind is film-made using method of electrostatic spinning and carries out the modified method of secondary spraying to film surface to prepare super-hydrophobic oleophobic composite membrane, is somebody's turn to do
Method is to construct reentrant features by the mutual overlap joint between electrospun fibers, but preparation process includes nano-silica
The preparation of SiClx sol solutions, the preparation of cellulose acetate solution, the preparation of electrostatic spinning precursor solution, hydrophobically modified nanometer two
Spray coating liquor, method of electrostatic spinning after silica sol liquid, modification prepare composite membrane, the modified two step spray coating methods in surface, this side
Method technique is excessively complicated, and step is excessively cumbersome, takes a long time.Also, method of electrostatic spinning is not the conventional method of preparative separation film,
It is not suitable for large scale preparation seperation film.
Summary of the invention
It is simple, time-consuming short super double the purpose of the present invention is in view of the above problems, providing a kind of preparation process
Dredge the preparation method of film.This method prepares polymer film using phase inversion, passes through the special fenestra formed during inversion of phases
Structure constructs reentrant features, the roughness of film matrix surface is further improved by the building of nano particle and using low
Surface energy substance is modified, and the super-amphiphobic film for all having anti-wellability to water and organic liquid is finally obtained.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of membrane distillation super-amphiphobic PS membrane:
(1) preparation has the PS membrane of interpenetrating networks pore structure: by polysulfones particle, pore-foaming agent and organic solvent according to one
Determine mass fraction to be added in round-bottomed flask, be stirred under certain temperature and revolving speed by oil bath agitating and heating device, until being formed equal
Phase solution, then constant temperature standing and defoaming.After deaeration, casting solution is cast on a glass, sprawls to be formed just by casting solution with scraper
Primary membrane is smoothly put into coagulating bath rapidly by filming, by the exchange of solvent and non-solvent, induce polysulfones gel solidification at
Film.
(2) building of film surface nanoscale rough structure: the ethyl orthosilicate of certain volume number and dehydrated alcohol are passed through
Uniform mixed solution is stirred into, A liquid is denoted as；It is again that the ammonium hydroxide of certain volume number and dehydrated alcohol is agitated at uniform mixed
Solution is closed, B liquid is denoted as.Polysulfones basement membrane obtained in step (1) is successively impregnated into the regular hour in A liquid and B liquid, through hydrolyzing
Condensation reaction growth in situ on PS membrane fenestra wall goes out uniform nano SiO 2 particle.
(3) film surface low-surface-energy is modified: will have the polysulfones base film of nanoscale rough structure obtained in step (2)
It is immersed in low-surface-energy small molecule/dehydrated alcohol mixed solution, low-surface-energy small molecule is made to be uniformly coated on PS membrane
Surface, put it into the baking oven with certain temperature a period of time later, make between low-surface-energy small molecule, low-surface-energy
Hydrolysis-condensation reaction occurs between small molecule and silica, forms the low-surface-energy thin layer of one layer of crosslinking in film surface.Pass through
The preparation of super-amphiphobic PS membrane may be implemented in above step.
Preferably, in above-mentioned steps 1, the mass fraction of polysulfones particle used is 8~20, and the mass fraction of pore-foaming agent is
2~7, the mass fraction of organic solvent is 73~90, organic solvent used be preferably N-Methyl pyrrolidone, dimethyl sulfoxide,
One of dimethyl acetamide, dimethylformamide, Isosorbide-5-Nitrae-dioxane, chloroform, methylene chloride or any two kinds mixed
Liquid is closed, pore-foaming agent used is one of polyethylene glycol, polyoxyethylene and polyvinylpyrrolidone or a variety of, polyethylene glycol used
Weight average molecular weight be preferably 3000kD~8000kD, polyoxyethylated weight average molecular weight used is preferably 1.5 × 104KD~1
×105KD, the weight average molecular weight of polyvinylpyrrolidone used are preferably 5 × 104KD~1.3 × 106kD。
Preferably, in above-mentioned steps 1, the heating temperature is 45 DEG C~85 DEG C, and heating time is 4~20h, stirring speed
Degree is 200~450rpm, and the glass plate includes smooth glass plate and abrasive glass plate, and the coagulating bath is double solidifications
Bath, the first coagulating bath are the mixed liquor of water and organic solvent, and the second gelation is deionized water, is had in first coagulating bath
Solvent and water volume ratio are 0:10~9:1, and the organic solvent in first coagulating bath is preferably N-Methyl pyrrolidone, two
Methyl sulfoxide, dimethyl acetamide, dimethylformamide, Isosorbide-5-Nitrae-dioxane, ethyl alcohol, normal propyl alcohol, isopropanol, in n-butanol
A kind of or any two kinds of mixed liquors, the soaking time in the first coagulating bath are 5~50s.
Preferably, in above-mentioned steps (1), the size of interpenetrating networks pore structure is 0.05 μm~8 μm.
Preferably, in above-mentioned steps (2), ethyl orthosilicate volume fraction is 10~50% in the A liquid, in A liquid
Soaking time is 1.5~8h；Ammonium hydroxide volume fraction is 15~45% in B liquid, and soaking time is 20~100min, institute in B liquid
The silica stated is preferably dimensioned to be 20nm~600nm.
Preferably, in above-mentioned steps (3), the low-surface-energy small molecule is 17 fluorine ruthenium trimethoxysilanes
(FAS), heptadecafluorodecyl triethoxysilane (FOTS), cross fluorine octyltrichlorosilane (PFTS), be perfluoro decyl trichlorosilane, hard
One of resin acid, in low-surface-energy small molecule/dehydrated alcohol mixed solution, small point of low-surface-energy in mixed solution
Daughter fraction is 1~14%, and standing time is 0.5~8h in an oven, and oven temperature is 35 DEG C~85 DEG C.
Application of the super-amphiphobic PS membrane in film distillation technology.
Advantage for present invention and the utility model has the advantages that
(1) present invention using the interpenetrating networks pore structure that classical non-solvent induction phase inversion is easily obtained in the process come
Reentrant features are constructed, using the growth in situ of silica dioxide granule, guarantee that nano SiO 2 particle is deposited in the stabilization of film matrix
Polycondensation reaction occurs with the silicone hydroxyl on the silica of film surface after the hydrolysis of, low-surface-energy small molecule, is formed stable low
Surface energy thin layer, film layer and the zygosity of polysulfones basement membrane are good, not easily to fall off.Operation is simple for preparation process, does not need valuableness
Equipment, large-scale film preparation can be completed in a short time.
(2) the film basis material that the present invention uses is polysulfones, it has, and excellent mechanical property, intensity is high, rigidity is big, In
Also it is able to maintain excellent mechanical property under high temperature, there is excellent inoxidizability, hydrolysis, thermal stability and high-temperature fusion to stablize
Property, furthermore polysulfone material also has excellent mechanical performance, electrical property, food hygiene, is most widely used membrane material
One of.
(3) super-amphiphobic PS membrane prepared by the present invention has dual anti-wellability to water droplet and organic drop, especially right
The extremely low n-hexane of surface tension also has nearly 90 ° of contact angle, has applied to during membrane distillation to the feed liquid containing organic drop
There is stable anti-wettability.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of PS membrane prepared by comparative example 1.
Fig. 2 is the contact angle figure of PS membrane prepared by comparative example 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of PS membrane prepared by comparative example 2.
Fig. 4 is the contact angle figure of PS membrane prepared by comparative example 2.
Fig. 5 is the scanning electron microscope (SEM) photograph of PS membrane prepared by comparative example 3.
Fig. 6 is the contact angle figure of PS membrane prepared by comparative example 3.
Fig. 7 is the scanning electron microscope (SEM) photograph after being roughened in embodiment 3 and is fluorinated modified.
Fig. 8 is the Contact-angle measurement result figure of the super-amphiphobic PS membrane in embodiment 3.
Specific embodiment
With reference to the accompanying drawing and by specific embodiment come present invention be described in more detail.It should be understood that following embodiments
It is to limit its protection scope for illustrating rather than.
Comparative example 1:
By 16 mass parts polysulfones particles, 4 mass parts polyvinylpyrrolidones, (weight average molecular weight is 1.3 × 106KD) and
80 mass parts dimethylformamides are added in round-bottomed flask, dissolve 10h under 80 DEG C of heating temperatures, 400rpm revolving speed until being formed
Homogeneous phase solution, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, is sprawled casting solution with scraper
Primary membrane is formed, primary membrane is smoothly put into rapidly in dimethylformamide/water (volume parts ratio 4:6) mixed liquor after 15s
It moves into deionized water, by the abundant exchange of solvent and non-solvent, induces polysulfones gel solidification film forming.It will be seen from figure 1 that
The PS membrane with interpenetrating networks reentrant features is successfully constructed, and the size in interpenetrating networks hole is about 5 μm, the film water drop contact
Angle is 0 °, is super hydrophilic super-oleophilic, it is impossible to be used in membrane distillation process.
Comparative example 2:
By 16 mass parts polysulfones particles, 4 mass parts polyvinylpyrrolidones, (weight average molecular weight is 1.3 × 106KD) and
80 mass parts dimethylformamides are added in round-bottomed flask, dissolve 10h under 80 DEG C of heating temperatures, 400rpm revolving speed until being formed
Homogeneous phase solution, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, is sprawled casting solution with scraper
Primary membrane is formed, primary membrane is smoothly put into rapidly in dimethylformamide/water (volume parts ratio 4:6) mixed liquor after 15s
It moves into deionized water, by the abundant exchange of solvent and non-solvent, induces polysulfones gel solidification film forming, can get pore size about
For 5 μm of interpenetrating networks hole.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
30%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction is 20%), note
Make B liquid.Obtained polysulfones basement membrane is impregnated into 4h respectively in sequence in A liquid, impregnates 50min in B liquid, it is anti-through hydrolytic condensation
Uniform, particle size about 200nm silica dioxide granule (Fig. 2) should be gone out by growth in situ on PS membrane fenestra wall.Obtain table
The PS membrane of face nanoscale rough structural modification.The film water droplet contact angle is 0 °, is super hydrophilic super-oleophilic, it is impossible to be used in film steams
Evaporate process.
Comparative example 3:
16 mass parts polysulfones particles and 84 mass parts dimethylformamides are added in round-bottomed flask, 80 DEG C of heating temperature
Degree, dissolution 10h is until form homogeneous phase solution under 400rpm revolving speed, then constant temperature standing and defoaming.After deaeration, casting solution is cast in slightly
Primary membrane is formed on rough glass plate, primary membrane is smoothly put into deionized water rapidly, passes through the abundant of solvent and non-solvent
Exchange, induction polysulfones gel solidification film forming.It can get the unsymmetric structure polysulfones base with dense layer surface and finger-like pore supporting layer
Film.
Ethyl orthosilicate and dehydrated alcohol is agitated at uniform mixed solution (ethyl orthosilicate volume fraction 30%),
It is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction 20%), it is denoted as B liquid.It will
Obtained polysulfones basement membrane impregnates 2h in A liquid respectively in sequence, impregnates 25min in B liquid, through hydrolysis-condensation reaction in polysulfones
Growth in situ goes out uniform, particle size about 100nm silica dioxide granule on film fenestra wall.Film surface is obtained completely by nanometer
The PS membrane of silica dioxide granule covering.
The film is immersed in heptadecafluorodecyl triethoxysilane/dehydrated alcohol mixed solution, ten in mixed solution
The volume fraction of seven fluorine ruthenium triethoxysilanes is 2%, and low-surface-energy small molecule is made to be uniformly coated on the surface of PS membrane,
0.5h in 85 DEG C of baking oven is put it into later, brings it about hydrolysis-condensation reaction, forms the low table of one layer of crosslinking in film surface
It face can thin layer.The PS membrane obtained by above step, 128 ° of water droplet contact angle, 52 ° of hexylene glycol contact angle, hexadecane contact
0 ° of angle, 0 ° of n-hexane contact angle, are applied to when membrane distillation process that salt-stopping rate is up to 99.30%, water vapor flux 10L/m2H, surely
Surely film surface starts to soak after running 0.5h.
Embodiment 1:
By 8 mass parts polysulfones particles, 2 mass parts polyoxyethylene, (weight average molecular weight is 1.0 × 105) and 90 mass parts kD
Dimethyl sulfoxide is added in round-bottomed flask, dissolves 4h under 55 DEG C of heating temperatures, 200rpm revolving speed until forming homogeneous phase solution, so
Constant temperature standing and defoaming afterwards.After deaeration, casting solution is cast on abrasive glass plate, sprawls casting solution to form primary membrane with scraper,
Primary membrane is smoothly put into rapidly in isopropanol/water (volume parts ratio 9:1) mixed liquor after 40s and is moved into deionized water, led to
The abundant exchange of solvent and non-solvent is crossed, induction polysulfones gel solidification film forming, available pore size is about 8 μm of interpenetrating networks
Hole.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
50%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction 45%), it is denoted as
B liquid.Obtained polysulfones basement membrane is impregnated into 1.5h respectively in sequence in A liquid, impregnates 100min in B liquid, through hydrolytic condensation
It reacts the growth in situ on PS membrane fenestra wall and goes out uniform, particle size about 600nm nano SiO 2 particle.Obtain table
The PS membrane of face nanoscale rough structural modification.
The film is immersed in heptadecafluorodecyl triethoxysilane/dehydrated alcohol mixed solution, ten in mixed solution
The volume fraction of seven fluorine ruthenium triethoxysilanes is 1%, and low-surface-energy small molecule is made to be uniformly coated on the surface of PS membrane,
0.5h in 85 DEG C of baking oven is put it into later, and hydrolytie polycondensation, low-surface-energy small molecule can occur between low-surface-energy small molecule
May also hydrolyze followed by silica on silicone hydroxyl occur polycondensation reaction, film surface formed one layer crosslinking low-surface-energy it is thin
Layer.Quasi- super-amphiphobic PS membrane is obtained by above step, 145 ° of water droplet contact angle, 132 ° of hexylene glycol contact angle, hexadecane connect
95 ° of feeler, 40 ° of n-hexane contact angle, are applied to when membrane distillation process that salt-stopping rate is up to 99.50%, water vapor flux 50L/
m2Film surface starts to soak after h, stable operation 2h.
Embodiment 2:
By 10 mass parts polysulfones particles, 7 mass parts polyethylene glycol (weight average molecular weight 8000kD) and 83 mass parts two
(mass parts ratio 60:40) is added in round-bottomed flask in chloromethanes/dimethyl acetamide mixed liquor, 45 DEG C of heating temperatures,
6h is dissolved under 250rpm revolving speed until forming homogeneous phase solution, then constant temperature standing and defoaming.After deaeration, casting solution casts in smooth glass
In glass plate, sprawls casting solution to form primary membrane with scraper, primary membrane is smoothly put into rapidly to n-propanol/water (volume parts
Than 7:3) it is moved into deionized water after 50s in mixed liquor, pass through the abundant exchange of solvent and non-solvent, induces polysulfones gel solidification
Film forming, the interpenetrating networks hole that available pore size is about 2 μm.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
30%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction is 20%), note
Make B liquid.Obtained polysulfones basement membrane is impregnated into 6h respectively in sequence in A liquid, impregnates 80min in B liquid, it is anti-through hydrolytic condensation
Uniform, particle size about 150nm nano SiO 2 particle should be gone out by growth in situ on PS membrane fenestra wall.Obtain surface
The PS membrane of nanoscale rough structural modification.
The film is immersed in stearic acid/dehydrated alcohol mixed solution, stearic acid obtains volume fraction and is in mixed solution
8%, so that low-surface-energy small molecule is uniformly coated on the surface of PS membrane, puts it into 6h in 50 DEG C of baking oven later, make it
Hydrolysis-condensation reaction occurs, forms the low-surface-energy thin layer of one layer of crosslinking in film surface.It is poly- that super-amphiphobic is obtained by above step
Sulfone film, 155 ° of water droplet contact angle, 152 ° of hexylene glycol contact angle, 125 ° of hexadecane contact angle, 75 ° of n-hexane contact angle, application
Salt-stopping rate is up to 99.87% when membrane distillation process, water vapor flux 25L/m2Film surface starts to moisten after h, stable operation 3.5h
It is wet.
Embodiment 3:
By 16 mass parts polysulfones particles, 4 mass parts polyvinylpyrrolidones, (weight average molecular weight is 1.3 × 106KD) and
80 mass parts dimethylformamides are added in round-bottomed flask, dissolve 10h under 80 DEG C of heating temperatures, 200rpm revolving speed until being formed
Homogeneous phase solution, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, is sprawled casting solution with scraper
Primary membrane is formed, primary membrane is smoothly put into rapidly in dimethylformamide/water (volume parts ratio 4:6) mixed liquor after 15s
It moves into deionized water, by the abundant exchange of solvent and non-solvent, induces polysulfones gel solidification film forming, can get pore size about
For 5 μm of interpenetrating networks hole.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
30%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume is that score is 20%),
It is denoted as B liquid.Obtained polysulfones basement membrane is impregnated into 4h respectively in sequence in A liquid, impregnates 50min in B liquid, through hydrolytic condensation
It reacts the growth in situ on PS membrane fenestra wall and goes out uniform, particle size about 200nm nano SiO 2 particle.Obtain table
The PS membrane of face nanoscale rough structural modification.
The film is immersed in 17 fluorine ruthenium trimethoxysilanes/dehydrated alcohol mixed solution, ten in mixed solution
The volume fraction of seven fluorine ruthenium trimethoxysilanes is 10%, and low-surface-energy small molecule is made to be uniformly coated on the table of PS membrane
Face puts it into 30min in 70 DEG C of baking oven later, brings it about hydrolysis-condensation reaction, forms one layer of crosslinking in film surface
Low-surface-energy thin layer.Super-amphiphobic PS membrane is obtained by above step, from figure 5 it can be seen that being attached to one layer in film surface
Silicon fluoride layer.154 ° of its water droplet contact angle, 150 ° of hexylene glycol contact angle, 121 ° of hexadecane contact angle, 67 ° of n-hexane contact angle,
Salt-stopping rate is up to 99.95% when applied to membrane distillation process, water vapor flux 20.5L/m2Film surface is opened after h, stable operation 4h
Begin to soak.
Embodiment 4:
By 20 mass parts polysulfones particles, 7 mass parts polyvinylpyrrolidones, (weight average molecular weight is 5 × 104) and 73 kD
Mass parts dimethyl acetamide is added in round-bottomed flask, dissolves 20h under 85 DEG C of heating temperatures, 450rpm revolving speed until being formed equal
Phase solution, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, and casting solution is sprawled shape with scraper
At primary membrane, primary membrane is smoothly put into rapidly in n-butanol/water (volume parts ratio 2:8) mixed liquor after 15s move into go from
In sub- water, by the abundant exchange of solvent and non-solvent, polysulfones gel solidification film forming is induced, available pore size is about 0.5 μm
Interpenetrating networks hole.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
10%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction is 15%), note
Make B liquid.Obtained polysulfones basement membrane is impregnated into 2h respectively in sequence in A liquid, impregnates 30min in B liquid, it is anti-through hydrolytic condensation
Uniform, particle size about 60nm nano SiO 2 particle should be gone out by growth in situ on PS membrane fenestra wall.Obtain surface
The PS membrane of nanoscale rough structural modification.
The film was immersed in fluorine octyltrichlorosilane/dehydrated alcohol mixed solution, fluorine octyl is crossed in mixed solution
The volume fraction of trichlorosilane is 14%, so that low-surface-energy small molecule is uniformly coated on the surface of PS membrane, is put later
Enter 8h in 35 DEG C of baking oven, bring it about hydrolysis-condensation reaction, forms the low-surface-energy thin layer of one layer of crosslinking in film surface.Pass through
Above step obtains super-amphiphobic PS membrane, 160 ° of water droplet contact angle, 149 ° of hexylene glycol contact angle, 80 ° of hexadecane contact angle, just
10 ° of hexane contact angle, it is applied to when membrane distillation process that salt-stopping rate is up to 99.99%, water vapor flux 5L/m2H, stable operation 1h
Film surface starts to soak afterwards.
Embodiment 5:
By 18 mass parts polysulfones particles, 6 mass parts polyoxyethylene, (weight average molecular weight is 1.5 × 104) and 86 mass kD
Part dimethylformamide is added in round-bottomed flask, is dissolved 12h under 60 DEG C of heating temperatures, 300rpm revolving speed and is mixed until being formed
Liquid, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, sprawls to be formed just by casting solution with scraper
Primary membrane is smoothly put into rapidly 30s in dimethylformamide/isopropanol/water (volume parts ratio 6:2:2) mixed liquor by filming
It moves into deionized water afterwards, by the abundant exchange of solvent and non-solvent, induces polysulfones gel solidification film forming, can get pore size
About 4 μm of interpenetrating networks hole.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
40%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction is 30%), note
Make B liquid.Obtained polysulfones basement membrane is impregnated into 5h respectively in sequence in A liquid, impregnates 60min in B liquid, it is anti-through hydrolytic condensation
Uniform, particle size about 300nm nano SiO 2 particle should be gone out by growth in situ on PS membrane fenestra wall.Obtain surface
The PS membrane of nanoscale rough structural modification.
The film is immersed in perfluoro decyl trichlorosilane/dehydrated alcohol mixed solution, perfluoro decyl in mixed solution
The volume fraction of trichlorosilane is 14%, so that low-surface-energy small molecule is uniformly coated on the surface of PS membrane, is put later
Enter 5h in 60 DEG C of baking oven, bring it about hydrolysis-condensation reaction, forms the low-surface-energy thin layer of one layer of crosslinking in film surface.Pass through
Above step obtain super-amphiphobic PS membrane, 160 ° of water droplet contact angle, 156 ° of hexylene glycol contact angle, 130 ° of hexadecane contact angle,
90 ° of n-hexane contact angle, it is applied to when membrane distillation process that salt-stopping rate is up to 99.91%, water vapor flux 25L/m2H stablizes fortune
Film surface starts to soak after row 4h.
Embodiment 6:
By 14 mass parts polysulfones particles, 6 mass parts polyethylene glycol (weight average molecular weight 3000kD) and 90 mass parts N-
Methyl pyrrolidone is added in round-bottomed flask, is dissolved 10h under 70 DEG C of heating temperatures, 300rpm revolving speed and is mixed until being formed
Liquid, then constant temperature standing and defoaming.After deaeration, casting solution is cast on abrasive glass plate, sprawls to be formed just by casting solution with scraper
Primary membrane is smoothly put into deionized water rapidly by filming, by the abundant exchange of solvent and non-solvent, induces polysulfones gel
Film-forming, the interpenetrating networks hole that available pore size is about 0.05 μm.
By ethyl orthosilicate and dehydrated alcohol, agitated at uniform mixed solution, (ethyl orthosilicate volume fraction is
30%), it is denoted as A liquid；It is again that ammonium hydroxide and dehydrated alcohol is agitated at uniform mixed solution (ammonium hydroxide volume fraction is 40%), note
Make B liquid.Obtained polysulfones basement membrane is impregnated into 1.5h respectively in sequence in A liquid, impregnates 20min in B liquid, through hydrolytic condensation
It reacts the growth in situ on PS membrane fenestra wall and goes out uniform, particle size about 20nm nano SiO 2 particle.Obtain table
The PS membrane of face nanoscale rough structural modification.
The film is immersed in perfluoro decyl trichlorosilane/dehydrated alcohol mixed solution, perfluoro decyl in mixed solution
The volume fraction of trichlorosilane is 12%, so that low-surface-energy small molecule is uniformly coated on the surface of PS membrane, is put later
Enter 6h in 55 DEG C of baking oven, bring it about hydrolysis-condensation reaction, forms the low-surface-energy thin layer of one layer of crosslinking in film surface.Pass through
Above step obtains quasi- super-amphiphobic PS membrane, 140 ° of water droplet contact angle, 130 ° of hexylene glycol contact angle, 80 ° of hexadecane contact angle,
10 ° of n-hexane contact angle, it is applied to when membrane distillation process that salt-stopping rate is up to 99.98%, water vapor flux 2L/m2H, stable operation
Film surface starts to soak after 1.5h.
Claims (7)
1. a kind of membrane distillation preparation method of super-amphiphobic PS membrane, which is characterized in that comprising the following three steps: preparation has
The PS membrane of interpenetrating networks pore structure；The building of film surface nanoscale rough structure；Film surface low-surface-energy is modified, specifically:
(1) preparation has the PS membrane of interpenetrating networks pore structure: by the polysulfones particle of certain mass number, pore-foaming agent and organic
Solvent is added in round-bottomed flask, is stirred under certain temperature and revolving speed by oil bath agitating and heating device, until homogeneous phase solution is formed,
Then constant temperature standing and defoaming, after deaeration, casting solution casting forms primary membrane on a glass, and primary membrane is smoothly put into rapidly
In coagulating bath, by the exchange of solvent and non-solvent, polysulfones gel solidification film forming is induced；
(2) building of film surface nanoscale rough structure: the ethyl orthosilicate of certain volume number and dehydrated alcohol is agitated
At uniform mixed solution, it is denoted as A liquid；It is again that the ammonium hydroxide of certain volume number is agitated molten at uniformly mixing with dehydrated alcohol
Liquid is denoted as B liquid, polysulfones basement membrane obtained in step (1) is successively impregnated the regular hour in A liquid and B liquid, through hydrolytic condensation
Reaction growth in situ on PS membrane fenestra wall goes out uniform nano SiO 2 particle；
(3) film surface low-surface-energy is modified: the polysulfones basement membrane obtained in step (1) with nanoscale rough structure is immersed in
In low-surface-energy small molecule/dehydrated alcohol mixed solution, low-surface-energy small molecule is made to be uniformly coated on the surface of PS membrane,
A period of time in the baking oven with certain temperature is put it into later, brings it about hydrolysis-condensation reaction, forms one in film surface
The low-surface-energy thin layer of layer crosslinking.
2. the membrane distillation according to claim 1 preparation method of super-amphiphobic PS membrane, which is characterized in that in step (1)
The mass fraction of the polysulfones particle is 8~20, and the mass fraction of pore-foaming agent is 2~7, and the mass fraction of organic solvent is 73
~90, the organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethylformamide, Isosorbide-5-Nitrae-
One of dioxane, chloroform, methylene chloride or any two kinds of mixed liquor, the pore-foaming agent are polyethylene glycol, gather
One of ethylene oxide and polyvinylpyrrolidone are a variety of, the weight average molecular weight of polyethylene glycol used be 3000kD~
8000kD, the polyoxyethylated weight average molecular weight are 1.5 × 104KD~1 × 105KD, the polyvinylpyrrolidone
Weight average molecular weight is 5 × 104KD~1.3 × 106kD。
3. the membrane distillation according to claim 1 preparation method of super-amphiphobic PS membrane, which is characterized in that in step (1)
The heating temperature is 45 DEG C~85 DEG C, and heating time is 4~20h, and mixing speed is 200~450rpm, the glass
Plate is smooth glass plate or abrasive glass plate, and the coagulating bath is dual-bath coagulation, and the first coagulating bath is water and organic solvent
Mixed liquor, the second gelation are deionized water, and organic solvent and water volume ratio are 0:10~9:1 in first coagulating bath,
The organic solvent is N-Methyl pyrrolidone, dimethyl sulfoxide, dimethyl acetamide, dimethylformamide, Isosorbide-5-Nitrae-dioxy
One of six rings, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol or any two kinds of mixed liquors, when immersion in the first coagulating bath
Between be 5~50s.
4. the membrane distillation according to claim 1 preparation method of super-amphiphobic PS membrane, which is characterized in that in step (1)
The size of the interpenetrating networks pore structure is 0.05 μm~8 μm.
5. the building of step 2) film surface silica nanometer coarse structure according to claim 1, which is characterized in that institute
Ethyl orthosilicate volume fraction is 10~50% in the A liquid stated, and soaking time is 1.5~8h in A liquid；Ammonium hydroxide volume in B liquid
Score is 15~45%, and soaking time is 20~100min in B liquid.
6. the building of step 2) film surface silica nanometer coarse structure according to claim 1, which is characterized in that institute
The size for the silica stated is 200nm~600nm.
7. step 3) film surface low-surface-energy according to claim 1 is modified, the low-surface-energy small molecule is 17
Fluorine ruthenium trimethoxysilane, heptadecafluorodecyl triethoxysilane, cross fluorine octyltrichlorosilane, perfluoro decyl trichlorosilane,
One of stearic acid, in low-surface-energy small molecule/dehydrated alcohol mixed solution, low-surface-energy is small in mixed solution
Molecular volume score is 1~14%, and standing time is 0.5~8h in an oven, and oven temperature is 35 DEG C~85 DEG C.
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| CN113731199A (en) * | 2021-07-20 | 2021-12-03 | 东华大学 | Super-amphiphobic membrane and preparation method and application thereof |
| CN113648678A (en) * | 2021-07-30 | 2021-11-16 | 珠海健科医用材料有限公司 | Polysulfone polymer and purification method thereof |
| CN113754308A (en) * | 2021-09-30 | 2021-12-07 | 常州大学 | Preparation method of super-amphiphobic antifouling transparent coating |
| CN113754308B (en) * | 2021-09-30 | 2022-07-26 | 常州大学 | Preparation method of super-amphiphobic antifouling transparent coating |
| CN114452719A (en) * | 2022-02-10 | 2022-05-10 | 吉林大学 | Preparation method of air filtration electrostatic spinning nanofiber membrane |
| CN114452719B (en) * | 2022-02-10 | 2023-09-15 | 吉林大学 | Preparation method of air filtration electrostatic spinning nanofiber membrane |
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