CN114713047A - Super-oleophobic oil-water separation membrane and preparation method thereof - Google Patents
Super-oleophobic oil-water separation membrane and preparation method thereof Download PDFInfo
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- CN114713047A CN114713047A CN202011524487.5A CN202011524487A CN114713047A CN 114713047 A CN114713047 A CN 114713047A CN 202011524487 A CN202011524487 A CN 202011524487A CN 114713047 A CN114713047 A CN 114713047A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000000926 separation method Methods 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 85
- 238000002791 soaking Methods 0.000 claims abstract description 38
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 3
- 125000004386 diacrylate group Chemical group 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims abstract description 3
- 239000002657 fibrous material Substances 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims abstract description 3
- 239000002759 woven fabric Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 66
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002105 nanoparticle Substances 0.000 claims description 34
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- 239000004408 titanium dioxide Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000013007 heat curing Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- GOCCREQJUBABAL-UHFFFAOYSA-N 2,2-dihydroxyacetic acid Chemical compound OC(O)C(O)=O GOCCREQJUBABAL-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 150000004662 dithiols Chemical class 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- -1 fluoro-decyl Chemical group 0.000 claims description 2
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- LHLRHWJTTUCDQA-UHFFFAOYSA-N 1-fluorodecane Chemical compound CCCCCCCCCCF LHLRHWJTTUCDQA-UHFFFAOYSA-N 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 11
- 235000019198 oils Nutrition 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- VUPXDAQNLSYDHS-UHFFFAOYSA-N decyl-(fluoromethoxy)-dimethoxysilane Chemical compound CCCCCCCCCC[Si](OC)(OC)OCF VUPXDAQNLSYDHS-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
The invention discloses a super-oleophobic oil-water separation membrane and a preparation method thereof, wherein the oil-water separation membrane comprises a base material and a super-oleophobic copolymer solidified on the surface of the base material, the base material is one or more of a porous fiber material, a porous ceramic material or a fiber woven fabric, the super-oleophobic copolymer is Rn-POSS-PEGDA-POSS-Rn, and the Rn-POSS-PEGDA-POSS-Rn is a copolymer formed by copolymerizing decyl fluoride polyhedral oligomeric silsesquioxane and hydrophilic polymer polyethylene glycol diacrylate; the molecular weight of the Rn-POSS in the polymer accounts for 5-15%, and R is a fluorodecyl group. The method specifically comprises the following steps: s1) surface modification treatment of the base material; s2) soaking the modified base material into the solution of the super-oleophobic copolymer, and thermally curing the soaked base material under the protection of nitrogen to obtain the super-oleophobic oil-water separation membrane. The super oleophobic oil-water separation membrane oil contact angle that this application file prepared can reach more than 160, and oil-water separation is respond well.
Description
Technical Field
The invention relates to the technical field of super-oleophobic materials, in particular to a super-oleophobic oil-water separation membrane and a preparation method thereof.
Background
With the rapid development of economy, a large amount of oily wastewater is generated in the chemical industry and frequent oil spill accidents, so that serious environmental pollution and ecological damage are caused, and the health and safety of human are harmed. Therefore, how to realize the efficient separation of oil and water and obtain clean water to avoid pollution still faces great challenges. At present, the traditional oil-water separation methods comprise a gravity method, a centrifugal method, an air floatation method and the like, and the treatment methods are simple and convenient to operate, but are only effective on simple oil-water mixtures and have the defects of low separation efficiency, high cost, poor recycling rate and the like. Low efficiency and easy secondary pollution. Although widely used for oil-water separation, common membrane materials are long in time consumption, easy to pollute, non-selective and limited in application due to the requirement of pretreatment. Therefore, there is a need to develop new processes and materials for oil-water separation with high separation efficiency, good selectivity and high stability. In recent years, inspired by biological phenomena such as 'self-cleaning' and 'fish scale' of lotus leaves, a series of membrane materials with special wettability are widely used for oil-water separation due to different wettability on oil and water. Compared with a super-hydrophobic/super-oleophilic oil film material, the super-hydrophilic/underwater super-oleophobic film material has the super-oleophobic property underwater, so that oil pollution can be effectively avoided in the oil-water separation process.
Patent CN103623709B reports a graphene oxide modified super-hydrophilic super-oleophobic oil-water separation membrane, and a preparation method and application thereof. The method comprises the following steps of mixing a hydrophilic polymer water-sensitive agent and a crosslinking film-forming agent according to the ratio of 1: 9-9: 1, mixing with nano silica sol according to a mass ratio of 1: 9-9: 1, dissolving the graphene oxide in water, uniformly stirring the solution by magnetic force to prepare a solution with the concentration of 1-99%, adding 0.5-1% of graphene oxide serving as an inorganic cross-linking agent, and uniformly dispersing the solution by ultrasonic; ultrasonically cleaning a 100-300-mesh fabric silk screen, airing at normal temperature, forming a film on the silk screen by adopting spraying, dip-coating or spin-coating, and drying and crosslinking to obtain the super-hydrophilic and underwater super-oleophobic oil-water separation net film. The oil-water separation mesh membrane has excellent swelling resistance and mechanical property after crosslinking modification of graphene, has contact angles of 0 degrees to water and oil in air, and has super-hydrophilicity; the contact angle of the paint to oil drops under water is more than 150 degrees, and the paint has the characteristic of low adhesion to the oil drops. The net film of the invention can be applied to the separation of oil-water mixture and the treatment of oily sewage.
According to the method, a TiO2 nanoparticle (TiO2 NPs) coated super-hydrophilic/underwater super-oleophobic stainless steel net film is prepared by a one-step dipping and in-situ curing method in the literature (Cao Si, preparation of a super-hydrophilic/underwater super-oleophobic membrane and research on oil-water separation performance [ J ], Shanxi university, 2016), the influence of the viscosity and concentration of a coating liquid on a contact angle and oil-water separation efficiency is investigated, a TiO2 nanowire (TiO2 NWs) modified super-hydrophilic/underwater super-oleophobic membrane material is prepared according to the result, the wettability is improved, the influence of the concentration of TiO2 NWs on the surface roughness, the wettability and the oil-water separation efficiency is investigated, and finally the influence of the synergistic effect of the pore diameter and the wettability on the oil-water separation efficiency is comprehensively researched. The main research result is that (1) the TiO2 NPs/PVP-SS oil-water separation membrane with hydrophilic/underwater super oleophobic property is successfully prepared by coating the mixed solution of TiO2 NPs and polyvinylpyrrolidone (PVP) on a stainless steel mesh (SS) through a one-step dipping and in-situ curing method.
In summary, the research focus of the superoleophobic separation material at present mainly focuses on modification by inorganic nanoparticles, which are high in cost and generally have high requirements for reaction condition control, so that another superoleophobic separation material needs to be developed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a super-oleophobic oil-water separation membrane and a preparation method thereof.
The specific technical scheme of the invention is as follows:
a super oleophobic oil-water separation membrane comprises a substrate and a super oleophobic copolymer solidified on the surface of the substrate, wherein the super oleophobic copolymer is Rn-POSS-PEGDA-POSS-Rn (POSS-oligomeric silsesquioxane, PEGDA-polyethylene glycol diacrylate).
Wherein the base material is any one of a porous fiber material, a porous ceramic material or a fiber woven fabric.
The Rn-POSS-PEGDA-POSS-Rn is a copolymer formed by copolymerizing fluorodecyl polyhedral oligomeric silsesquioxane and a hydrophilic polymer; the molecular weight of the Rn-POSS in the polymer accounts for 5-15%.
Wherein R is a fluorodecyl group; and n is a natural number which is more than 4 and less than 10.
The fluoro-decyl polyhedral oligomeric silsesquioxane is synthesized by hydrosilylation after vinyl trimethoxy silane and fluoro-decyl trimethoxy silane are subjected to condensation reaction.
The invention also discloses a preparation method of the super-oleophobic oil-water separation membrane, which comprises the following steps:
s1) surface modification treatment of the base material;
s2) soaking the modified base material into the solution of the super-oleophobic copolymer, and thermally curing the soaked base material under the protection of nitrogen to obtain the super-oleophobic oil-water separation membrane.
Further, in the step S1), the surface modification treatment of the substrate employs silica and/or titania nanoparticles.
Further, in the step S1), the modifying of the base material specifically includes the following steps: cleaning and drying the base material, soaking the base material in acid liquor to activate the surface of the base material in acid, soaking the base material after acid activation in turbid liquid formed by dispersing silicon dioxide and/or titanium dioxide nano particles, and carrying out ultrasonic treatment under a heating condition to uniformly load the silicon dioxide and/or titanium dioxide nano particles on the surface of the base material.
Further, in the step S1), the acid solution is a mixed solution of hydrochloric acid having a concentration of 15 to 25% and hypochlorite having a concentration of 10 to 15%.
Further, in the step S1), the substrate is soaked in the acid solution for 5-15 min; and ultrasonically soaking the base material in turbid liquid formed by dispersing silicon dioxide and/or titanium dioxide nano particles for 15-30 min, wherein the heating temperature is 70-85 ℃.
Further, in the step S2), the concentration of the suspension of the superoleophobic copolymer is 3-10%.
Further, in the step S2), the heat curing temperature is 350-370 ℃.
The invention has the following technical effects:
the invention discloses a super-oleophobic oil-water separation membrane and a preparation method thereof.
The invention provides a super-oleophobic oil-water separation membrane and a preparation method thereof, aiming at the technical problems of high cost and reaction condition control requirement in the existing oil-water separation technology. The super oleophobic oil-water separation membrane prepared by the application file has an oil contact angle which can reach more than 160 degrees, and has good oil-water separation effect.
Detailed Description
The present invention is further illustrated by the following examples.
The Rn-POSS-PDMS-POSS-Rn used in the following examples was prepared by the following method:
s1) preparation of fluorodecyl polyhedral oligomeric silsesquioxane:
s11) in a molar ratio of 1: 1, adding vinyltrimethoxysilane and fluorodecyltrimethoxysilane into acidified acetone alternately and slowly to ensure that the concentration of the vinyltrimethoxysilane is 5 percent, heating to 75 ℃ simultaneously, stirring, reacting and refluxing for 48 hours, filtering and washing the precipitate to obtain an intermediate product;
s12) adding the intermediate product into anhydrous ether, stirring and dissolving, then dropwise adding 10% anhydrous ether solution of dithiol dihydroxyacetic acid into the solution to ensure that the mass ratio of the dithiol dihydroxyacetic acid to the intermediate product is 5:1, stirring and heating to 55 ℃, refluxing for 24h, cooling, then adding activated carbon, continuing refluxing and stirring, filtering and concentrating, then adding a solvent, refluxing for 4h, filtering and concentrating to obtain the fluorodecyl polyhedral oligomeric silsesquioxane.
S2) adding PEGDA into diethyl ether solution of the fluorodecyl polyhedral oligomeric silsesquioxane under the protection of nitrogen and heating at 145 ℃ to ensure that the mass fraction of the fluorodecyl polyhedral oligomeric silsesquioxane in the solution is 5%, stirring for reaction for 3h, and then filtering under reduced pressure to obtain the superoleophobic copolymer.
Example 1
A super-oleophobic oil-water separation membrane comprises the following preparation steps:
s1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 15% hydrochloric acid and 15% hypochlorite for 5min to activate the surface of the base material in an acid manner, then soaking the base material after the acid activation in a suspension formed by dispersing silicon dioxide nano particles, performing ultrasonic soaking for 30min at 70 ℃ to uniformly load the silicon dioxide and/or titanium dioxide nano particles on the surface of the base material, stopping ultrasonic soaking, continuing to soak for 10min, taking out and performing vacuum drying to obtain the base material with the loaded silicon dioxide nano particles.
S2) soaking the substrate loaded with the silicon dioxide nanoparticles into a 3% super-oleophobic copolymer solution, and heating the soaked substrate to 350 ℃ under the protection of nitrogen for heat curing for 8h to obtain the super-oleophobic oil-water separation membrane.
Example 2
A super-oleophobic oil-water separation membrane comprises the following preparation steps:
s1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 25% hydrochloric acid and 10% hypochlorite for 15min to activate the surface of the base material in an acid manner, soaking the base material after the acid activation in a suspension formed by dispersing silica nanoparticles, performing ultrasonic soaking for 15min at 85 ℃ to uniformly load the silica nanoparticles on the surface of the base material, stopping the ultrasonic treatment, continuing to soak for 5min, and taking out the base material for vacuum drying to obtain the base material with the silica and/or titanium dioxide nanoparticles loaded.
S2) soaking the substrate loaded with the silicon dioxide nanoparticles into a 10% super-oleophobic copolymer solution, and heating the soaked substrate to 370 ℃ under the protection of nitrogen for heat curing for 3h to obtain the super-oleophobic oil-water separation membrane.
Example 3
A super-oleophobic oil-water separation membrane comprises the following preparation steps:
s1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 15% hydrochloric acid and 15% hypochlorite for 5min to activate the surface of the base material in an acid manner, soaking the base material after the acid activation in a suspension formed by dispersing titanium dioxide nanoparticles, performing ultrasonic soaking for 30min at 70 ℃ to uniformly load the titanium dioxide nanoparticles on the surface of the base material, stopping the ultrasonic treatment, continuing to soak for 5min, and taking out and vacuum-drying to obtain the base material with the loaded titanium dioxide nanoparticles.
S2) soaking the base material loaded with the titanium dioxide nanoparticles into a 3% super-oleophobic copolymer solution, and heating the soaked base material to 350 ℃ under the protection of nitrogen for heat curing for 8h to obtain the super-oleophobic oil-water separation membrane.
Example 4
S1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 25% hydrochloric acid and 10% hypochlorite for 15min to activate the surface of the base material in an acid manner, soaking the base material after the acid activation in a suspension formed by dispersing titanium dioxide nanoparticles, performing ultrasonic soaking for 15min at 85 ℃ to uniformly load the titanium dioxide nanoparticles on the surface of the base material, stopping the ultrasonic treatment, continuing to soak for 10min, and taking out for vacuum drying to obtain the base material with the loaded titanium dioxide nanoparticles.
S2) soaking the base material loaded with the titanium dioxide nanoparticles into 10% of super-oleophobic copolymer solution, and heating the soaked base material to 370 ℃ under the protection of nitrogen for heat curing for 3h to obtain the super-oleophobic oil-water separation membrane.
Example 5
S1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 15% hydrochloric acid and 15% hypochlorite for 5min to activate the surface of the base material in an acid manner, soaking the base material after the acid activation in a suspension formed by dispersing silicon dioxide and titanium dioxide nanoparticles, performing ultrasonic soaking for 30min at 70 ℃ to uniformly load the silicon dioxide and titanium dioxide nanoparticles on the surface of the base material, stopping ultrasonic soaking, continuing soaking for 5min, taking out, and performing vacuum drying to obtain the base material with the silicon dioxide and titanium dioxide nanoparticles loaded completely.
S2) soaking the substrate loaded with the silicon dioxide and titanium dioxide nanoparticles into a 3% super-oleophobic copolymer solution, and heating the soaked substrate to 350 ℃ under the protection of nitrogen for heat curing for 8h to obtain the super-oleophobic oil-water separation membrane.
Example 6
S1) surface modification treatment of the base material;
cleaning and drying the base material, soaking the base material in a mixed solution formed by 25% hydrochloric acid and 10% hypochlorite for 15min to activate the surface of the base material in an acid manner, soaking the base material after the acid activation in a suspension formed by dispersing silicon dioxide and titanium dioxide nanoparticles, performing ultrasonic soaking for 15min at 85 ℃ to uniformly load the silicon dioxide and titanium dioxide nanoparticles on the surface of the base material, stopping ultrasonic soaking, continuing soaking for 10min, taking out, and performing vacuum drying to obtain the base material with the silicon dioxide and titanium dioxide nanoparticles loaded completely.
S2) soaking the substrate loaded with the silicon dioxide and titanium dioxide nanoparticles into a 10% super-oleophobic copolymer solution, and heating the soaked substrate to 370 ℃ under the protection of nitrogen for heat curing for 3h to obtain the super-oleophobic oil-water separation membrane.
The surfaces of the superoleophobic oil-water separation membranes obtained in examples 1 to 6 were subjected to oil contact angle measurement using diesel oil, and an oil-water separation effect test using an oil-water mixture formed by dyed deionized water and diesel oil was performed, and the test results are shown in table 1. As can be seen from Table 1, the superoleophobic oil-water separation membrane prepared by the invention has an oil contact angle of more than 160 degrees and has good oil-water separation effect.
| Sample (I) | Oil contact Angle (°) | Water yield (%) of oil-water separation |
| Example 1 | 161.1 | 97.5 |
| Example 2 | 160.3 | 98.1 |
| Example 3 | 160.4 | 96.3 |
| Example 4 | 161.0 | 97.7 |
| Example 5 | 161.3 | 98.2 |
| Example 6 | 162.4 | 98.5 |
Claims (12)
1. A super-oleophobic oil-water separation membrane is characterized by comprising a base material and a super-oleophobic copolymer solidified on the surface of the base material, wherein the base material is one or more of a porous fiber material, a porous ceramic material or a fiber woven fabric, the super-oleophobic copolymer is Rn-POSS-PEGDA-POSS-Rn, and the Rn-POSS-PEGDA-POSS-Rn is a copolymer formed by copolymerizing decyl polyhedral oligomeric silsesquioxane and a hydrophilic polymer polyethylene glycol diacrylate; the molecular weight of the Rn-POSS in the polymer accounts for 5-15%, and R is a fluorodecyl group.
2. The separation membrane according to claim 1, wherein n is a natural number of more than 4 and less than 10.
3. The separation membrane according to claim 1, wherein the fluorodecyl polyhedral oligomeric silsesquioxane is synthesized by hydrosilylation after condensation reaction of vinyltrimethoxysilane and fluorodecyl trimethoxysilane.
4. The preparation method of the superoleophobic oil-water separation membrane in any one of claims 1-3, characterized by comprising the following steps:
s1) carrying out surface modification treatment on the base material;
s2) carrying out condensation reaction on vinyltrimethoxysilane and fluorodecyl trimethoxysilane, and synthesizing the fluorodecyl polyhedral oligomeric silsesquioxane through hydrogen sulfide addition; the fluoro-decyl polyhedral oligomeric silsesquioxane is copolymerized with the hydrophilic polymer to form a super oleophobic copolymer;
s3) soaking the modified base material into the solution of the super-oleophobic copolymer, and thermally curing the soaked base material under the protection of nitrogen to obtain the super-oleophobic oil-water separation membrane.
5. The method according to claim 4, wherein in step S1), the surface modification treatment of the substrate employs silica and/or titania nanoparticles.
6. The method according to claim 5, characterized in that in step S1), the modification of the substrate comprises in particular the steps of: cleaning and drying the base material, soaking the base material in acid liquor to activate the surface of the base material in acid, soaking the base material after acid activation in turbid liquid formed by dispersing silicon dioxide and/or titanium dioxide nano particles, and carrying out ultrasonic treatment under a heating condition to uniformly load the silicon dioxide and/or titanium dioxide nano particles on the surface of the base material.
7. The method according to claim 6, wherein in step S1), the acid solution is a mixed solution of hydrochloric acid with a concentration of 15-25% and hypochlorite with a concentration of 10-15%.
8. The method according to claim 6, wherein in step S1), the substrate is soaked in the acid solution for 5-15 min; and ultrasonically soaking the base material in turbid liquid formed by dispersing silicon dioxide and/or titanium dioxide nano particles for 15-30 min, wherein the heating temperature is 70-85 ℃.
9. The method according to claim 4, wherein the step of preparing the fluorodecyl polyhedral oligomeric silsesquioxane in the step S2) comprises:
mixing a mixture of 1: 1, adding vinyltrimethoxysilane and fluorodecyltrimethoxysilane into acidified acetone alternately and slowly to ensure that the concentration of the vinyltrimethoxysilane is 4-6 percent, heating to 70-80 ℃, stirring, reacting and refluxing for 48 hours, filtering and washing the precipitate to obtain an intermediate product;
adding the intermediate product into anhydrous ether, stirring and dissolving, dropwise adding 8-12% dithiol dihydroxyacetic acid anhydrous ether solution into the solution to enable the mass ratio of dithiol dihydroxyacetic acid to the intermediate product to be 4-6:1, stirring and heating to 50-60 ℃, refluxing for 20-28h, cooling, adding activated carbon, continuously refluxing and stirring, filtering and concentrating, adding a solvent, refluxing for 3-5h, filtering and concentrating to obtain the fluorodecyl polyhedral oligomeric silsesquioxane.
10. The method according to claim 4, characterized in that in step S2), the step of copolymerizing to form a superoleophobic copolymer comprises: under the protection of nitrogen and at the temperature of 140 ℃ and 150 ℃, PEGDA is added into diethyl ether solution of the fluorodecyl polyhedral oligomeric silsesquioxane to ensure that the mass fraction of the fluorodecyl polyhedral oligomeric silsesquioxane in the solution is 4-6%, the mixture is stirred and reacted for 2-4h, and then the mixture is filtered under reduced pressure to obtain the super oleophobic copolymer.
11. The method according to claim 4, wherein in step S3), the superoleophobic copolymer is formed into a suspension with a concentration of 3-10%.
12. The method according to claim 4, wherein the heat curing temperature in step S3) is 350-370 ℃.
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