CN104117294A - Preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane - Google Patents
Preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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Abstract
The invention relates to a preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane. The preparation method comprises the following steps: stirring polyvinylidene fluoride, a pore-forming agent, a coupling agent, a hydrophilic monomer, an initiator, a solvent initiator and a solvent at a temperature of 60-80 DEG C for 24-36 hours so as to prepare a casting membrane solution; filtering, removing bubbles and preparing an elementary hollow fiber membrane by use of a dry-wet spinning device; solidifying the hollow fiber membrane by use of a coagulating bath or irradiating the hollow fiber membrane with high-energy electronic beam when a winding device winds; soaking with water; treating with a pore former; drying to obtain the hydrophilia polyvinylidene fluoride hollow fiber membrane. The prepared polyvinylidene fluoride hollow fiber membrane has relatively high hydrophilia; the water flux is increased; the stretching intensity is improved; the hydrophilia polymers are uniformly distributed at the surface and interior of the hollow fiber membrane and the preparation method is simple to operate.
Description
Technical field
The present invention relates to the hydrophilic modification method of Pvdf Microporous Hollow Fiber Membrane, be specifically related to a kind of preparation method of hydrophilicity kynoar hollow-fibre membrane.
Background technology
Kynoar is a kind of semicrystalline polymer, has the features such as heat-resisting, resistance to impact, mechanical performance are good, corrosion-resistant, easy film forming.Therefore become the raw material of preparing membrane for water treatment of current main flow, but because polyvinylidene fluoride surface energy is low, can not form hydrogen bond action with hydrone, so there is extremely strong hydrophobicity, in the use procedure that is prepared into membrane for water treatment, the very easily lyophobic dust such as adhesion protein, colloidal particle and stop up fenestra, thereby producing film pollutes, reduce result of use, therefore need Pvdf Microporous Hollow Fiber Membrane to carry out hydrophilic modification, to improve its resistance tocrocking, increase water flux, increase the service life.At present polyvinylidene fluoride film is carried out to hydrophilic modification and mainly contain coating, surface grafting and three kinds of methods of blending and modifying.
Surface graft modification is that activation processing is carried out to through alkali lye or alternate manner in the surface of polyvinylidene fluoride film, carry out graft copolymerization with hydrophilic monomer again, patent CN 103263861A discloses a kind of film hydrophilically modified method of polyvinylidene fluoride flat, be about to first be immersed in highly basic alcoholic solution taking PET as base material polyvinylidene fluoride flat film, make film surface aggregate thing remove HF Formed carbon unsaturated bond, and then adopt method and the acrylic acid of free radical grafting to carry out glycerol polymerization, thereby form the hydrophilic polyacrylic acid molecule of one deck on film surface.The method need to be processed hollow-fibre membrane in aqueous alkali, and the alkali resistance of Kynoar is poor, therefore easily produces the problems such as goods jaundice, mechanical properties decrease and complex treatment process that make; Patent CN 102626592A discloses a kind of method that hydrophilic PVDF hollow-fibre membrane is prepared in high-energy electron beam irradiation grafting, first the PVDF hollow-fibre membrane preparing is immersed in the hydrophilic monomers such as acrylic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid, then adopt high-energy irradiation grafting, form grafting hydrophilic substance on Pvdf Microporous Hollow Fiber Membrane surface.This method of modifying is comparatively complicated, and need to carry out pretreatment to hollow-fibre membrane, and also need further processing after irradiation, therefore length consuming time, complex process, hydrophilic polymer easily comes off, and is unfavorable for suitability for industrialized production.This kind of method exists the high and surface treatment of step complexity, cost easily to cause degradation shortcoming under the mechanical performance of Kynoar matrix.
Blending and modifying is that water miscible polymer or inorganic nano-filler and Kynoar are carried out to direct blend, and then make film, patent CN 102961975A discloses a kind of preparation method of hydrophilicity kynoar hollow-fibre membrane, the method is that amphipathic nature block polymer polydimethylacrylamiin and dimethyl siloxane and Kynoar are carried out to blending and modifying, to improve the hydrophily of Pvdf Microporous Hollow Fiber Membrane.But the method need to be prepared complicated amphipathic nature block polymer, and exist hydroaropic substance to be difficult to be dispersed in uniformly the defect such as the surface of Pvdf Microporous Hollow Fiber Membrane, the easily loss of amphipathic copolymer, water-soluble polymer or inorganic nano-filler skewness, easy reunion.
Summary of the invention
The preparation method who the object of the present invention is to provide the fine film of a kind of hydrophilicity kynoar hollow, the Pvdf Microporous Hollow Fiber Membrane that adopts method provided by the invention to obtain has excellent hydrophily, and technique is simple, is convenient to suitability for industrialized production.
Technical scheme of the present invention provides a kind of preparation method of hydrophilicity kynoar hollow-fibre membrane, comprises the following steps:
1) after being uniformly mixed at 60-80 DEG C, Kynoar, pore-foaming agent, coupling agent, hydrophilic monomer, initator and solvent be prepared into casting solution;
2) by the casting solution obtaining after filtration, be prepared into elementary hollow-fibre membrane after bubble removing;
3) elementary hollow-fibre membrane is solidified after processing and received silk by coagulating bath, and carry out irradiation with high energy electron simultaneously in the process of solidifying and/or receives thread;
4) by step 3) in hollow-fibre membrane after polymerization be soaked in water, and be dried through protecting after hole agent is processed, obtain hydrophilic Pvdf Microporous Hollow Fiber Membrane.
The method providing according to technique scheme, pore-foaming agent is one or more mixtures in polyethylene glycol, polyvinylpyrrolidone, lithium chloride, content is the 1-10% of casting solution quality.
The method providing according to technique scheme, coupling agent is one or both mixtures in APTES, 3-glycidyl ether oxygen propyl trimethoxy silicane, content is the 0.5-5% of casting solution quality.
The method providing according to technique scheme, hydrophilic monomer is that content is the 0.5-15% of casting solution quality containing the monomer of two keys, hydroxyl or carboxyl.
The method providing according to technique scheme, hydrophilic monomer is acrylicacidandesters class and phenylethylene.
The method providing according to technique scheme, initator is one or more mixtures in ammonium persulfate, potassium peroxydisulfate, azodiisobutyronitrile, content is the 0.01-1% of casting solution quality.
The method providing according to technique scheme, the content of Kynoar is the 15-25% of casting solution quality.
The method providing according to technique scheme, solvent is N, one or more mixtures in N dimethylacetylamide, DMF, dimethyl sulfoxide (DMSO), triethyl phosphate, content is the 50-80% of casting solution quality.
The method providing according to technique scheme, step 3) SMIS liquid is deionized water, and coagulating bath is deionized water or deionized water and the mixing of organic solvent, and coagulation bath temperature is 25-35 DEG C.
The method providing according to technique scheme, the organic solvent adopting in coagulating bath is one or more the combination in methyl alcohol, ethanol, acetone, DMF, DMA, dimethyl sulfoxide (DMSO), content is the 0-50% of coagulating bath quality
The method providing according to technique scheme, the irradiation dose of middle high-energy electron beam irradiation is 150-300kGy.
In some embodiments of the present invention, to protect hole agent be boiling point higher than the water soluble alcohols of 100 DEG C.
In some embodiments of the invention, protect hole agent and can be selected from glycerine, butanediol and n-butanol.
In some embodiments of the present invention, described heating mixing plant is flask or reactor.
In some embodiments of the present invention, the material of filtering the filter membrane of casting solution is selected from stainless steel or nylon, and pore size is 300-800 order.
In some embodiments of the present invention, the preparation of casting solution is to carry out in the device such as reactor, glassware with stirring and heater.
In some embodiments of the present invention, step 1) in while preparing casting solution mixing time be 24-36 hour.
Unless clearly state in contrast, otherwise all scopes that the present invention quotes comprised end value.For example, mixing time is " 24-36 hour ", represents that the scope of mixing time is 24h≤t≤36h.
In some embodiments of the present invention, institute's water is deionized water.
Beneficial effect of the present invention is:
(1) prepared Pvdf Microporous Hollow Fiber Membrane has excellent hydrophily, can be reduced to below 45 ° with the contact angle of water, and water flux increases, hot strength increases;
(2) hydrophilic monomer is added in casting solution, because hydrophilic monomer molecular weight is little, easily in film, be evenly distributed, therefore the hydrophilic polymer after polymerization on hollow-fibre membrane surface and inside be uniformly distributed and be difficult for separating out, and due to the existence of hydroaropic substance, increase greatly the hydrophily of Pvdf Microporous Hollow Fiber Membrane, reduced its absorption to the lyophobic dust such as albumen and colloidal particle, thereby avoided the obstruction of fenestra or the pollution of film;
(3) the present invention adopts high-energy irradiation to carry out glycerol polymerization, by the irradiation of high-power electron beam, on Kynoar matrix, form avtive spot, this avtive spot can cause hydrophilic monomer around and carry out autohemagglutination and copolymerization, do not need complicated post processing, simplified preparation process, technique is simple, easily industrialization, has also avoided traditional alkali lye to process the damage to basement membrane simultaneously.
Detailed description of the invention
The following stated be the preferred embodiment of the present invention, what the present invention protected is not limited to following preferred embodiment.It should be pointed out that on the basis of conceiving in these innovation and creation for a person skilled in the art, some distortion and the improvement made, all belong to protection scope of the present invention.Raw material used in embodiment all can obtain by commercial sources.
Embodiment 1
The preparation of casting solution: the Kynoar that is 15% by mass content, 3% PEG400,1% APTES, 3% styrene, 0.06% ammonium persulfate and 78% N, N-dimethylacetylamide joins in the reactor with stirring and heater, at 60 DEG C, stir 24h, it is uniformly dissolved, stand-by after standing 12h after filtering with 400 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid and coagulating bath are that the temperature of deionization coagulating bath is 25 DEG C, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 150kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, finally protect hole with glycerine.
Prepared hydrophilic hollow fibre film is carried out to the test of water flux, rejection and contact angle, and method of testing is as follows:
Water flux:
Adopt external-compression type method of testing, by measuring the volume V that flows through water in the unit interval
w, the film silk area A of passing through and the time t of outflow, according to formula:
calculate the water flux of polyvinylidene fluoride film.
Rejection:
Use ultraviolet-visible-infrared spectrophotometer to test, under 0.1MPa, adopt external-compression type to measure, the bovine serum albumin using the molecular weight of 1g/L as 80000 is as tested object.Determine the rejection of polyvinylidene fluoride film by the residual quantity of bovine serum albumin on test membrane.Rejection
wherein C
pfor bovine serum albumin concentration in water inlet, C
ffor bovine serum albumin concentration in water purification.
Contact angle:
Adopt the contact angle of contact angle tester test membrane silk and water.
Hot strength:
Use the hot strength of universal material puller system test polyvinylidene fluoride film.
The result of test is: the pure water flux under 0.1MPa is 760Lm
-2h
-1, bovine serum albumin (bovine serum albumin) rejection to 1g/L is 85.9%, the contact angle of water is 40.2 °, hot strength 4.5MPa.
Embodiment 2
The preparation of casting solution: the Kynoar that is 17% by mass percent, 5% PEG400,2%3-aminopropyltriethoxywerene werene, 8% styrene, 0.5% ammonium persulfate and 68% N, N-dimethylacetylamide joins in the reactor with stirring and heater, at 65 DEG C, stir 26h, it is uniformly dissolved, after filtering with 500 object filters, leaves standstill 12h stand-by;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid is deionized water, coagulating bath is to be 5% N, the solution of dinethylformamide, its temperature is 30 DEG C, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 200kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with glycerine, test thereafter, test condition is with embodiment 1, test result is that the pure water flux under 0.1MPa is 800Lm
-2h
-1, be 87.9% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 37.9 °, hot strength 5.3MPa.
Embodiment 3
The preparation of casting solution: the Kynoar that is 19% by mass percent, 8% PEG400,5%3-aminopropyltriethoxywerene werene, 10% styrene, 0.8% ammonium persulfate and 60% N, N-dimethylacetylamide joins with in the reactor stirring and heat, at 70 DEG C, stir 30h, it is uniformly dissolved, stand-by after standing 12h after filtering with 500 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid is deionized water, coagulating bath is that concentration is 10% N, N-dimethylacetamide solution, wherein, coagulation bath temperature is 25 DEG C, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 250kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with glycerine, test thereafter, test condition is with embodiment 1, test result is that the pure water flux under 0.1MPa is 900Lm
-2h
-1, be 92.8% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 41.2 °, hot strength 6.0MPa.
Embodiment 4
The preparation of casting solution: the Kynoar that is 15% by mass percent, 2% PEG400,1%3-glycidyl ether oxygen propyl trimethoxy silicane, 15% acrylic acid, 1% azodiisobutyronitrile and 64% dimethyl sulfoxide (DMSO) join with stir and the reactor of heating in, at 60 DEG C, stir 24h, it is uniformly dissolved, stand-by after standing 12h after filtering with 600 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid deionized water, coagulating bath is that concentration is 20% N, N-dimethylacetamide solution, 35 DEG C of coagulation bath temperatures, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 200kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with glycerine, test thereafter, test condition is with embodiment 1, test result is that the pure water flux under 0.1MPa is 7000Lm
-2h
-1, be 90.8% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 37.2 °, hot strength 4.9MPa.
Embodiment 5
The preparation of casting solution: the Kynoar that is 20% by mass percent, 6% polyvinylpyrrolidone, 4%3-glycidyl ether oxygen propyl trimethoxy silicane, 0.5% methyl methacrylate, 0.01% potassium peroxydisulfate and 73% dimethyl sulfoxide (DMSO) join with stir and the reactor of heating in, at 70 DEG C, stir 30h, it is uniformly dissolved, stand-by after standing 12h after filtering with 800 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid deionized water, coagulating bath is that concentration is 30% dimethyl sulphoxide solution, 30 DEG C of coagulation bath temperatures, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 100kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with glycerine, test thereafter, test condition is with embodiment 1, and test result is that the pure water flux under 0.1MPa is 860Lm
-2h
-1, be 86.8% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 50.2 °, hot strength 5.7MPa.
Embodiment 6
The preparation of casting solution: the Kynoar that is 25% by mass percent, 5% lithium chloride, 3%3-glycidyl ether oxygen propyl trimethoxy silicane, 1% allyl alcohol, 0.2% potassium peroxydisulfate and 67% dimethyl formamide join with stir and the reactor of heating in, at 80 DEG C, stir 36h, it is uniformly dissolved, stand-by after standing 12h after filtering with 300 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid and coagulating bath are deionized water, 25 DEG C of coagulation bath temperatures, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 150kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with n-butanol, test thereafter, test condition is with embodiment 1, and test result is that the pure water flux under 0.1MPa is 850Lm
-2h
-1, be 84.8% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 47.8 °, hot strength 6.3MPa.
Embodiment 7
The preparation of casting solution: the Kynoar that is 20% by mass percent, 1% Macrogol 200,0.5%3-aminopropyltriethoxywerene werene, 10% methyl acrylate, 0.8% potassium peroxydisulfate and 63% dimethyl formamide join with stir and the reactor of heating in, at 80 DEG C, stir 30h, it is uniformly dissolved, stand-by after standing 12h after filtering with 800 object filters;
The preparation of hydrophilic hollow fibre film: adopt dry-jet wet-spinning silk equipment to carry out spinning the casting solution preparing, core liquid deionized water, coagulating bath is that concentration is 25 DEG C of 50% methanol solution coagulation bath temperatures, after entering coagulating bath, elementary doughnut starts electron beam irradiation glycerol polymerization, irradiation dose is 250kGy, by deionized water soak 24h thereafter, to remove pore-foaming agent and a small amount of unreacted monomer wherein, after protecting hole with butanediol, test thereafter, test condition is with embodiment 1, and test result is that the pure water flux under 0.1MPa is 650Lm
-2h
-1, be 89.8% to the bovine serum albumin rejection of 1g/L, the contact angle of water is 32.0 °, hot strength 5.3MPa.
Known according to embodiment 1-embodiment 7, the Pvdf Microporous Hollow Fiber Membrane of being prepared by technical solution of the present invention has splendid hydrophily, the contact angle of its water is within the scope of 30 °-50 °, and owing to having adopted, monomer is dispersed in casting solution in advance, and then carry out irradiation polymerization with high-power electron beam, therefore compared with existing surface graft modification and blending and modifying technology, improving the hydrophilic while of Pvdf Microporous Hollow Fiber Membrane, also its hot strength and water flux have been strengthened, thereby effectively raise the contamination resistance of Pvdf Microporous Hollow Fiber Membrane, extend its service life.
Claims (10)
1. a preparation method for hydrophilicity kynoar hollow-fibre membrane, is characterized in that comprising the following steps:
1) after being uniformly mixed at 60-80 DEG C, Kynoar, pore-foaming agent, coupling agent, hydrophilic monomer, initator and solvent be prepared into casting solution;
2) will after the casting solution filtration obtaining, bubble removing, be prepared into elementary hollow-fibre membrane;
3) elementary hollow-fibre membrane is solidified after processing and received silk by coagulating bath, and carry out irradiation with high energy electron simultaneously in the process of solidifying and/or receives thread;
4) by step 3) in hollow-fibre membrane after polymerization be soaked in water, and be dried through protecting after hole agent is processed, obtain hydrophilic Pvdf Microporous Hollow Fiber Membrane.
2. preparation method according to claim 1, is characterized in that, described pore-foaming agent is one or more mixtures in polyethylene glycol, polyvinylpyrrolidone, lithium chloride, and content is the 1-10% of casting solution quality.
3. preparation method according to claim 1, is characterized in that, described coupling agent is one or more mixtures in APTES, 3-glycidyl ether oxygen propyl trimethoxy silicane, and content is the 0.5-5% of casting solution quality.
4. preparation method according to claim 1, is characterized in that, hydrophilic monomer is the monomer of the two keys of band, hydroxyl or carboxyl, and content is the 0.5-15% of casting solution quality.
5. preparation method according to claim 1, is characterized in that, described initator is one or more mixtures in ammonium persulfate, potassium peroxydisulfate, azodiisobutyronitrile, and content is the 0.01-1% of casting solution quality.
6. preparation method according to claim 1, is characterized in that, the content of described Kynoar is the 15-25% of casting solution quality.
7. preparation method according to claim 1, is characterized in that, described solvent is one or more mixtures in DMA, DMF, dimethyl sulfoxide (DMSO), triethyl phosphate, and content is the 50-80% of casting solution quality.
8. preparation method according to claim 1, is characterized in that step 3) SMIS liquid is deionized water, and coagulating bath is deionized water or deionized water and the mixing of organic solvent, and coagulation bath temperature is 25-35 DEG C.
9. preparation method according to claim 8, described organic solvent is one or more the combination in methyl alcohol, ethanol, acetone, DMF, DMA, dimethyl sulfoxide (DMSO), content is the 0-50% of coagulating bath quality.
10. preparation method according to claim 1, is characterized in that, described high-energy electron beam irradiation, irradiation dose is 150-300kGy.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104524998A (en) * | 2014-12-31 | 2015-04-22 | 云南云天化股份有限公司 | Hydrophilia hollow fiber membrane and preparation method thereof |
| CN104587853A (en) * | 2014-12-12 | 2015-05-06 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for hydrophilic polyvinylidene fluoride flat membrane |
| CN106492643A (en) * | 2016-11-01 | 2017-03-15 | 宁波水艺膜科技发展有限公司 | A kind of hydrophilic modification method of polymer separation film |
| CN108479425A (en) * | 2018-04-08 | 2018-09-04 | 哈尔滨工业大学（威海） | A kind of preparation method of PVDF ultrafiltration sterilizing membrane |
| CN109806777A (en) * | 2017-11-22 | 2019-05-28 | 乐清腾祥膜技术有限公司 | A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film |
| CN113546529A (en) * | 2021-09-23 | 2021-10-26 | 清大国华环境集团股份有限公司 | Preparation method of hydrophilic modified PVDF (polyvinylidene fluoride) separation membrane |
| CN113828162A (en) * | 2020-06-23 | 2021-12-24 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN114471192A (en) * | 2021-12-28 | 2022-05-13 | 江苏久吾高科技股份有限公司 | PVDF hollow fiber membrane and preparation method and application thereof |
| CN114917768A (en) * | 2022-05-24 | 2022-08-19 | 江苏诺莱智慧水务装备有限公司 | Preparation method of large-flux polyvinylidene fluoride hollow fiber membrane |
| CN115501765A (en) * | 2022-10-27 | 2022-12-23 | 安徽大学 | Hollow fiber membrane, method for constructing hydrophilic network thereof and application thereof |
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| CN102626592A (en) * | 2012-01-12 | 2012-08-08 | 天津工业大学 | Method for preparing hydrophilic PVDF hollow fiber membrane by high energy electron beam mutual irradiation grafting |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102626592A (en) * | 2012-01-12 | 2012-08-08 | 天津工业大学 | Method for preparing hydrophilic PVDF hollow fiber membrane by high energy electron beam mutual irradiation grafting |
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| CN104587853A (en) * | 2014-12-12 | 2015-05-06 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for hydrophilic polyvinylidene fluoride flat membrane |
| CN104524998A (en) * | 2014-12-31 | 2015-04-22 | 云南云天化股份有限公司 | Hydrophilia hollow fiber membrane and preparation method thereof |
| CN106492643A (en) * | 2016-11-01 | 2017-03-15 | 宁波水艺膜科技发展有限公司 | A kind of hydrophilic modification method of polymer separation film |
| CN106492643B (en) * | 2016-11-01 | 2019-03-19 | 宁波水艺膜科技发展有限公司 | A kind of hydrophilic modification method of polymer separation film |
| CN109806777A (en) * | 2017-11-22 | 2019-05-28 | 乐清腾祥膜技术有限公司 | A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film |
| CN108479425A (en) * | 2018-04-08 | 2018-09-04 | 哈尔滨工业大学（威海） | A kind of preparation method of PVDF ultrafiltration sterilizing membrane |
| CN113828162A (en) * | 2020-06-23 | 2021-12-24 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN113828162B (en) * | 2020-06-23 | 2022-12-20 | 三达膜科技（厦门）有限公司 | Preparation method of sustainable hydrophilic modified polyvinylidene fluoride hollow membrane |
| CN113546529A (en) * | 2021-09-23 | 2021-10-26 | 清大国华环境集团股份有限公司 | Preparation method of hydrophilic modified PVDF (polyvinylidene fluoride) separation membrane |
| CN114471192A (en) * | 2021-12-28 | 2022-05-13 | 江苏久吾高科技股份有限公司 | PVDF hollow fiber membrane and preparation method and application thereof |
| CN114917768A (en) * | 2022-05-24 | 2022-08-19 | 江苏诺莱智慧水务装备有限公司 | Preparation method of large-flux polyvinylidene fluoride hollow fiber membrane |
| CN115501765A (en) * | 2022-10-27 | 2022-12-23 | 安徽大学 | Hollow fiber membrane, method for constructing hydrophilic network thereof and application thereof |
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