CN101721927A - Ultrafiltration membrane copoly(phthalazinone aryl ether sulfone) and preparation method thereof - Google Patents
Ultrafiltration membrane copoly(phthalazinone aryl ether sulfone) and preparation method thereof Download PDFInfo
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- CN101721927A CN101721927A CN 200910220545 CN200910220545A CN101721927A CN 101721927 A CN101721927 A CN 101721927A CN 200910220545 CN200910220545 CN 200910220545 CN 200910220545 A CN200910220545 A CN 200910220545A CN 101721927 A CN101721927 A CN 101721927A
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- ether sulfone
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- aryl ether
- additive
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- 239000012528 membrane Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000000108 ultra-filtration Methods 0.000 title abstract description 12
- 229920001577 copolymer Chemical class 0.000 title abstract 2
- -1 ether sulfone Chemical class 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 238000005266 casting Methods 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000007334 copolymerization reaction Methods 0.000 claims description 18
- 239000011521 glass Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005345 coagulation Methods 0.000 claims description 12
- 230000015271 coagulation Effects 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical group [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical group C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 abstract 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 3
- MXVLMYZRJAHEIS-UHFFFAOYSA-N 1-(2-phenylphenyl)naphthalene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 MXVLMYZRJAHEIS-UHFFFAOYSA-N 0.000 abstract 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000000614 phase inversion technique Methods 0.000 abstract 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 abstract 1
- 125000000542 sulfonic acid group Chemical group 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 15
- 230000004907 flux Effects 0.000 description 11
- 229920006393 polyether sulfone Polymers 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000004695 Polyether sulfone Substances 0.000 description 6
- 150000003457 sulfones Chemical class 0.000 description 6
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 description 4
- 241000500881 Lepisma Species 0.000 description 4
- 229950009789 cetomacrogol 1000 Drugs 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 150000002576 ketones Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229960003511 macrogol Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明公开了一类新型含二氮杂萘酮结构共聚芳醚砜超滤膜及其制备方法。该超滤膜是以含二氮杂萘酮结构共聚芳醚砜为膜材料料，以氯仿、二氯甲烷、二甲基亚砜、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基-2-吡咯烷酮或它们的混合液为溶剂，加入适当的添加剂，配制铸膜溶液，经相转化方法制得。由于含二氮杂萘酮结构共聚芳醚砜分子链中含有全芳环扭曲非共平面的杂萘联苯结构，具有较高的玻璃化转变温度，化学稳定性优异，由其所制备的新型超滤膜具有优良的耐高温、耐酸碱、耐氧化性能。含二氮杂萘酮结构共聚芳醚砜的结构简式如下：其中R1、R2、R3、R4都可以为氢原子、卤素原子、甲基、芳基或磺酸基；X可以为
。The invention discloses a novel type of copolyaryl ether sulfone ultrafiltration membrane containing a phthalazinone structure and a preparation method thereof. The ultrafiltration membrane is based on a phthalazinone-containing copolymer polyaryl ether sulfone as a membrane material, and chloroform, dichloromethane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-di Methyl acetamide, N-methyl-2-pyrrolidone or their mixed solution is used as a solvent, and appropriate additives are added to prepare a film casting solution, which is obtained by a phase inversion method. Since the molecular chain of the copolymerized aryl ether sulfone containing phthalazinone structure contains a non-coplanar non-coplanar naphthyl biphenyl structure with all aromatic rings, it has a high glass transition temperature and excellent chemical stability. The new type prepared by it The ultrafiltration membrane has excellent high temperature resistance, acid and alkali resistance, and oxidation resistance. The structural formula of the copolymerized aryl ether sulfone containing phthalazinone structure is as follows:
Wherein R 1 , R 2 , R 3 , R 4 can all be hydrogen atom, halogen atom, methyl group, aryl group or sulfonic acid group; X can be .
Description
Technical field
The invention belongs to the polymeric membrane for separation technical field, specially refer to and contain naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter and preparation method thereof.
Background technology
Membrane separation technique is as the efficient new and high technology of separating, concentrating, purifying and purify, compare with traditional isolation technics have easy to operate, facility compact, working environment safety, energy-conservation and reduce advantage such as chemical reagent use, be widely used in every field such as water treatment, electronics, food, environmental protection, chemical industry, metallurgy, medicine, biology, the energy, oil.Membrane separation technique can be divided into micro-filtration, ultrafiltration, nanofiltration, counter-infiltration and gas by separation process and separate etc.
Along with the development of membrane separation technique, hyperfiltration technique has been widely used in many industrial circles such as Industrial Wastewater Treatment, metal processing, coating, biological product processing, drinking water preparation, food industry, pharmaceuticals industry, PETROLEUM PROCESSING.Ultrafiltration can be used for the being purified preliminary treatment of thing concentrates purification of protein and other organic matters from suspension.The purifying that can be used for ultra-pure water, the manufacturing that protein and animal blood are handled, bleaching effluent is handled in the filtration of fruit juice, and reclaims in the pulp and the lignin in the paper industry or the like.Ultrafiltration can be used for holding back virus, bacterium, thermal source, endotoxin, but can not hold back ion.The diffusion barrier that ultra-filtration process adopts is a milipore filter, and milipore filter surface effectively catching layer thickness is thin (0.1-10 μ m), and membrane aperture is 10
-3-10
-1Between the μ m, operating pressure is generally 0.1-0.4MPa.Expansion day by day along with the hyperfiltration technique application, promoted the Application and Development of milipore filter material on the one hand, the milipore filter material is also expanded to macromolecular materials such as polysulfones, polyether sulfone, polyamide, polysulfonamides, polyacrylonitrile and Kynoar by cellulose, more and more to the demand of milipore filter kind on the other hand, performance requirement is also more and more higher, and present business-like milipore filter often exists flux lower or acid and alkali-resistance is not good enough, the relatively poor grade of resistance to elevated temperatures is not enough, can't satisfy the demand of each industrial circle.The character of membrane material and the structure of film play decisive role to the milipore filter performance, and desirable membrane material should have good film forming, heat endurance, chemical stability, acid and alkali resistance, microbial attack and oxidation resistent susceptibility etc.Yet existing milipore filter with macromolecular material all exist heat resistance not good enough, be difficult to satisfy simultaneously problems such as high-permeability and high selectivity requirement, its application in a lot of fields is restricted, so the high temperature resistant milipore filter material and the novel diffusion barrier of exploitation function admirable are significant.
Polyether sulfone is the thermoplastic polymer that contains sulfuryl and aromatic ring on the class main chain, have better heat-resisting, chemically-resistant and solvent stability, mechanical property and electrical property etc., be widely used in various fields such as electronic apparatus, machinery, medical treatment, food, space flight and aviation.As separation membrane material, also be widely used in the basement membrane of milipore filter, composite membrane etc.Though the hear resistance of poly (ether-sulfone) ultrafiltration membrane is compared with milipore filters such as polysulfones, polyacrylonitrile and increased,, be difficult to the high-throughout milipore filter of preparation owing to himself design feature.Phenolic polyether sulphone is the polyether sulfone that contains the Cardo group on the main chain, because the introducing of phenolphthalein side group makes the hear resistance of phenolic polyether sulphone and water flux slightly improve, and the corresponding reduction of its acid-proof alkaline.Patent CN93109180.2 is incorporated into naphthyridine ketone structure on the polyether sulfone molecular backbone, announced a class novel contain the naphthyridine ketone structure polyether sulfone, because the diazanaphthalene terphenyl structure of complete fragrant non-copline distortion is introduced, and gives novel polyether sulphone high temperature resistant, soluble characteristic.Because the introducing of the non-coplanar structure of full virtue distortion, by containing the prepared milipore filter of naphthyridine ketone structure polyether sulfone, compare with the bisphenol a polysulfone milipore filter with poly (ether-sulfone) ultrafiltration membrane have better choice, higher flux and better heat endurance.But the toughness that contains naphthyridine ketone structure poly (ether-sulfone) ultrafiltration membrane dry film is compared with polysulphone super-filter membrane slightly and is reduced.The novel naphthyridine ketone structure copolymerization aryl ether sulfone that contains is when keeping the polymer excellent heat resistance, improved the toughness of polymer, and still be dissolvable in water N-methyl pyrrolidone, N, system membrane solvents commonly used such as N-dimethylacetylamide have extraordinary application prospect in the diffusion barrier field.
Summary of the invention
The invention provides the novel naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter and preparation method thereof that contains of a class.The present invention adopts novel copolymerized aryl ether sulfone to prepare high flux, high rejection, resistant to elevated temperatures milipore filter.
The novel skeleton symbol that contains naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter material of the present invention is:
R wherein
1, R
2, R
3, R
4Can be hydrogen atom, halogen atom, methyl, aryl or sulfonic group; X can for
Wherein working as X is
The time synthetic copolymerization aryl ether sulfone, can be called and contain naphthyridine ketone structure hydroquinones type copolyether sulfone (PPHES); When X is
The time synthetic copolymerization aryl ether sulfone, can be called and contain naphthyridine ketone structure '-biphenyl diphenol type copolyether sulfone (PPBES); When X is
The time synthetic copolymerization aryl ether sulfone, can be called and contain naphthyridine ketone structure bisphenol S type copolyether sulfone; When X is
The time synthetic copolymerization aryl ether sulfone, can be called and contain naphthyridine ketone structure naphthalenediol type copolyether sulfone.
The present invention is a membrane material with the above-mentioned novel naphthyridine ketone structure copolymerization aryl ether sulfone that contains, and adopts the phase inversion preparation to contain naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter, and step is as follows:
1) will contain naphthyridine ketone structure copolymerization aryl ether sulfone membrane material and additive and be dissolved in the solvent, and remove by filter impurity, leave standstill or vacuum defoamation, be mixed with casting solution;
2) casting solution is poured on glass plate or the nonwoven, scrapes with scraper and make certain thickness film, expose 1-60s in the air after, change in 5-50 ℃ the coagulation bath, the cohesion film forming is soaked flush away solvent, additive etc. then in water, promptly make the finished product milipore filter.
The quality percentage composition that contains naphthyridine ketone structure copolymerization aryl ether sulfone membrane material in the casting solution of the present invention is 10-25%, and the quality percentage composition of additive is 1-25%, and the quality percentage composition of solvent is 50-89%.
It can be chloroform, carrene, dimethyl sulfoxide (DMSO), N that the present invention prepares the solvent that casting solution adopts, dinethylformamide, N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-or their mixed liquor, preferred solvent is N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-or their mixed liquor.
Additive of the present invention can be lithium chloride, lithium nitrate, organic molecule, polyvinylpyrrolidone, polyethylene glycol or their mixture.The organic molecule additive can be formic acid, acetate, oxalic acid, ethanol, propyl alcohol, ethylene glycol, propane diols, glycerine, butanone, ether, oxolane, dioxane, EGME, diglycol, ethyl acetate etc.Preferable additives is lithium chloride, oxalic acid, propyl alcohol, butanone, oxolane, EGME, diglycol, polyethylene glycol etc.
The coagulation bath that the present invention adopts is the aqueous solution that contains the aqueous solution of 0～5% solvent or contain 0～5% surfactant, and the coagulation bath temperature is 5～50 ℃, 5～30 ℃ of preferred coagulation bath temperature.
The present invention can expose 1-60s in air in film-forming process, preferably expose 5-30s.
Obtained milipore filter soaks in water so that remove solvent, additive etc. fully.
The invention has the beneficial effects as follows to have made to contain naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter that such milipore filter has high flux, high rejection, high temperature resistant, characteristics such as chemical stability is good; Can be directly used in the ultra-filtration and separation field, also can be used as the support counterdie, be used to prepare compounding permeation vaporizing film, composite nanometer filtering film, complex reverse osmosis membrane and gas separation membrane etc.
The specific embodiment
Be described in detail embodiments of the invention below in conjunction with technical scheme.
Embodiment 1
Is 15% with the naphthyridine ketone structure '-biphenyl diphenol type copolyether sulfone (PPBES) that contains after the vacuum drying by the quality percentage composition, EGME is 15% to be dissolved in the N-methyl pyrrolidone and to become homogeneous phase solution by the quality percentage composition, filter, deaeration, leave standstill casting solution.Casting solution is cast on the glass plate,, stop evaporation 15s in the air, change in 5 ℃ the coagulation bath dipping film forming over to glass slicker striking film forming.Treat that film comes off from glass plate, transfer to and soak in the deionized water more than the 24h, after exchange of solvent is complete, measure its structure, performance.Under room temperature, 0.2MPa, with deionized water precompressed 30min, test pure water flux and rejection down for 15 ℃ in operating pressure 0.1MPa, operating temperature then, the pure water flux of film is about 235L/m
2H is 95% to the rejection of cetomacrogol 1000 0.
Embodiment 2
PPBES after the vacuum drying and additive EGME (EGME) are 15% by the quality percentage composition are dissolved in N, become homogeneous phase solution in the N-dimethylacetylamide, filter, deaeration, leave standstill casting solution.Casting solution is cast on the glass plate,, stop evaporation 15s in the air, change in 20 ℃ the coagulation bath dipping film forming over to glass slicker striking film forming.Treat that film comes off from glass plate, transfer to and soak in the deionized water more than the 24h, after exchange of solvent is complete, measure its structure, performance.0.2MPa down, with deionized water precompressed 30min, the performance of test membrane then.Under operating pressure was 25 ℃ of 0.1MPa, operating temperature, the pure water flux of film was about 360L/m
2H is 98% to the rejection of cetomacrogol 1000 0, is 71% to the rejection of Macrogol 6000.
Embodiment 3
Is 20% with the PPBES after the vacuum drying by mass fraction, lithium chloride (LiCl) is dissolved in N by mass fraction 2% and EGME (EGME) by mass fraction 8%, becomes homogeneous phase solution in the N-dimethylacetylamide (DMAc), filters, deaeration, leave standstill casting solution.Casting solution is cast on the glass plate,, stop evaporation 15s in the air, change in 15 ℃ the coagulation bath dipping film forming over to glass slicker striking film forming.Treat that film comes off from glass plate, transfer to and soak in the deionized water more than the 24h, after exchange of solvent is complete, measure its structure, performance.Under room temperature, 0.2MPa, with deionized water precompressed 30min, in operating pressure 0.1MPa, 15 ℃ of following test membrane performances of operating temperature, the pure water flux of film is about 140L/m then
2H is 96% to the rejection of cetomacrogol 1000.
Embodiment 4
With after the vacuum drying to contain naphthyridine ketone structure bisphenol S type copolyether sulfone be 15% by the quality percentage composition, EGME is 15% to be dissolved in the N-methyl pyrrolidone and to become homogeneous phase solution by the quality percentage composition, filter, deaeration, leave standstill casting solution.Casting solution is cast on the glass plate,, stop evaporation 15s in the air, change in 5 ℃ the coagulation bath dipping film forming over to glass slicker striking film forming.Treat that film comes off from glass plate, transfer to and soak in the deionized water more than the 24h, after exchange of solvent is complete, measure its structure, performance.Under room temperature, 0.2MPa, with deionized water precompressed 30min.Test pure water flux and rejection down for 25 ℃ in operating pressure 0.1MPa, operating temperature.The pure water flux of film is about 382L/m
2H is 85% to the rejection of cetomacrogol 1000 0.
Claims (6)
1. contain naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter, it is characterized in that the polymer architecture skeleton symbol for preparing such milipore filter is:
R wherein
1, R
2, R
3, R
4All be hydrogen atom, halogen atom, methyl, aryl or sulfonic group; X is
2. the described preparation method who contains naphthyridine ketone structure copolymerization aryl ether sulfone milipore filter of claim 1 may further comprise the steps:
1) will contain naphthyridine ketone structure copolymerization aryl ether sulfone membrane material and additive and be dissolved in the solvent, and remove by filter impurity, leave standstill or vacuum defoamation, be mixed with casting solution;
2) casting solution is poured on glass plate or the nonwoven, scrapes with scraper and make certain thickness film, expose 1-60s in the air after, change in 5-50 ℃ the coagulation bath, gel becomes milipore filter, soaks flush away solvent, additive etc. and promptly make the finished product milipore filter in water;
The quality percentage composition that contains naphthyridine ketone structure copolymerization aryl ether sulfone membrane material in the casting solution is 10-25%, and the quality percentage composition of additive is 1-25%, and the quality percentage composition of solvent is 50-89%;
The preparation solvent that casting solution adopted is chloroform, carrene, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, and N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-or their mixed liquor are the solvent of preparation casting solution;
Additive is lithium chloride, lithium nitrate, organic molecule, polyvinylpyrrolidone, polyethylene glycol or their mixture;
With the aqueous solution that contains 0～5% solvent or the aqueous solution that contains 0～5% surfactant is coagulation bath; The coagulation bath temperature is 5～50 ℃, exposes 1-60s in air.
3. preparation method according to claim 2 is characterized in that: the organic molecule additive is formic acid, acetate, oxalic acid, ethanol, propyl alcohol, butanols, ethylene glycol, propane diols, glycerine, butanone, ether, oxolane, dioxane, EGME, diglycol or ethyl acetate.
4. according to claim 2 and 3 described preparation methods, it is characterized in that: additive is lithium chloride, oxalic acid, propyl alcohol, butanone, oxolane, EGME, diglycol, polyethylene glycol.
5. preparation method according to claim 2 is characterized in that: the coagulation bath temperature is 5-30 ℃, exposes 5-30s in air.
6. preparation method according to claim 2 is characterized in that: solvent is N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-or their mixed liquor.
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| CN101955586A (en) * | 2010-09-30 | 2011-01-26 | 中南大学 | Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof |
| CN102304224A (en) * | 2011-07-22 | 2012-01-04 | 大连理工大学 | Phthalaznone-containing poly(aryl ether nitrile) end-capped with maleimide and preparation method thereof |
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| CN104096484A (en) * | 2014-08-11 | 2014-10-15 | 中国科学院长春应用化学研究所 | Ultrafiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101955586A (en) * | 2010-09-30 | 2011-01-26 | 中南大学 | Epoxy terminated polyarylether resins with phthalonitrile side group and curing materials and preparation methods thereof |
| CN102304224A (en) * | 2011-07-22 | 2012-01-04 | 大连理工大学 | Phthalaznone-containing poly(aryl ether nitrile) end-capped with maleimide and preparation method thereof |
| CN103111195A (en) * | 2013-03-13 | 2013-05-22 | 株洲时代新材料科技股份有限公司 | High-temperature resistance polyamide composite membrane and preparation method thereof |
| CN104096484A (en) * | 2014-08-11 | 2014-10-15 | 中国科学院长春应用化学研究所 | Ultrafiltration membrane and preparation method thereof |
| CN109152981A (en) * | 2015-10-23 | 2019-01-04 | 膜技术研究股份有限公司 | Gas separation membrane based on fluorination and fluoridized polymer |
| CN109152981B (en) * | 2015-10-23 | 2021-12-31 | 膜技术研究股份有限公司 | Gas separation membranes based on fluorinated and perfluorinated polymers |
| CN112221360A (en) * | 2020-09-15 | 2021-01-15 | 大连理工大学 | Copolyethersulfone hemodialysis membrane containing naphthalenone structure and preparation method thereof |
| CN112221361A (en) * | 2020-09-15 | 2021-01-15 | 大连理工大学 | Polyethersulfone/copolyethersulfone-containing naphthalene structure copolyethersulfone blended hollow fiber hemodialysis membrane and preparation method thereof |
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