CN100553752C - A kind of preparation method of vinylidene difluoride planar ultrafiltration membrane with gradient structure - Google Patents
A kind of preparation method of vinylidene difluoride planar ultrafiltration membrane with gradient structure Download PDFInfo
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- CN100553752C CN100553752C CNB2007100678607A CN200710067860A CN100553752C CN 100553752 C CN100553752 C CN 100553752C CN B2007100678607 A CNB2007100678607 A CN B2007100678607A CN 200710067860 A CN200710067860 A CN 200710067860A CN 100553752 C CN100553752 C CN 100553752C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 239000012528 membrane Substances 0.000 title claims abstract description 22
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 13
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 title claims description 5
- 239000007788 liquid Substances 0.000 claims abstract description 38
- 230000001112 coagulating effect Effects 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 238000000576 coating method Methods 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 150000003014 phosphoric acid esters Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 abstract description 19
- 239000002033 PVDF binder Substances 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 210000002615 epidermis Anatomy 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
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Abstract
The invention discloses the preparation method of a kind of gradient-structure polyvinylidene fluoride flat ultrafiltration.At first Kynoar and additive at high temperature are dissolved in the phosphoric acid ester solvent, to filter preparation liquid blade coating after the final vacuum deaeration then on nonwoven, in air, place certain hour, to scrape the nonwoven that scribbles preparation liquid at last immerses in the definite composition coagulating bath, successively, form the gradient-structure milipore filter through low temperature and two processes of high temperature gel.Such milipore filter can directly apply to the ultra-filtration and separation field, also can be used as support membrane and prepares various composite membranes.By the polyvinylidene fluoride (PVDF) ultrafiltration membrane of this method preparation, be the partially crystallizable layer near the film surface, lower floor is the amorphous layer of network-like pore structure, and the shrinkage factor of film is low, and mechanical property is superior.The inventive method is simple, and raw material is cheap and easy to get.
Description
Technical field
The present invention relates to polymeric membrane preparation and film separation field, relate in particular to the preparation method of a kind of gradient-structure polyvinylidene fluoride flat ultrafiltration.
Background technology
PVDF is a kind of crystalline polymer, and density is 1.78g/cm
3, vitrification point is-39 ℃, and crystalline melt point is 180 ℃, and decomposition temperature still can keep good intensity more than 316 ℃ under uniform temperature and pressurized.Excellent anticorrosive ageing-resistant performance is arranged, its film in outdoor placement one, do not become fragile in 20 years yet, have excellent acid and alkali resistance, oxidant, UV resistant and ageing resistace, chemical stability is good, organic solvents such as aliphatic hydrocarbon, alcohol, aldehyde do not have influence to it yet.Therefore, Kynoar (PVDF) micro-filtration membrane and milipore filter are widely used in fields such as medical treatment, environmental protection, water treatment, petrochemical industry, food industry, can also be applied to aspects such as film distillation, gas purification, organic solvent be refining.
Wrasidlo is at United States Patent (USP) 4,629, proposes the notion of asymmetric membrane in 563 and 4,774,039 for the first time, thinks that film cross-sectional aperture from the epidermis to the supporting layer gradually changes.Benzinger is at United States Patent (USP) U.S.4, uses TEP to make solvent in 384,047, and many hydroxy compounds are that non-solvent prepares the PVDF milipore filter.This film has fine and close top layer and network-like supporting layer, but water flux is less.Josefiak is at United States Patent (USP) U.S.4, the pvdf membrane that the method preparation of using hot dipping to go in 666,607 is made of porous shaped body.
Kynoar adopts immersion precipitation to prepare microporous barrier more at present, and the polymer solution concentration scope is between 8%-40%.The too low film-strength of solution concentration is poor, and the too high then polymer dissolution of concentration is not in good state.The solvent that adopts has dimethyl formamide (DMF), dimethylacetylamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-methyl arsenic pyrrolidone (NMP) isopolarity water-soluble solvent; The mixture of small-molecule substances such as water, acetone, glycerine, ethylene glycol, ethanol, methyl alcohol or itself and aforementioned optimum solvent can be used as the non-solvent coagulating bath; Some little molecule (as LiCL etc.) or polyethylene alkane ketone (PVP), polyethylene glycol big molecules such as (PEG) are often used as the system film additive and add in the preparation liquid; Can control the structure of PVDF microporous barrier by the selection of preparation liquid being formed film forming conditions such as (containing additive), coagulation bath composition and temperature, evaporation time, ambient humidity.Wherein the composition of coagulation bath has a significant impact film properties.Big more such as NaCl concentration in the coagulation bath, film is fine and close more, and porosity is also low more.Ethanol in the coagulating bath is different fully with NaCl to the influence of film morphosis in addition, do not contain ethanol in the coagulation bath, when having only water, easily form finger, increase along with ethanol content in the coagulation bath, corresponding prolongation hardening time of polymer helps the formation of spongelike structure when carrying out the mass transfer exchange.General when the solubility parameter of precipitating reagent changes from small to large, gradually excessively to finger, at the transition point place of two kinds of structures half and half, porosity and average pore size all are in minimum of a value to the form of film from spongelike structure.
The PVDF milipore filter not only is directly used in water treatment, environmental protection and biochemical field of medicaments, can also be used to prepare the support membrane of compounding permeation vaporizing film, composite nanometer filtering film and complex reverse osmosis membrane.Milipore filter as support membrane should have less surface holes and the good hole, cross section of permeability, is beneficial to improve the performance of composite membrane.
Summary of the invention
The invention provides the preparation method of a kind of hole density gradient structural polyvinylidene fluoride flat plate ultrafiltration membrane.The milipore filter shrinkage factor that obtains is low, has superior stretch-proof, shock resistance.
A kind of preparation method of vinylidene difluoride planar ultrafiltration membrane with gradient structure comprises the steps:
(1) Kynoar and additive are dissolved in the phosphoric acid ester solvent under 110～140 ℃, are placed to gel state in room temperature then, under solution temperature, placed 1～5 hour again, in 80～90 ℃ of insulations 1～5 hour, make preparation liquid at last;
(2) blade coating after preparation liquid filtration, the vacuum defoamation was placed in air 10～120 seconds on nonwoven;
(3) will scrape the nonwoven that scribbles preparation liquid at last and immerse in the coagulating bath,, form milipore filter through low temperature gel and two processes of high temperature gel.
Described Kynoar intrinsic viscosity is 0.8～1.7dl/g
In preparation method's the step (1), described preparation liquid mass percent consists of:
Kynoar 10-25%
Additive 0-10%
Phosphoric acid ester solvent 65-90%
The preferred mass percent of preparation liquid consists of:
Polymer 16-21%
Additive 1-6%
Phosphoric acid ester solvent 73-83%
In preparation method's the step (1), described phosphoric acid ester solvent is triethyl phosphate (TEP); Described additive is water, phosphoric acid, small molecular alcohol or LiCL.
Described coagulating bath is deionized water or contains a kind of deionized water solution among system membrane solvent, surfactant or the NaCl.
Low temperature gelling temp described in preparation method's the step (3) is 5～30 ℃, and the time is 0.5～3 hour, and the high temperature gel temperature is 35～60 ℃, and the time is 2～24 hours.
The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
This patent is the fact of macromolecule concentrated solution based on preparation liquid in essence, adopt to immerse the gel phase conversion method, a class milipore filter of the coagulation bath Processing of Preparation by two temperature.For characteristics of the present invention can better be described, " gradient-structure " defined, according to the present invention, the PVDF milipore filter is made up of same chemical substance, its surface is a porous, and the PVDF by crystallization forms near the subgrade on top layer, and subgrade is formed to the PVDF of bottom by indefiniteness; The hole, cross section of film increases gradually from little, and connects mutually.Because like this film of gradient is made up of crystalline portion and amorphous fraction, has good mechanical property, resistance to pressure preferably, less shrinkage.The density and gradient sectional porous ultrafiltration membrane of Zhi Zuoing for a better understanding of the present invention can be referring to accompanying drawing 1,2 and 3.
The invention has the advantages that: the vinylidene difluoride planar ultrafiltration membrane with gradient structure that the inventive method makes can directly apply to the ultra-filtration and separation field, also can be used as support membrane and prepares various composite membranes.By the polyvinylidene fluoride (PVDF) ultrafiltration membrane of this method preparation, be the partially crystallizable layer near the film surface, lower floor is the amorphous layer of network-like pore structure, the shrinkage factor of film is low, the water flux height.
Description of drawings
Fig. 1 is the gradient PVDF milipore filter cross section structure figure of the inventive method preparation;
Fig. 2 be among Fig. 1 gradient PVDF milipore filter near the structure chart of upper epidermis;
Fig. 3 is the approaching structure chart on top layer down of gradient PVDF milipore filter among Fig. 1.
The specific embodiment
Under 110 ℃, 16g Kynoar and 1g lithium chloride are dissolved among the 83gTEP, be placed to gel state in room temperature then, placed 5 hours down in 110 ℃ again, in 90 ℃ of insulations 5 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 10 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 30 ℃, and the time is 0.5 hour; High temperature gel stage gelling temp is 60 ℃, and the time is 24 hours.Obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 2
Under 140 ℃, the 25g Kynoar is dissolved among the 75gTEP, be placed to gel state in room temperature then, placed 1 hour down in 140 ℃ again, in 80 ℃ of insulations 1 hour, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 120 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 10 ℃, and the time is 5 hours; High temperature gel stage gelling temp is 35 ℃, and the time is 2 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 3
Under 130 ℃, the 20g Kynoar is dissolved in 1g water and the 79gTEP mixed solution, be placed to gel state in room temperature then, placed 1 hour down in 130 ℃ again, in 80 ℃ of insulations 3 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 30 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 5 hours; High temperature gel stage gelling temp is 40 ℃, and the time is 12 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 4
Under 120 ℃, 20g Kynoar and 4g glycerine are dissolved among the 76gTEP, be placed to gel state in room temperature then, placed 3 hours down in 120 ℃ again, in 85 ℃ of insulations 3 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 60 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 4 hours; High temperature gel stage gelling temp is 50 ℃, and the time is 8 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 5
Under 120 ℃, with the 20g Kynoar with in 2g water and 78gTEP mixed solution, be placed to gel state in room temperature then, placed 3 hours down in 120 ℃ again, in 85 ℃ of insulations 3 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 60 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 4 hours; High temperature gel stage gelling temp is 50 ℃, and the time is 8 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 6
Under 130 ℃, 20g Kynoar and 2g glycerine are dissolved among the 78gTEP, be placed to gel state in room temperature then, placed 3 hours down in 130 ℃ again, in 85 ℃ of insulations 2 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 20 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 4 hours; High temperature gel stage gelling temp is 40 ℃, and the time is 6 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 7
Under 130 ℃, 20g Kynoar and 3g phosphoric acid are dissolved among the 77gTEP, be placed to gel state in room temperature then, placed 3 hours down in 130 ℃ again, in 85 ℃ of insulations 2 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 40 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 5 hours; High temperature gel stage gelling temp is 50 ℃, and the time is 6 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Embodiment 8
Under 120 ℃, 21g Kynoar and 6g glycerine are dissolved among the 73gTEP, be placed to gel state in room temperature then, placed 3 hours down in 120 ℃ again, in 90 ℃ of insulations 5 hours, make preparation liquid at last; Blade coating after preparation liquid filtration, the vacuum defoamation was placed 30 seconds in air on nonwoven; To scrape the nonwoven that scribbles preparation liquid at last and immerse in the deionized water coagulating bath, low temperature gel phase gelling temp is 15 ℃, and the time is 5 hours; High temperature gel stage gelling temp is 60 ℃, and the time is 9 hours, has obtained the milipore filter of gradient-structure.The gained film is placed on for a long time in the distilled water and preserves until use, or soaks in distilled water after 5 days, uses soaked in absolute ethyl alcohol 20 hours, dries in air.
Claims (6)
1, a kind of preparation method of vinylidene difluoride planar ultrafiltration membrane with gradient structure comprises the steps:
(1) Kynoar and additive are dissolved in the phosphoric acid ester solvent under 110～140 ℃, are placed to gel state in room temperature then, under solution temperature, placed 1～5 hour again, in 80～90 ℃ of insulations 1～5 hour, make preparation liquid at last; Described Kynoar intrinsic viscosity is 0.8～1.7dl/g;
(2) blade coating after preparation liquid filtration, the vacuum defoamation was placed in air 10～120 seconds on nonwoven;
(3) will scrape the nonwoven that scribbles preparation liquid at last and immerse in the coagulating bath,, form the gradient-structure milipore filter through low temperature gel and two processes of high temperature gel.
2, preparation method as claimed in claim 1 is characterized in that: described preparation liquid mass percent consists of:
Kynoar 16-21%
Additive 1-6%
Phosphoric acid ester solvent 73-83%.
3, preparation method as claimed in claim 1 or 2 is characterized in that: described phosphoric acid ester solvent is a triethyl phosphate.
4, preparation method as claimed in claim 1 or 2 is characterized in that: described additive is water, phosphoric acid, small molecular alcohol or LiCL.
5, preparation method as claimed in claim 1 is characterized in that: described coagulating bath is a deionized water.
6, preparation method as claimed in claim 1 is characterized in that: described low temperature gel process gelling temp is 5～30 ℃; High temperature gel process gelling temp is 35～60 ℃.
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| CN102061049B (en) * | 2010-11-30 | 2013-03-27 | 天津工业大学 | Temperature sensitive polyvinylidene fluoride gel film and preparation method thereof |
| CN102002835B (en) * | 2010-12-10 | 2012-06-13 | 绍兴圣世机械有限公司 | Composite membrane machine for manufacturing flat membrane |
| CN102179189A (en) * | 2011-04-01 | 2011-09-14 | 河北科技大学 | Preparation method of pollution-resisting polyvinylidene fluoride ultrafiltration membrane |
| CN103981659B (en) * | 2014-05-08 | 2016-01-20 | 浙江圣世机械有限公司 | A kind of flat membrane compounding production equipment |
| CN105854624A (en) * | 2016-05-09 | 2016-08-17 | 天津工业大学 | High-water-flux polymer separation film |
| CN108744977A (en) * | 2018-06-29 | 2018-11-06 | 安得膜分离技术工程(北京)有限公司 | Ultrafiltration membrane and preparation method thereof |
| CN118179295A (en) * | 2022-12-13 | 2024-06-14 | 杭州科百特过滤器材有限公司 | Asymmetric PVDF (polyvinylidene fluoride) degerming membrane and preparation method thereof |
| CN117298869B (en) * | 2023-09-01 | 2024-06-25 | 麦博睿新材料科技(重庆)有限公司 | Preparation method of symmetrical polyvinylidene fluoride microfiltration membrane and microfiltration membrane prepared by same |
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Non-Patent Citations (4)
| Title |
|---|
| 制膜条件对PVDF膜形态结构的影响. 陆茵，陈欢林，李伯耿.功能高分子学报，第15卷第2期. 2002 |
| 制膜条件对PVDF膜形态结构的影响. 陆茵，陈欢林，李伯耿.功能高分子学报，第15卷第2期. 2002 * |
| 添加剂对PVDF相转化过程及膜孔结构的影响. 陆茵，陈欢林，李伯耿.高分子学报，第5期. 2002 |
| 添加剂对PVDF相转化过程及膜孔结构的影响. 陆茵，陈欢林，李伯耿.高分子学报，第5期. 2002 * |
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