CN116212656A - Preparation method of amphiphilic terpolymer ultrafiltration membrane - Google Patents
Preparation method of amphiphilic terpolymer ultrafiltration membrane Download PDFInfo
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- CN116212656A CN116212656A CN202310438831.6A CN202310438831A CN116212656A CN 116212656 A CN116212656 A CN 116212656A CN 202310438831 A CN202310438831 A CN 202310438831A CN 116212656 A CN116212656 A CN 116212656A
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- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 40
- 229920001897 terpolymer Polymers 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000005266 casting Methods 0.000 claims abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 16
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 12
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 238000007790 scraping Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- -1 hydroxymethyl propyl Chemical group 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 4
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 claims description 4
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical group CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 239000010840 domestic wastewater Substances 0.000 claims description 2
- 239000010842 industrial wastewater Substances 0.000 claims description 2
- 229950010765 pivalate Drugs 0.000 claims description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 230000004907 flux Effects 0.000 description 16
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 5
- 229940098773 bovine serum albumin Drugs 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QJNYIFMVIUOUSU-UHFFFAOYSA-N chloroethene;ethenyl acetate;furan-2,5-dione Chemical compound ClC=C.CC(=O)OC=C.O=C1OC(=O)C=C1 QJNYIFMVIUOUSU-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000001043 yellow dye Substances 0.000 description 1
Classifications
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of an amphiphilic terpolymer ultrafiltration membrane. The method comprises the following steps: (1) Stirring deionized water, a dispersing agent and an initiator for 0.1-0.5h to obtain a mixed solution; (2) Polymerizing the mixed solution, acrylonitrile, dimethylaminoethyl acrylate and vinyl chloride for 4-8 hours to obtain a copolymer; (3) Stirring the copolymer, the solvent and the additive to obtain a casting solution; (4) And (3) scraping and casting the casting membrane solution to form a membrane, standing, and immersing in deionized water to obtain the PVC ultrafiltration membrane. The invention has simple polymerization process and adjustable chemical structure, and the prepared ultrafiltration membrane has stable structure, excellent hydrophilicity and capability of absorbing micro pollutants.
Description
Technical Field
The invention relates to the field of membrane separation, in particular to an amphiphilic copolymer ultrafiltration membrane, and particularly relates to a method for preparing a PVC copolymer ultrafiltration membrane by in-situ suspension polymerization.
Background
Currently, polymeric ultrafiltration membrane materials mainly include polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), polyethersulfone (PES), polyamide (PA), polyacrylonitrile (PAN), and the like. Among them, PVC has been widely used in the manufacture of ultrafiltration membranes due to its excellent properties such as low cost, excellent mechanical properties, and chemical resistance. However, polymeric ultrafiltration membranes are susceptible to contamination during water treatment due to their inherent hydrophobic character, which greatly affects the lifetime of the ultrafiltration membranes.
Membrane fouling is mainly due to the accumulation of large amounts of contaminants in the membrane surface and internal pore channels, which not only reduces the permeation flux of the membrane, but also significantly shortens the service life of the membrane. To date, there have been various processes to improve the anti-fouling properties of films, mainly including: surface coating, surface grafting, additive blending and other modification methods. However, the existing methods have the problems of pore blocking on the surface of the membrane, damage to the structure of a polymer matrix, leakage of additives, incompatibility of components, uneven dispersion, functional deficiency and the like, so that the PVC copolymer ultrafiltration membrane which has the advantages of stable structure, excellent anti-pollution performance and strong capability of adsorbing micro pollutants has important significance.
At present, research on amphiphilic polyvinyl chloride terpolymers and a preparation method thereof are reported at home and abroad. The comparison is typically: chinese patent (CN 101402701A) discloses a method for producing a vinyl chloride-vinyl acetate-maleic anhydride terpolymer, which has good hydrophilicity and can be used for preparing hydrophilic components of a PVC filtering membrane. However, most of the comonomers in the existing vinyl chloride copolymer are oil-soluble monomers (such as vinyl acetate, acrylic ester and the like), but the prepared copolymer has poor hydrophilicity. When water-soluble monomers (e.g. maleic anhydride, acrylic acid, etc.) are used as comonomers, on the one hand, copolymerization with vinyl chloride monomers is difficult and, on the other hand, there is a lack of further functionality. In addition, the patent requires the addition of a bridging agent (any of methanol, ethanol, propanol, and butanol) during the synthesis process, which increases the complexity of the reaction. Chinese patent (CN 2015100591133) discloses a nonionic functionalized vinyl chloride polymer and a method for preparing the same. The functional vinyl chloride polymer is an active precursor polymer with a main chain containing an atom transfer radical polymerization active side group and polymerized in an aqueous phase dispersion system by taking chlorine-containing monomers, a graftable active monomer and a hydrophilic functional monomer as comonomers, and then the active side group is used for initiating the nonionic functional monomer to carry out interfacial atom transfer radical polymerization on a solid-liquid interface, so that the nonionic functional vinyl chloride polymer containing nonionic side chains is polymerized. However, the hydrophilic segment of the patent is a graft copolymer grafted on the polymer main chain as a graft segment, not a conventional copolymer on the main chain, which results in great differences in properties of the main chain and the graft chain in the polymer chain, defects of easy phase separation or performance in the preparation of polymer products, and the chemical bond of the connection of the graft segment and the main chain is not very stable; in the process of grafting modification, the main chain structure is damaged to a certain extent, so that active sites and defect points are added, and then other monomers are grafted to the main chain by utilizing the active sites and the defect points.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a preparation method of an amphiphilic terpolymer ultrafiltration membrane. The method adopts an in-situ suspension copolymerization method, and realizes that all polymerization components are positioned on a polymer main chain through a free radical polymerization mechanism and the bridging action of acrylonitrile. The invention has simple polymerization process and adjustable chemical structure, and the prepared ultrafiltration membrane has stable structure, excellent hydrophilicity and capability of absorbing micro pollutants.
The technical scheme of the invention is as follows:
a method for preparing an amphiphilic terpolymer ultrafiltration membrane, comprising the following steps:
(1) Stirring deionized water, a dispersing agent and an initiator for 0.1-0.5h to obtain a mixed solution;
wherein, the mass ratio of deionized water, dispersant and initiator is (600-800): (10-20): (2-5);
the dispersing agent is polyvinyl alcohol, hydroxymethyl propyl cellulose or a combination of the two.
The initiator is tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate or pivalate peroxypivalate;
(2) Mixing the mixed solution obtained in the step (1), acrylonitrile, dimethylaminoethyl acrylate and vinyl chloride, stirring for 0.3-0.5h, and then carrying out polymerization reaction for 4-8h at 50-70 ℃ to obtain a copolymer;
wherein the mass ratio of the mixed solution to the vinyl chloride to the acrylonitrile to the dimethylaminoethyl acrylate is (612-825): (200-300): (50-150) is (5-20);
(3) Stirring the copolymer, the solvent and the additive obtained in the step (2) for 10-18 hours at 50-70 ℃, and then standing for 12-24 hours to obtain a casting solution;
wherein, the mass ratio of the copolymer, the solvent and the additive is (10-20): (60-80): (5-15);
(4) Scraping and casting the casting solution obtained in the step (3) into a membrane, and immersing the membrane into deionized water for 0.5-5 min to obtain a PVC ultrafiltration membrane;
wherein the thickness of the scratch casting is 150-250 mu m;
the stirring speed in the step (1) is 100-500r/min.
The stirring speed in the step (2) is 500-800r/min.
The solvent in step (3) comprises one or a mixture of several of DMAc, DMF, NMP.
The additive in step (3) comprises one or more of PEG400, PEG800, PEG1000, PVP (K30) or their mixture.
The application of the amphiphilic terpolymer ultrafiltration membrane prepared by the method is used for adsorbing micro pollutants in domestic or industrial wastewater.
The pollutant is sunset yellow or copper ions.
The method specifically comprises the following steps: soaking in sunset yellow solution with pH of 3-5 and 10-50ppm at normal temperature for 2-6 hr; or soaking in copper ion solution of pH6-7 and 1-10 ppm at normal temperature for 1-3 hr;
10-100 mg of film is added per 100mL of solution containing the pollutant.
The regeneration method of the amphiphilic terpolymer ultrafiltration membrane comprises the following steps: washing an ultrafiltration membrane for adsorbing sunset yellow solution by using sodium hydroxide solution with pH of 9-11; the ultrafiltration membrane that adsorbs the copper ion solution is washed with a hydrochloric acid solution having a pH of 3 to 5.
The invention has the substantial characteristics that:
in the prior art, because vinyl chloride and a hydrophilic monomer (dimethylaminoethyl acrylate) are difficult to copolymerize, acrylonitrile which is easily copolymerized with both vinyl chloride and dimethylaminoethyl acrylate is added as a third comonomer to participate in copolymerization, and the hydrophilic dimethylaminoethyl acrylate can be more easily and stably introduced into a PVC chain main chain by utilizing the strong hydrophilicity, environmental responsiveness and the capability of adsorbing charged pollutants of the dimethylaminoethyl acrylate, so that the PVC ultrafiltration membrane which has the advantages of stable structure, excellent anti-pollution performance and strong capability of adsorbing micro pollutants is prepared.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the acrylonitrile which is easily copolymerized with vinyl chloride and dimethylaminoethyl acrylate is selected to polymerize the two monomers which are not easily copolymerized together through a simple polymerization method, so that the performance of the film is greatly improved.
(2) The invention can change the components and the distribution of the amphiphilic terpolymer chain segment to adjust the performance of the membrane by adjusting the proportion of the monomers.
(3) According to the invention, the prepared amphiphilic terpolymer is prepared into the ultrafiltration membrane by adopting a non-solvent induced phase separation method, so that the synthesized polymer is uniformly distributed in the membrane, and the loss in the preparation process is avoided, and the comprehensive performance of the membrane is more durable and stable.
Detailed Description
The invention is described below in connection with examples which are provided solely for the purpose of further illustrating the features and advantages of the invention and are not intended to limit the scope of the claims.
Example 1
The embodiment provides a preparation method of an amphiphilic terpolymer ultrafiltration membrane, which comprises the following steps:
(1) Mixing 800g of deionized water, 20g of polyvinyl alcohol and 5g of tert-butyl peroxyneodecanoate, and stirring at 200r/min for 0.3h to obtain a mixed solution;
(2) Mixing all the mixed solution obtained in the step (1), 50g of acrylonitrile, 5g of dimethylaminoethyl acrylate and 300g of vinyl chloride, adding into a reaction kettle, sealing, stirring at 600r/min for 0.4h, then carrying out polymerization at 60 ℃ and 0.75Mpa for 5h to obtain a copolymer, and washing the copolymer with deionized water;
(3) Heating 10g of the copolymer obtained in the step (2), 60g of DMAc and 5g of PEG400 to 60 ℃, stirring for 12 hours under the heat preservation condition, and standing for 18 hours to obtain a casting solution;
(4) And (3) carrying out scraping casting film forming on the film casting solution obtained in the step (3) by using a 200 mu m film coater, and immersing the film casting solution in deionized water for 1min to obtain the 104 mu m PVC ultrafiltration film.
Example 2
The embodiment provides a preparation method of an amphiphilic terpolymer ultrafiltration membrane, which comprises the following steps:
(1) 700g of deionized water, 15g of hydroxymethyl propyl cellulose and 3g of tervalproate peroxide are mixed, and stirred for 0.5h at 100r/min to obtain a mixed solution; (2) Mixing all the mixed solution obtained in the step (1), 100g of acrylonitrile, 10g of dimethylaminoethyl acrylate and 250g of vinyl chloride, adding into a reaction kettle, sealing, stirring at 800r/min for 0.3h, then carrying out polymerization at 70 ℃ and 0.8Mpa for 8h to obtain a copolymer, and washing the copolymer with deionized water; (3) Heating 20g of the copolymer obtained in the step (2), 80g of NMP and 15g of PEG800 to 50 ℃, stirring for 18 hours under the heat preservation condition, and standing for 24 hours to obtain a casting solution; the mass ratio of the copolymer to NMP to PEG800 is 20:80:15;
(4) Scraping and casting the film casting solution obtained in the step (3) into a film by using a 200 mu m film coater, standing and immersing the film casting solution in deionized water for 1min to obtain a 95 mu m PVC ultrafiltration film;
example 3
The embodiment provides a preparation method of an amphiphilic terpolymer ultrafiltration membrane, which comprises the following steps:
(1) 600g of deionized water, 10g of hydroxymethyl propyl cellulose and 2g of cumyl peroxyneodecanoate are mixed, and stirred for 0.1h at 500r/min to obtain a mixed solution; (2) Mixing all the mixed solution obtained in the step (1), 150g of acrylonitrile, 20g of dimethylaminoethyl acrylate and 200g of vinyl chloride, adding into a reaction kettle, sealing, stirring at 500r/min for 0.5h, then carrying out polymerization at 50 ℃ and 0.7Mpa for 4h to obtain a copolymer, and washing the copolymer with deionized water; (3) Heating 15g of the copolymer obtained in the step (2), 75g of DMF and 10g of PEG1000 to 70 ℃, stirring for 10 hours under the condition of heat preservation, and standing for 12 hours to obtain a casting solution; (4) Scraping and casting the film casting solution obtained in the step (3) into a film by using a 200 mu m film coater, standing and immersing the film casting solution in deionized water for 1min to obtain a 96 mu m PVC ultrafiltration film;
comparative example 1
This comparative example provides a method for preparing a PVC film comprising the steps of:
respectively weighing 20g of polyvinyl alcohol, 2g of tert-butyl peroxyneodecanoate and 800g of deionized water, adding into a reaction kettle, and mixing and stirring for 6min at a rotating speed of 200r/min to obtain a uniform aqueous solution;
respectively weighing 300g of chloroethylene, putting into a reaction kettle, sealing, mixing and stirring for 0.3h at the rotating speed of 500r/min, heating to 60 ℃, discharging unreacted monomers after the reaction for 4h, and repeatedly cleaning the products with deionized water to obtain a copolymerization product;
weighing 10g of copolymer, 60g of DMAc and 5g of PEG400, respectively putting into a flask, stirring for 10 hours at 50 ℃, and standing for 12 hours after the reaction is finished to obtain casting solution;
the casting solution is scraped and cast into a film by using a 200 mu m film coater, and is immersed into deionized water after standing, so as to obtain the 86 mu m PVC ultrafiltration film.
The films obtained in examples 1 to 3 and comparative example 1 were subjected to performance tests, respectively, the test items including:
tensile strength, i.e., the tensile strength at which the film breaks is measured.
The water contact angle, i.e. the hydrophilicity of the detection film.
Pure water flux, i.e. the pure water flux of the membrane was evaluated by measuring the filtrate volume by filtration for 30min under 0.1MPa (25 ℃). Before the experiment, the film was pre-pressed for 30min at 0.15MPa (25 ℃).
Pure water flux calculation formula:
in the formula, J w For pure water flux, V (L) is the osmotic water quantity, A (m) 2 ) Is the effective area of the membrane, (t (h) is the test time.
The anti-pollution capability is that 1g/L bovine serum albumin solution is used as filtrate, and the filtration is continuously carried out for 1h under 0.1MPa, and the rejection rate and flux reduction rate of the membrane are detected. The rejection rate of the membrane was calculated by measuring the concentration of bovine serum albumin before and after filtration by means of an ultraviolet spectrophotometer at a wavelength of 286 nm. The flux decrease rate was calculated by measuring the flux after filtering the bovine serum albumin solution and the value of pure water flux before measurement.
The retention rate calculation formula:
in the formula, r is the retention rate, C p And C f (mg·L -1 ) The concentration of the bovine serum albumin solution in the filtrate and the feed solution respectively.
Flux reduction rate calculation formula:
in the formula, DR t J is the flux decrease rate p For flux when the feed solution is bovine serum albumin solution, J w Is the pure water flux of the membrane.
The adsorption capacity test of micro pollutants, namely the adsorption capacity test of sunset yellow and copper ion solutions, comprises the following steps: two 60mg copolymer films are taken and respectively added into 100mL of sunset yellow solution with the pH value of 3 and 50ppm and 50mL of cupric chloride ion solution with the pH value of 6 and 5ppm, and soaked and adsorbed for 2 hours at the temperature of 25 ℃;
regeneration performance test: the two adsorbed films obtained above are respectively washed by sodium hydroxide with pH of 10 and hydrochloric acid solution with pH of 3 to regenerate the films, and then are put into sunset yellow solution with pH of 3,50ppm and cupric chloride ion solution with pH of 6,5ppm for adsorption. And washing with 10 pH sodium hydroxide and 3 pH hydrochloric acid solution respectively to regenerate the membrane, and then adding 3,50ppm sunset yellow solution and 6,5ppm cupric chloride ion solution again to adsorb at 25deg.C for 2 hr.
The tensile strength, rejection rate of the film, flux decrease rate, sunset yellow dye, adsorption capacity of copper ions, and adsorption capacity after regeneration of the film are shown in table 1.
TABLE 1 Effect of different examples on the performance of amphiphilic terpolymer ultrafiltration membranes
As can be seen from the table, the pure water flux, the anti-pollution capability and the micro-pollutant adsorption capability of the amphiphilic terpolymer ultrafiltration membrane are all improved to a great extent compared with the comparative example. In addition, as the content of the hydrophilic monomer dimethylaminoethyl acrylate in the copolymer is increased, the pure water flux, the dirt resistance and the adsorption performance of the membrane are also obviously improved.
The invention is not a matter of the known technology.
Claims (8)
1. The preparation method of the amphiphilic terpolymer ultrafiltration membrane is characterized by comprising the following steps of:
(1) Stirring deionized water, a dispersing agent and an initiator for 0.1-0.5h to obtain a mixed solution;
wherein, the mass ratio of deionized water, dispersant and initiator is (600-800): (10-20): (2-5);
the dispersing agent is polyvinyl alcohol, hydroxymethyl propyl cellulose or a combination of the polyvinyl alcohol and the hydroxymethyl propyl cellulose;
the initiator is tert-butyl peroxyneodecanoate, cumyl peroxyneodecanoate or pivalate peroxypivalate;
(2) Mixing the mixed solution obtained in the step (1), acrylonitrile, dimethylaminoethyl acrylate and vinyl chloride, stirring for 0.3-0.5h, and then carrying out polymerization reaction for 4-8h at 50-70 ℃ to obtain a copolymer;
wherein the mass ratio of the mixed solution to the vinyl chloride to the acrylonitrile to the dimethylaminoethyl acrylate is (612-825): (200-300): (50-150) is (5-20);
(3) Stirring the copolymer, the solvent and the additive obtained in the step (2) for 10-18 hours at 50-70 ℃, and then standing for 12-24 hours to obtain a casting solution;
wherein, the mass ratio of the copolymer, the solvent and the additive is (10-20): (60-80): (5-15);
(4) And (3) scraping and casting the casting solution obtained in the step (3) into a membrane, and immersing the membrane into deionized water for 0.5-5 min to obtain the PVC ultrafiltration membrane.
2. The method for preparing an amphiphilic terpolymer ultrafiltration membrane according to claim 1, wherein the scratch casting thickness is 150-250 μm.
3. The method for preparing an amphiphilic terpolymer ultrafiltration membrane according to claim 1, wherein the stirring rate in the step (1) is 100-500r/mi; the stirring speed in the step (2) is 500-800r/min.
4. The method for preparing an amphiphilic terpolymer ultrafiltration membrane according to claim 1, wherein the solvent in the step (3) is one or a mixture of a plurality of DMAc, DMF, NMP;
the additive in the step (3) is one or more of PEG400, PEG800, PEG1000 and PVP (K30).
5. The use of an amphiphilic terpolymer ultrafiltration membrane prepared by the method of claim 1, characterized by being used for adsorbing micro-pollutants in domestic or industrial wastewater.
6. The use according to claim 5, wherein the contaminant is sunset yellow or copper ions.
7. The use according to claim 5, characterized in that it comprises in particular the following steps: adsorbing in sunset yellow solution of pH3-5 and 10-50ppm at normal temperature for 2-6 hr; or adsorbing in copper ion solution of pH6-7 and 1-10 ppm at normal temperature for 1-3 hr;
10-100 mg of film is added per 100mL of solution containing the pollutant.
8. The use according to claim 7, characterized in that the regeneration method of the amphiphilic terpolymer ultrafiltration membrane comprises the following steps: washing an ultrafiltration membrane for adsorbing sunset yellow solution by using sodium hydroxide solution with pH of 9-11; the ultrafiltration membrane that adsorbs the copper ion solution is washed with a hydrochloric acid solution having a pH of 3 to 5.
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