CN104117294B - A kind of preparation method of hydrophilia polyvinylidene fluoride hollow fiber membrane - Google Patents
A kind of preparation method of hydrophilia polyvinylidene fluoride hollow fiber membrane Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of hydrophilia polyvinylidene fluoride hollow fiber membrane, it is prepared as casting solution after Kynoar, porogen, coupling agent, hydrophilic monomer, initiator and solvent initiator and solvent being stirred 24 36 hours at 60 80 DEG C, it is prepared as primary hollow fibrous membrane with dry and wet spinning equipment after filtration, bubble removing, this hollow-fibre membrane is after coagulating bath solidification processes and/or carries out irradiation with high-power electron beam in time receiving silk equipment and receive silk, it is soaked in water, protects after hole agent processes and be dried, obtain hydrophilic Pvdf Microporous Hollow Fiber Membrane.Pvdf Microporous Hollow Fiber Membrane prepared by the method has higher hydrophilic, and water flux increases, and hot strength increases, and hydrophilic polymer is evenly distributed on hollow-fibre membrane surface and inside, and this kind of 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 the preparation method of a kind of hydrophilia polyvinylidene fluoride hollow fiber membrane.
Background technology
Kynoar is a kind of semicrystalline polymer, has the features such as heat-resisting, resistance to impact, good mechanical performance, corrosion-resistant, easy film forming.Therefore the raw material preparing membrane for water treatment of current main flow is become, but owing to polyvinylidene fluoride surface energy is low, can not form hydrogen bond action with hydrone, so having extremely strong hydrophobicity, during the use being prepared as membrane for water treatment, easily the lyophobic dust such as adhesion protein, colloidal particle and block fenestra, thus produce fouling membrane, reduce using effect, it is therefore desirable to Pvdf Microporous Hollow Fiber Membrane is carried out hydrophilic modification, to improve its resistance tocrocking, increase water flux, increase the service life.Polyvinylidene fluoride film is carried out hydrophilic modification mainly coating, surface grafting and three kinds of methods of blending and modifying at present.
Surface graft modification is that through alkali liquor or alternate manner, the surface of polyvinylidene fluoride film is carried out activation processing, graft copolymerization is carried out again with hydrophilic monomer, patent CN 103263861A discloses a kind of film hydrophilically modified method of polyvinylidene fluoride flat, will be submerged initially in highly basic alcoholic solution with PET for base material polyvinylidene fluoride flat film, film surface polymer removing HF is made to generate unsaturated carbon carbon bond, the method using free radical grafting the most again carries out glycerol polymerization with acrylic acid, thus forms one layer of hydrophilic polyacrylic acid molecule on film surface.The method needs to process hollow-fibre membrane in aqueous alkali, and the alkali resistance of Kynoar is poor, therefore easily produces problems such as making goods jaundice, mechanical properties decrease and complex treatment process；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 prepared is immersed in the hydrophilic monomers such as acrylic acid, methacrylic acid, 2-acrylamide-2-methylpro panesulfonic acid, then use high-energy irradiation grafting, form grafting property hydrophilic substance on Pvdf Microporous Hollow Fiber Membrane surface.This method of modifying is complex, also needs to process further after needing hollow-fibre membrane is carried out pretreatment, and irradiation, the longest, and complex process, hydrophilic polymer easily comes off, and is unfavorable for industrialized production.There is step complexity, cost height and surface and process degradation shortcoming under the mechanical performance easily causing Kynoar matrix in this kind of method.
Blending and modifying is water miscible polymer or inorganic nano-filler to be directly blended with Kynoar, make film the most again, patent CN 102961975A discloses the preparation method of a kind of hydrophilia polyvinylidene fluoride hollow fiber membrane, the method is that amphipathic nature block polymer polydimethylacrylamiin and dimethyl siloxane are carried out blending and modifying, to improve the hydrophilic of Pvdf Microporous Hollow Fiber Membrane with Kynoar.But the method needs the amphipathic nature block polymer that preparation is complicated, and have that hydroaropic substance is difficult to be uniformly dispersed in the surface of Pvdf Microporous Hollow Fiber Membrane, amphipathic copolymer is easy to run off, the defect such as water-soluble polymer or inorganic nano-filler skewness, easy reunion.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of hydrophilicity kynoar hollow fibre film, the Pvdf Microporous Hollow Fiber Membrane that the method using the present invention to provide obtains has the hydrophilic of excellence, and technique is simple, it is simple to industrialized production.
Technical scheme provides the preparation method of a kind of hydrophilia polyvinylidene fluoride hollow fiber membrane, comprises the following steps:
1) it is prepared as casting solution after Kynoar, porogen, coupling agent, hydrophilic monomer, initiator and solvent being stirred at 60-80 DEG C mixing；
2) casting solution obtained is prepared as primary hollow fibrous membrane after filtration, bubble removing；
3) receive silk after being processed by coagulating bath solidification by primary hollow fibrous membrane, and carry out irradiation with high energy electron during solidification and/or receipts silk simultaneously；
4) by step 3) in hollow-fibre membrane after polymerization be soaked in water, and be dried after protecting hole agent and processing, obtain hydrophilic Pvdf Microporous Hollow Fiber Membrane.
The method provided according to technique scheme, porogen is one or more mixture in Polyethylene Glycol, polyvinylpyrrolidone, lithium chloride, and content is the 1-10% of casting solution quality.
The method provided according to technique scheme, coupling agent is one or both mixture in APTES, 3-glycidyl ether oxygen propyl trimethoxy silicane, and content is the 0.5-5% of casting solution quality.
The method provided according to technique scheme, hydrophilic monomer is the monomer containing double bond, hydroxyl or carboxyl, and content is the 0.5-15% of casting solution quality.
The method provided according to technique scheme, hydrophilic monomer is acrylicacidandesters class and phenylethylene.
The method provided according to technique scheme, initiator is one or more mixture in Ammonium persulfate., potassium peroxydisulfate, azodiisobutyronitrile, and content is the 0.01-1% of casting solution quality.
The method provided according to technique scheme, the content of Kynoar is the 15-25% of casting solution quality.
The method provided according to technique scheme, solvent is N, one or more mixture in N dimethyl acetamide, DMF, dimethyl sulfoxide, triethyl phosphate, and content is the 50-80% of casting solution quality.
The method provided according to technique scheme, step 3) SMIS liquid is deionized water, coagulating bath is the mixing of deionized water or deionized water and organic solvent, and coagulation bath temperature is 25-35 DEG C.
The method provided according to technique scheme, organic solvent employed in coagulating bath is the combination of one or more in methanol, ethanol, acetone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide, content is the 0-50% of coagulating bath quality
The method provided according to technique scheme, the irradiation dose of middle high-energy electron beam irradiation is 150-300kGy.
In certain embodiments of the present invention, protecting hole agent is the water soluble alcohols that boiling point is higher than 100 DEG C.
In some embodiments of the invention, protect hole agent and be selected from glycerol, butanediol and n-butyl alcohol.
In certain embodiments of the present invention, described heated and stirred equipment is flask or reactor.
In certain embodiments of the present invention, the material of the filter membrane filtering casting solution is selected from rustless steel or nylon, and pore size is 300-800 mesh.
In certain embodiments of the present invention, the preparation of casting solution is to carry out in devices such as stirring and the reactor of heater, glass drying ovens.
In certain embodiments of the present invention, step 1) in when preparing casting solution mixing time be 24-36 hour.
The most in contrast, otherwise, all scopes that the present invention quotes include end value.Such as, mixing time is " 24-36 hour ", represents that mixing time is in the range of 24h t 36h.
In certain embodiments of the present invention, water used is deionized water.
The beneficial effects of the present invention is:
(1) Pvdf Microporous Hollow Fiber Membrane prepared by has the hydrophilic of excellence, can be reduced to less than 45 ° with the contact angle of water, and water flux increases, hot strength increases；
(2) hydrophilic monomer is added to casting solution, owing to hydrophilic monomer molecular weight is little, easily it is evenly distributed in film, therefore the hydrophilic polymer after polymerization is distributed on hollow-fibre membrane surface and inner homogeneous and is difficult to separate out, and due to the existence of hydroaropic substance, significantly increase the hydrophilic of Pvdf Microporous Hollow Fiber Membrane, reduce its absorption to the lyophobic dust such as albumen and colloidal particle, thus avoid the blocking of fenestra or the pollution of film；
(3) present invention uses high-energy irradiation to carry out glycerol polymerization, by the irradiation of high-power electron beam, Kynoar matrix is formed avtive spot, this avtive spot can cause the hydrophilic monomer of surrounding to carry out autohemagglutination and copolymerization, need not the post processing of complexity, simplify preparation process, technique is simple, easily industrialization, it also avoid the damage to basement membrane of traditional base extraction simultaneously.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention, and what the present invention was protected is not limited to following preferred embodiment.It should be pointed out that, for a person skilled in the art on the basis of these innovation and creation are conceived, the some deformation made and improvement, broadly fall into protection scope of the present invention.Raw material used in embodiment all can be by being either commercially available.
Embodiment 1
The preparation of casting solution: by Kynoar, the PEG400 of 3%, the APTES of 1%, the styrene of 3%, the Ammonium persulfate. of 0.06% and the N of 78% that mass content is 15%, N-dimethyl acetylamide joins in the reactor with stirring and heater, 24h is stirred at 60 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 400 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid and the temperature that coagulating bath is deionization coagulating bath are 25 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 150kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, finally carry out protecting hole with glycerol.
Obtained Hydrophilic hollow fiber membrane carries out the test of water flux, rejection and contact angle, and method of testing is as follows:
Water flux:
Use external-compression type method of testing, by flowing through the volume V of water in measuring the unit intervalw, the film silk area A passed 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, use external-compression type to measure, using the bovine serum albumin that molecular weight is 80000 of 1g/L as test object.The rejection of polyvinylidene fluoride film is determined by the residual quantity of bovine serum albumin on test membrane.RejectionWherein CpFor bovine serum albumin concentration, C in water inletfFor bovine serum albumin concentration in water purification.
Contact angle:
Use the contact angle of contact angle tester test film 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 760L m-2·h-1, bovine serum albumin (bovine serum albumin) rejection to 1g/L is 85.9%, and the contact angle of water is 40.2 °, hot strength 4.5MPa.
Embodiment 2
The preparation of casting solution: by Kynoar, the PEG400 of 5%, 2%3-aminopropyltriethoxywerene werene, the styrene of 8%, the Ammonium persulfate. of 0.5% and the N of 68% that mass percent is 17%, N-dimethyl acetylamide joins in the reactor with stirring and heater, 26h is stirred at 65 DEG C, make it be uniformly dissolved, stand 12h after filtering with the filter of 500 mesh stand-by；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid is deionized water, coagulating bath be 5% N, the solution of dinethylformamide, its temperature is 30 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 200kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with glycerol, test condition is with embodiment 1, test result be the pure water flux under 0.1MPa be 800L m-2·h-1, the bovine serum albumin rejection to 1g/L is 87.9%, and the contact angle of water is 37.9 °, hot strength 5.3MPa.
Embodiment 3
The preparation of casting solution: by Kynoar, the PEG400 of 8%, 5%3-aminopropyltriethoxywerene werene, the styrene of 10%, the Ammonium persulfate. of 0.8% and the N of 60% that mass percent is 19%, N-dimethyl acetylamide joins in the reactor with stirring and heating, 30h is stirred at 70 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 500 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid is deionized water, coagulating bath be concentration be the N of 10%, N-dimethylacetamide solution, wherein, coagulation bath temperature is 25 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 250kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with glycerol, test condition is with embodiment 1, test result be the pure water flux under 0.1MPa be 900L m-2·h-1, the bovine serum albumin rejection to 1g/L is 92.8%, and the contact angle of water is 41.2 °, hot strength 6.0MPa.
Embodiment 4
The preparation of casting solution: the dimethyl sulfoxide of Kynoar, the PEG400 of 2%, 1%3-glycidyl ether oxygen propyl trimethoxy silicane, the acrylic acid of 15%, the azodiisobutyronitrile of 1% and 64% that mass percent is 15% is joined in the reactor with stirring and heating, 24h is stirred at 60 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 600 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid deionized water, coagulating bath be concentration be the N of 20%, N-dimethylacetamide solution, coagulation bath temperature 35 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 200kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with glycerol, test condition is with embodiment 1, test result be the pure water flux under 0.1MPa be 700L m-2·h-1, the bovine serum albumin rejection to 1g/L is 90.8%, and the contact angle of water is 37.2 °, hot strength 4.9MPa.
Embodiment 5
The preparation of casting solution: the dimethyl sulfoxide of Kynoar, the polyvinylpyrrolidone of 6%, 4%3-glycidyl ether oxygen propyl trimethoxy silicane, the methyl methacrylate of 0.5%, the potassium peroxydisulfate of 0.01% and 73% that mass percent is 20% is joined in the reactor with stirring and heating, 30h is stirred at 70 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 800 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid deionized water, coagulating bath be concentration be the dimethyl sulphoxide solution of 30%, coagulation bath temperature 30 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 100kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with glycerol, test condition with embodiment 1, test result be the pure water flux under 0.1MPa be 860L m-2·h-1, the bovine serum albumin rejection to 1g/L is 86.8%, and the contact angle of water is 50.2 °, hot strength 5.7MPa.
Embodiment 6
The preparation of casting solution: the dimethylformamide of Kynoar, the lithium chloride of 5%, 3%3-glycidyl ether oxygen propyl trimethoxy silicane, the 1-propenol-3 of 1%, the potassium peroxydisulfate of 0.2% and 67% that mass percent is 25% is joined in the reactor with stirring and heating, 36h is stirred at 80 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 300 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid and coagulating bath are deionized water, coagulation bath temperature 25 DEG C, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 150kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with n-butyl alcohol, test condition with embodiment 1, test result be the pure water flux under 0.1MPa be 850L m-2·h-1, the bovine serum albumin rejection to 1g/L is 84.8%, and the contact angle of water is 47.8 °, hot strength 6.3MPa.
Embodiment 7
The preparation of casting solution: the dimethylformamide of Kynoar, the polyethylene glycol 200 of 1%, 0.5%3-aminopropyltriethoxywerene werene, the acrylic acid methyl ester. of 10%, the potassium peroxydisulfate of 0.8% and 63% that mass percent is 20% is joined in the reactor with stirring and heating, 30h is stirred at 80 DEG C, it is made to be uniformly dissolved, stand-by after standing 12h with the filter of 800 mesh after filtering；
The preparation of Hydrophilic hollow fiber membrane: the casting solution prepared employing dry and wet spinning equipment is carried out spinning, core liquid deionized water, coagulating bath be concentration be the methanol solution coagulation bath temperature 25 DEG C of 50%, electron beam irradiation glycerol polymerization is i.e. started after primary hollow fiber enters coagulating bath, irradiation dose is 250kGy, thereafter 24h is soaked with deionized water, to remove porogen therein and a small amount of unreacted monomer, thereafter test after carrying out protecting hole with butanediol, test condition with embodiment 1, test result be the pure water flux under 0.1MPa be 650L m-2·h-1, the bovine serum albumin rejection to 1g/L is 89.8%, and the contact angle of water is 32.0 °, hot strength 5.3MPa.
According to embodiment 1 embodiment 7, the Pvdf Microporous Hollow Fiber Membrane prepared by technical solution of the present invention has splendid hydrophilic, the contact angle of its water is in the range of 30 °-50 °, and owing to have employed, monomer is pre-dispersed in casting solution, irradiation polymerization is carried out the most again with high-power electron beam, therefore compared with existing surface graft modification and blend modification technology, improve Pvdf Microporous Hollow Fiber Membrane hydrophilic while, also enhance its hot strength and water flux, thus effectively raise the contamination resistance of Pvdf Microporous Hollow Fiber Membrane, extend its service life.
Claims (8)
1. the preparation method of a hydrophilia polyvinylidene fluoride hollow fiber membrane, it is characterised in that comprise the following steps:
1) Kynoar, porogen, coupling agent, hydrophilic monomer, initiator and solvent are stirred at 60-80 DEG C mixing
After be prepared as casting solution；
2) after the casting solution obtained filtration, bubble removing, carry out spinning by dry and wet spinning equipment together with core liquid, be prepared as primary
Hollow-fibre membrane；
3) receive silk after being processed by coagulating bath solidification by primary hollow fibrous membrane, and use during solidification and/or receipts silk simultaneously
High-power electron beam carries out radiation grafting copolymerization；
4) by step 3) in hollow-fibre membrane after polymerization be soaked in water, and be dried after protecting hole agent and processing, obtain hydrophilic
The Pvdf Microporous Hollow Fiber Membrane of property；
Described hydrophilic monomer is acrylicacidandesters class and phenylethylene, and content is the 0.5-15% of casting solution quality；
The irradiation dose of described high-energy electron beam irradiation is 150-300kGy.
Preparation method the most according to claim 1, it is characterised in that described porogen is Polyethylene Glycol, polyethylene pyrrole
One or more mixture in pyrrolidone, lithium chloride, content is the 1-10% of casting solution quality.
Preparation method the most according to claim 1, it is characterised in that described coupling agent is 3-aminopropyl triethoxy
One or more mixture in silane, 3-glycidyl ether oxygen propyl trimethoxy silicane, content is the 0.5-5% of casting solution quality.
Preparation method the most according to claim 1, it is characterised in that described initiator be Ammonium persulfate., potassium peroxydisulfate,
One or more mixture in azodiisobutyronitrile, content is the 0.01-1% of casting solution quality.
Preparation method the most according to claim 1, it is characterised in that the content of described Kynoar is casting solution quality
15-25%.
Preparation method the most according to claim 1, it is characterised in that described solvent is N,N-dimethylacetamide, N, N-
One or more mixture in dimethylformamide, dimethyl sulfoxide, triethyl phosphate, content is the 50-80% of casting solution quality.
Preparation method the most according to claim 1, it is characterised in that step 2) SMIS liquid is deionized water；Step 3)
Middle coagulating bath is the mixing of deionized water or deionized water and organic solvent, and coagulation bath temperature is 25-35 DEG C.
Preparation method the most according to claim 7, described organic solvent is methanol, ethanol, acetone, N, N-dimethyl methyl
The combination of one or more in amide, N,N-dimethylacetamide, dimethyl sulfoxide, content is the 0-50% of coagulating bath quality.
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| CN110548412A (en) * | 2019-09-18 | 2019-12-10 | 山东华象环保科技有限公司 | Hydrophilic polypropylene hollow fiber membrane and preparation method thereof |
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| CN104587853B (en) * | 2014-12-12 | 2017-02-22 | 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 |
| 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 |
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| 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 |
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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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