CN104248917B - A kind of reverse osmosis membrane and preparation method thereof - Google Patents
A kind of reverse osmosis membrane and preparation method thereof Download PDFInfo
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- CN104248917B CN104248917B CN201310268019.XA CN201310268019A CN104248917B CN 104248917 B CN104248917 B CN 104248917B CN 201310268019 A CN201310268019 A CN 201310268019A CN 104248917 B CN104248917 B CN 104248917B
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- osmosis membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 84
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 83
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 83
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 28
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- 150000002431 hydrogen Chemical class 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 125000006833 (C1-C5) alkylene group Chemical group 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 230000032050 esterification Effects 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 44
- 239000000178 monomer Substances 0.000 description 28
- 239000000126 substance Substances 0.000 description 27
- 150000003839 salts Chemical class 0.000 description 25
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 22
- 239000011780 sodium chloride Substances 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 17
- 238000001326 spin-polarised Auger electron spectroscopy Methods 0.000 description 17
- 238000000108 ultra-filtration Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 238000006277 sulfonation reaction Methods 0.000 description 12
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 125000000542 sulfonic acid group Chemical group 0.000 description 11
- 229930185605 Bisphenol Natural products 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000003929 acidic solution Substances 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 8
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 7
- 239000005708 Sodium hypochlorite Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000006482 condensation reaction Methods 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000012024 dehydrating agents Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000012466 permeate Substances 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 125000001174 sulfone group Chemical group 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 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 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- -1 methylene, ethylene, propylene, butylene Chemical group 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 description 2
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
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- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 102100038968 WAP four-disulfide core domain protein 1 Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
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- 239000011550 stock solution Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a kind of reverse osmosis membrane, a kind of preparation method of reverse osmosis membrane and the reverse osmosis membrane that prepared by the method.Described reverse osmosis membrane comprises the supporting layer and separating layer that stack together, wherein, described separating layer for have structure shown in formula (I) there is esterification in a heated condition containing carboxyl polyether sulfone and the crosslinking agent with at least two hydroxyls after the cross-linked network structure layer that obtains; R
1-R
8, R
11-R
24be hydrogen or C independently of one another
1-C
5alkyl, R
9not exist or for C
1-C
5alkylidene, R
10for hydrogen or C
1-C
5alkyl, m:n=0.1-10:1, the described number-average molecular weight containing carboxyl polyether sulfone is 10,000-10 ten thousand; Reverse osmosis membrane provided by the invention, while having higher salt-stopping rate, shows good oxidation resistent susceptibility too.
Description
Technical Field
The invention relates to a reverse osmosis membrane, a preparation method of the reverse osmosis membrane and the reverse osmosis membrane prepared by the method.
Background
Membrane separation is a new technique of separation that emerged at the beginning of the 20 th century and rises rapidly after the 60's of the 20 th century. The core of membrane separation technology is the separation membrane. The porous membrane can be classified into a microfiltration membrane, an ultrafiltration membrane, a nanofiltration membrane and a reverse osmosis membrane according to the pore size of the membrane.
Among them, the reverse osmosis membrane is one of the key technologies for water treatment because of its advantages of good separation performance for organic small molecules and inorganic salt ions, safety, environmental protection, easy operation, etc. Up to now, the main applications of reverse osmosis membranes are in the fields of seawater and brackish water desalination, hard water softening, reclaimed water recovery, industrial wastewater treatment, and ultrapure water preparation. Currently, 90% of the reverse osmosis membranes on the market are composite membranes, i.e. consisting of a separation layer and a support layer. The preparation method of the composite membrane mainly comprises the following steps: dilute solution coating, interfacial polymerization, and plasma polymerization. Composite membranes currently widely used in the water treatment industry are mainly based on interfacial polymerization, for example, a polyamide film can be laminated on the surface of a microporous support base membrane. However, the chemical structure of polyamide makes such composite films weak against chlorine and oxidation, and the tolerance of all commercial polyamide composite films to free chlorine is almost zero, thereby increasing the pretreatment cost of the film and reducing the service life thereof. Therefore, improving the oxidation resistance of membranes is one of the important tasks in current reverse osmosis membrane research.
Therefore, with the development of science, research on a novel reverse osmosis membrane having a high salt rejection rate and also exhibiting good oxidation resistance has become a hot point of research.
Disclosure of Invention
The invention aims to provide a novel reverse osmosis membrane, a preparation method of the reverse osmosis membrane and the reverse osmosis membrane prepared by the method.
The invention provides a reverse osmosis membrane, which comprises a supporting layer and a separation layer which are superposed together, wherein the separation layer is a cross-linked network structure layer which is obtained by esterification reaction of carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups under a heating condition;
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand; preferably, R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
The invention also provides a preparation method of the reverse osmosis membrane, wherein the method comprises the following steps:
(1) dissolving dried carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups in a solvent to prepare a coating liquid;
(2) coating the coating liquid on a support layer, and carrying out esterification reaction on the carboxyl-containing polyether sulfone and the cross-linking agent with at least two hydroxyl groups under the heating condition;
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand; preferably, R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
The invention also provides a reverse osmosis membrane prepared by the method.
The inventors of the present invention have made intensive studies and have unexpectedly found that a network structure layer is produced by dissolving a carboxyl group-containing polyethersulfone and a cross-linking agent having at least two hydroxyl groups in a solvent to prepare a coating solution, coating the coating solution on a support layer, and subjecting the carboxyl group-containing polyethersulfone and the cross-linking agent having at least two hydroxyl groups to an esterification reaction under heating, and the thus-obtained reverse osmosis membrane has both good oxidation resistance and a high salt cut-off rate.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The reverse osmosis membrane provided by the invention comprises a supporting layer and a separation layer which are stacked together, wherein the separation layer is a cross-linked network structure layer which is obtained by esterification reaction of carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups under the heating condition;
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand; preferably, R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
Wherein m represents the number of moles of the structural unit (V) relative to 1mol of the carboxyl group-containing polyethersulfone; n represents the number of moles of the structural unit (VI) relative to 1mol of the carboxyl group-containing polyethersulfone;
the above formula (i) is used only for showing the kind and ratio of the structural units of the carboxyl group-containing polyethersulfone, and does not show the connection relationship between the structural units, that is, the carboxyl group-containing polyethersulfone may be a random copolymer or a block copolymer.
According to the invention, said C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of alkylene groups of (a) may be, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
The inventors of the present invention found in their research that the specific R1-R24The reverse osmosis membrane prepared by matching the carboxyl-containing polyether sulfone with the components has higher oxidation resistance and salt rejection rate, so that preferably,
R1-R8is hydrogen, R9Is ethylene, R10Is methyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is ethyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is propyl, R11-R24Is hydrogen.
According to the present invention, the carboxyl group-containing polyethersulfone having the structure represented by formula (i) may be prepared according to conventional methods, for example, the preparation method may comprise: reacting a bisphenol monomer with a structure shown in a formula (II), a non-sulfonated diphenyl sulfone monomer with a structure shown in a formula (III) and a sulfonated diphenyl sulfone monomer with a structure shown in a formula (IV) under condensation reaction conditions in the presence of a catalyst, and contacting the reaction product with an acidic solution to obtain carboxyl group-containing polyether sulfone with the structure shown in the formula (I), wherein the number average molecular weight of the carboxyl group-containing polyether sulfone can be 1 ten thousand to 10 ten thousand, and preferably 5 to 8 ten thousand;
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl of R25-R28Is halogen, m: n = 0.1-10: 1; preferably, R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl of R25-R28Each independently fluorine or chlorine, m: n = 0.4-4: 1.
as described above, the C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of alkylene groups of (a) may be, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
The amount of the bisphenol monomer, the non-sulfonated diphenyl sulfone monomer and the sulfonated diphenyl sulfone monomer used in the present invention is not particularly limited as long as the carboxyl group-containing polyether sulfone having the structure represented by the formula (i) can be obtained, and for example, the ratio of the number of moles of the bisphenol monomer to the total number of moles of the non-sulfonated diphenyl sulfone monomer and the sulfonated diphenyl sulfone monomer may be 0.8 to 1.2: 1. further, the molar ratio of the non-sulfonated diphenyl sulfone monomer to the sulfonated diphenyl sulfone monomer is preferably 0.1 to 10: 1. more preferably 0.4 to 4: 1.
according to the present invention, the bisphenol monomer may be any of various compounds having a structure represented by formula (II) known in the art, and for example, may be selected from one or more of 4,4 ' -bis (4-hydroxyphenyl) -2-pentanoic acid, 4 ' -bis (4-hydroxyphenyl) -3-hexanoic acid, and 4,4 ' -bis (4-hydroxyphenyl) -4-heptanoic acid. From the viewpoint of availability of raw materials, the bisphenol monomer is particularly preferably 4, 4' -bis (4-hydroxyphenyl) -2-pentanoic acid.
According to the present invention, the non-sulfonated diphenyl sulfone monomer may be various compounds having a structure represented by formula (iii) known in the art, and for example, may be selected from one or more of 4,4 ' -dichlorodiphenyl sulfone, 4 ' -difluorodiphenyl sulfone, and 4,4 ' -dibromodiphenyl sulfone. From the viewpoint of availability of raw materials, the dichlorodiphenyl sulfone is particularly preferably 4,4 '-dichlorodiphenyl sulfone and/or 4, 4' -difluorodiphenyl sulfone.
According to the present invention, the sulfonated diphenyl sulfone monomer may be various compounds having a structure represented by formula (iv) known in the art, and for example, may be selected from one or more of 3,3 '-disulfonated-4, 4' -difluorodiphenyl sulfone disodium salt, 3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt, and 3,3 '-disulfonated-4, 4' -dibromodiphenyl sulfone disodium salt. From the viewpoint of availability of raw materials, the sulfonated diphenyl sulfone monomer is particularly preferably 3,3 '-disulfonated-4, 4' -difluorodiphenyl sulfone disodium salt and/or 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt.
The amount of the catalyst used according to the present invention may be conventionally selected in the art, and for example, the amount of the catalyst may be 1 to 2.5mol based on 1mol of the bisphenol monomer. The catalyst may be any of various catalysts known to those skilled in the art that can be used for the condensation reaction, and for example, may be selected from one or more of potassium carbonate, sodium carbonate, calcium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, and calcium hydride. From the viewpoint of catalytic effect, the catalyst is preferably potassium carbonate and/or sodium carbonate.
According to the present invention, in order to allow the bisphenol monomer, the non-sulfonated diphenyl sulfone monomer and the sulfonated diphenyl sulfone monomer to be more sufficiently contacted and to better control the degree of polymerization of the resulting carboxyl group-containing polyethersulfone having the structure represented by formula (i), it is preferable that the reaction between the bisphenol monomer, the non-sulfonated diphenyl sulfone monomer and the sulfonated diphenyl sulfone monomer is carried out in the presence of an organic solvent and an azeotropic dehydrating agent. The organic solvent may be any organic solvent capable of dissolving the bisphenol monomer, the non-sulfonated diphenyl sulfone monomer and the sulfonated diphenyl sulfone monomer, and may be one or more selected from sulfolane, N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, for example. The azeotropic dehydrating solvent may be any of various substances which are known to be capable of azeotroping with water generated in the reaction system and bringing out water in the reaction system at an azeotropic temperature, and for example, the azeotropic dehydrating solvent may be one or more selected from benzene, toluene, xylene and chlorobenzene.
In addition, the amounts of the organic solvent and the azeotropic dehydrating agent can be selected and varied within a wide range, and for example, the amount of the organic solvent can be 1500 mL-450 mol and the amount of the azeotropic dehydrating agent can be 600 mL-200 mol based on 1mol of the bisphenol monomer, which can facilitate the reaction.
According to the present invention, the condensation reaction conditions may be conventional in the art. For example, the condensation reaction conditions include a reaction temperature and a reaction time, the reaction temperature can be performed in a wide temperature range, and in general, the reaction temperature is preferably 120-220 ℃ in order to further facilitate the reaction. The extension of the reaction time is advantageous for the improvement of the conversion rate of the reactant or the yield of the reaction product, but the extension of the reaction time is not significant for the improvement of the conversion rate of the reactant or the yield of the reaction product, and thus the reaction time is preferably 2 to 24 hours in consideration of efficiency and effect.
According to the present invention, generally, the boiling point of the azeotropic dehydrating solvent is low, so that the reaction cannot be carried out at a high temperature. Therefore, in order to improve the conversion rate of reactants and the yield of reaction products, the preparation method of the carboxyl group-containing polyether sulfone provided by the invention preferably further comprises distilling off the azeotropic dehydrating agent after the reaction for a period of time, and continuing the reaction of the rest materials. Accordingly, the condensation reaction comprises two stages carried out in sequence, wherein the first stage is carried out in the presence of an azeotropic dehydrating agent and the second stage is carried out under conditions to remove the azeotropic dehydrating agent. The reaction conditions of the first stage comprise a reaction temperature of 120-150 ℃ and a reaction time of 1-4 hours, and the reaction conditions of the second stage comprise a reaction temperature of 150-220 ℃ and a reaction time of 1-20 hours, so that the two condensation reaction stages are better cooperated.
According to the invention, after the condensation reaction is completed, the obtained reaction product contains sodium sulfonate groups on the side chain of the molecular chain, and the purpose of contacting the reaction product with an acidic solution is to convert the sodium sulfonate groups into sulfonic acid groups, so that the obtained polymer can meet the requirements of being applied to a reverse osmosis membrane.
The kind and amount of the acidic solution are not particularly limited in the present invention, and for example, the amount of the acidic solution may be 2 to 4mol based on 1mol of the sulfonated diphenyl sulfone monomer. The acidic solution may be selected from, for example, one or more of hydrochloric acid, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution, and the like. Generally, when the concentration of the acidic solution is 0.5-2mol/L, the use requirement can be met. It should be noted that the amount of the above-mentioned acidic solution is 2 to 4mol excluding the amount of the solvent in the acidic solution.
In addition, the carboxyl-containing polyether sulfone obtained by the method provided by the invention has a large molecular weight and is generally sticky, but the catalyst, the organic solvent and the azeotropic dehydrating agent are still remained in the carboxyl-containing polyether sulfone. Therefore, in order to purify the carboxyl group-containing polyethersulfone, the preparation method of the carboxyl group-containing polyethersulfone preferably further comprises the steps of crushing and filtering a product obtained after contacting the reaction product with an acidic solution by using a crusher, then boiling and washing the product with distilled water, filtering the product, and drying the solid-phase product.
In the present invention, the ion exchange capacity of the sulfonated polyarylethersulfone containing carboxyl groups may be 0.5 to 2.5mmol/g, preferably 1.0 to 2.0 mmol/g. The ion exchange capacity of the carboxyl-containing sulfonated polyarylethersulfone refers to the mole number of sulfonic groups in 1g of carboxyl-containing sulfonated polyarylethersulfone, and can be determined by adopting an acid-base titration method.
According to the invention, although the thicknesses of the supporting layer and the separation layer can be selected and changed in a wide range, in order to enable the two layers to have better synergistic cooperation effect and enable the obtained reverse osmosis membrane to have higher salt rejection rate and stronger oxidation resistance, the thickness of the supporting layer is preferably 40-200 micrometers, and the thickness of the separation layer is 100-500 nanometers; more preferably, the thickness of the support layer is 40-150 μm, and the thickness of the separation layer is 100 nm-300 nm.
According to the invention, in order to enable the obtained reverse osmosis membrane to have good oxidation resistance and high salt rejection, the use amount of the carboxyl group-containing polyether sulfone and the cross-linking agent in the esterification reaction process for forming the separation layer is preferably 1-100: 1, more preferably 1 to 50: 1.
according to the invention, the supporting layer can be various existing supporting layers which have certain pore diameter and strength and can be used for a reverse osmosis membrane, and can be an ultrafiltration membrane supported by non-woven fabrics, and the polymer material for forming the ultrafiltration membrane is one or more of phenolphthalein type polyarylethersulfone, polyethersulfone and bisphenol A type polysulfone.
According to the invention, the crosslinking agent is a crosslinking agent having at least two hydroxyl groups. Preferably, the cross-linking agent is one or more of polyvinyl alcohol, polyethylene glycol, ethylene glycol, butylene glycol and glycerol. More preferably, the crosslinking agent is polyvinyl alcohol. In the present invention, the number average molecular weight of the polyvinyl alcohol may be 500-500000, preferably 5000-100000; the number average molecular weight of the polyethylene glycol can be 200-100000, preferably 1000-50000. In the present invention, the number average molecular weight of the polymer is measured by gel permeation chromatography.
The invention also provides a preparation method of the reverse osmosis membrane, which comprises the following steps:
(1) dissolving dried carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups in a solvent to prepare a coating liquid;
(2) coating the coating liquid on a support layer, and carrying out esterification reaction on the carboxyl-containing polyether sulfone and the cross-linking agent with at least two hydroxyl groups under the heating condition;
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand; preferably, R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
Wherein m represents the number of moles of the structural unit (V) relative to 1mol of the carboxyl group-containing polyethersulfone; n represents the number of moles of the structural unit (VI) relative to 1mol of the carboxyl group-containing polyethersulfone;
the above formula (i) is used only to indicate the kind and ratio of the structural units of the sulfonated polyethersulfone containing carboxyl groups, and does not indicate the connection relationship between the structural units, that is, the polyethersulfone containing carboxyl groups may be a random copolymer or a block copolymer.
According to the invention, said C1-C5Specific examples of the alkyl group of (a) may be, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of alkylene groups of (a) may be, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
The inventors of the present invention found in their research that the specific R1-R24The reverse osmosis membrane prepared by matching the carboxyl-containing polyether sulfone with the components has higher oxidation resistance and salt rejection rate, so that preferably,
R1-R8is hydrogen, R9Is ethylene, R10Is methyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is ethyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is propyl, R11-R24Is hydrogen.
According to the invention, the carboxyl group-containing polyether sulfone with the structure shown in the formula (I) can be prepared according to the preparation method, and the details are not repeated.
The amount of the coating liquid used in the present invention is not particularly limited, but in order to obtain a reverse osmosis membrane having good oxidation resistance and high salt rejection, the amount of the coating liquid is preferably such that the thickness of the separation layer is 100-500 nm, preferably 100-300 nm. The thickness of the support layer can also be chosen within wide limits, for example from 40 to 200. mu.m, preferably from 40 to 150. mu.m.
According to the present invention, as described above, the support layer may be any of the existing support layers having a certain pore size and strength and capable of being used for a reverse osmosis membrane, and may be an ultrafiltration membrane supported by a non-woven fabric, and the polymer material constituting the ultrafiltration membrane may be one or more of phenolphthalein type polyarylethersulfone, polyethersulfone and bisphenol a type polysulfone.
According to the invention, the content of the individual components in the coating liquid can be selected and varied within wide limits, for example, the amount of the carboxyl group-containing polyethersulfone can be 0.5 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of the coating liquid; the inorganic particles may be used in an amount of 0.001 to 1 wt%, and preferably, the crosslinking agent is used in an amount of 0.01 to 1 wt%, and more preferably, 0.01 to 0.5 wt%; the weight ratio of the carboxyl-containing polyether sulfone to the cross-linking agent can be 1-100: 1, preferably, the weight ratio of the carboxyl group-containing polyether sulfone to the inorganic particles is 1-50: 1.
according to the present invention, the solvent may be an existing inert medium capable of dissolving the carboxyl group-containing polyethersulfone and additives, and for example, may be selected from one or more of formic acid, acetic acid, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, acetone, and deionized water. Preferably, the solvent is a mixed solvent of formic acid, ethylene glycol monomethyl ether and deionized water, wherein the weight ratio of formic acid, ethylene glycol monomethyl ether and deionized water is preferably 6-8: 1-3: 1, more preferably 7: 2: 1.
in addition, in order to make the obtained reverse osmosis membrane more flat, it is preferable that the preparation method of the reverse osmosis membrane provided by the present invention further comprises fixing the support layer on the glass plate before coating the coating liquid on the support layer.
According to the present invention, the present inventors have unexpectedly found that: under the heating condition, the crosslinking network structure layer can be obtained after the carboxyl-containing polyether sulfone with the structure shown in the formula (I) and the crosslinking agent with at least two hydroxyl groups are subjected to esterification reaction. Preferably, in order to obtain a reverse osmosis membrane with strong oxidation resistance and good salt rejection, the heating conditions include: the temperature is 20-120 deg.C, and the time is 5-50 minutes. More preferably, the specific process of performing the esterification reaction under heating condition comprises: heat treatment is carried out for 10-30 minutes at 50-70 ℃, and heat treatment is carried out for 10-30 minutes at 70-90 ℃ after the solvent is volatilized to be dry. Most preferably, the specific process of performing the esterification reaction under heating conditions comprises: heat treatment is carried out for 10 minutes at 60 ℃, and heat treatment is carried out for 30 minutes at 80 ℃ after the solvent is volatilized to be dry.
The invention also provides a reverse osmosis membrane prepared by the method.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
(1) measuring the ion exchange capacity of the polyether sulfone containing carboxyl by adopting an acid-base titration method;
(2) the salt rejection of the reverse osmosis membrane is obtained by testing the following method: the reverse osmosis membrane is loaded into a membrane pool, the concentration change of the sodium chloride aqueous solution with the initial concentration of 2000ppm within 1h is measured under the conditions that the pressure is 2.0MPa and the temperature is 25 ℃, and the reverse osmosis membrane is obtained by calculating according to the following formula:
R=(Cp-Cf)/Cp× 100%, wherein R is salt cut rate, CpIs the concentration of sodium chloride in the stock solution, CfIs the concentration of sodium chloride in the permeate.
(3) The oxidation resistance of the reverse osmosis membrane is tested by the following method: and (3) soaking the reverse osmosis membrane in 2000ppm sodium hypochlorite aqueous solution for 24h, washing with water, and then measuring the water flux and the salt rejection rate of NaCl according to the test method in (2).
Preparation example 1
This preparation was used to prepare the carboxyl group-containing polyethersulfone D1.
0.025mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.015mol of 4, 4' -dichlorodiphenyl sulfone, 0.01mol of 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt and 0.05mol of anhydrous potassium carbonate were added to a three-necked flask equipped with a mechanical stirrer and a thermometer. Adding 35mL of N-methylpyrrolidone and 15mL of toluene under the protection of nitrogen, heating to 120 ℃ for reaction for 4 hours, evaporating the toluene, heating to 190 ℃ for reaction for 8 hours, pouring the reaction liquid into 0.02L of dilute hydrochloric acid aqueous solution with the concentration of 1mol/L, crushing by using a crusher, filtering, boiling and washing the polymer by using distilled water, filtering, repeating the process for 6 times, and drying in an oven to obtain the carboxyl-containing polyether sulfone D1 with the number-average molecular weight of 5 ten thousand, m: n = 1.5: 1, yield 95%. The theoretical degree of sulfonation, the actual degree of sulfonation and the ion exchange capacity are shown in Table 1.
1HNMR analysis: the signal peak at the chemical shift of 8.3ppm corresponds to a hydrogen atom on a carbon adjacent to a sulfonic acid group, the signal peak at the chemical shift of 7.9ppm represents a hydrogen atom on the ortho position of a sulfone group of the non-sulfonated diphenyl sulfone, the signal peak within the chemical shift range of 6.8-7.5ppm corresponds to a hydrogen atom on other positions on a benzene ring, the signal peak at the chemical shift of 4.4ppm corresponds to a hydrogen atom on the sulfonic acid group, and the signal peaks at the chemical shifts of 1.6-2.6ppm respectively correspond to hydrogen atoms on an aliphatic chain, which indicates that the polyether sulfone containing carboxyl groups is successfully synthesized.
Preparation example 2
This preparation was used to prepare the carboxyl group-containing polyethersulfone D2.
0.025mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.0125mol of 4, 4' -dichlorodiphenyl sulfone, 0.0125mol of 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt and 0.05mol of anhydrous potassium carbonate were added to a three-necked flask equipped with a mechanical stirrer, thermometer. Adding 35mL of N-methylpyrrolidone and 15mL of toluene under the protection of nitrogen, heating to 140 ℃, reacting for 2 hours, evaporating the toluene, heating to 160 ℃, reacting for 20 hours, pouring the reaction liquid into 0.03L of dilute hydrochloric acid aqueous solution with the concentration of 1mol/L, crushing by using a crusher, filtering, boiling and washing the polymer by using distilled water, filtering, repeating for 6 times, and drying in an oven to obtain the carboxyl-containing polyether sulfone D2 with the number-average molecular weight of 6.1 ten thousand, m: n = 1: 1, yield 94%. The theoretical degree of sulfonation, the actual degree of sulfonation and the ion exchange capacity are shown in Table 1.
1HNMR analysis: the signal peak at the chemical shift of 8.3ppm corresponds to a hydrogen atom on a carbon adjacent to a sulfonic acid group, the signal peak at the chemical shift of 7.9ppm represents a hydrogen atom on the ortho position of a sulfone group of the non-sulfonated diphenyl sulfone, the signal peaks within the chemical shift range of 6.8-7.5ppm correspond to hydrogen atoms on other positions on a benzene ring, the signal peak at the chemical shift of 4.4ppm corresponds to a hydrogen atom on the sulfonic acid group, and the signal peaks at the chemical shifts of 2.3ppm, 2.0ppm and 1.6ppm respectively correspond to hydrogen atoms on an aliphatic chain, which indicates that the carboxyl group-containing polyether sulfone has been successfully synthesized.
Preparation example 3
This preparation was used to prepare the carboxyl group-containing polyethersulfone D3.
0.025mol of 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid, 0.01mol of 4, 4' -dichlorodiphenyl sulfone, 0.015mol of 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt and 0.05mol of anhydrous potassium carbonate were added to a three-necked flask equipped with a mechanical stirrer and a thermometer. Adding 35mL of N-methylpyrrolidone and 15mL of toluene under the protection of nitrogen, heating to 140 ℃, reacting for 4 hours, evaporating the toluene, heating to 200 ℃, reacting for 6 hours, pouring the reaction liquid into 0.06L of dilute hydrochloric acid aqueous solution with the concentration of 1mol/L, crushing by using a crusher, filtering, boiling and washing the polymer by using distilled water, filtering, repeating for 6 times, and drying in an oven to obtain the carboxyl-containing polyether sulfone D3 with the number-average molecular weight of 7.6 ten thousand, m: n = 1: 1.5, yield 92%. The theoretical degree of sulfonation, the actual degree of sulfonation and the ion exchange capacity are shown in Table 1.
1HNMR analysis: the signal peak at the chemical shift of 8.3ppm corresponds to a hydrogen atom on a carbon adjacent to a sulfonic acid group, the signal peak at the chemical shift of 7.9ppm represents a hydrogen atom on the ortho position of a sulfone group of the non-sulfonated diphenyl sulfone, the signal peaks within the chemical shift range of 6.8-7.5ppm correspond to hydrogen atoms on other positions on a benzene ring, the signal peak at the chemical shift of 4.4ppm corresponds to a hydrogen atom on the sulfonic acid group, and the signal peaks at the chemical shifts of 2.3ppm, 2.0ppm and 1.6ppm respectively correspond to hydrogen atoms on an aliphatic chain, which indicates that the carboxyl group-containing polyether sulfone has been successfully synthesized.
Preparation example 4
This preparation was used to prepare the carboxyl group-containing polyethersulfone D4.
A carboxyl group-containing polyethersulfone was prepared according to the procedure of preparation example 1 except that the 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid was replaced with the same number of moles of 4, 4' -bis (4-hydroxyphenyl) -3-hexanoic acid, the 4,4 '-dichlorodiphenyl sulfone was replaced with the same number of moles of 4, 4' -difluorodiphenyl sulfone, and the 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt was replaced with the same number of moles of 3,3 '-disulfonated-4, 4' -difluorodiphenyl sulfone disodium salt to give a carboxyl group-containing polyethersulfone D4 having a number average molecular weight of 8.2 ten thousand, m: n = 1.5: 1, yield 90%. The theoretical degree of sulfonation, the actual degree of sulfonation and the ion exchange capacity are shown in Table 1.
1HNMR analysis: a signal peak at a chemical shift of 8.3ppm corresponds to a hydrogen atom on a carbon adjacent to a sulfonic acid group, a signal peak at a chemical shift of 7.9ppm represents a hydrogen atom at an ortho position to a sulfone group of non-sulfonated diphenyl sulfone, signal peaks in a chemical shift range of 6.8 to 7.5ppm correspond to hydrogen atoms at other positions on a benzene ring, a signal peak at a chemical shift of 4.4ppm corresponds to a hydrogen atom on a sulfonic acid group, and signal peaks at chemical shifts of 1.6 to 2.6ppm correspond to hydrogen atoms on an aliphatic chain, respectively, indicating thatThe polyether sulfone containing carboxyl is successfully synthesized.
Preparation example 5
This preparation was used to prepare the carboxyl group-containing polyethersulfone D5.
A carboxyl group-containing polyethersulfone was prepared according to the procedure of preparation example 1 except that the 4,4 '-bis (4-hydroxyphenyl) -2-pentanoic acid was replaced with the same number of moles of 4, 4' -bis (4-hydroxyphenyl) -4-heptanoic acid, the 4,4 '-dichlorodiphenyl sulfone was replaced with the same number of moles of 4, 4' -dibromodiphenyl sulfone, and the 3,3 '-disulfonated-4, 4' -dichlorodiphenyl sulfone disodium salt was replaced with the same number of moles of 3,3 '-disulfonated-4, 4' -dibromodiphenyl sulfone disodium salt to give a carboxyl group-containing polyethersulfone D5 having a number average molecular weight of 7.7 ten thousand, m: n = 1.5: 1, yield 89%. The theoretical degree of sulfonation, the actual degree of sulfonation and the ion exchange capacity are shown in Table 1.
1HNMR analysis: the signal peak at the chemical shift of 8.3ppm corresponds to a hydrogen atom on a carbon adjacent to a sulfonic acid group, the signal peak at the chemical shift of 7.9ppm represents a hydrogen atom on a position adjacent to a sulfone group of the non-sulfonated diphenyl sulfone, the signal peak within the chemical shift range of 6.8-7.5ppm corresponds to a hydrogen atom on other positions on a benzene ring, the signal peak at the chemical shift of 4.4ppm corresponds to a proton on the sulfonic acid group, and the signal peaks at the chemical shifts of 1.5-2.5ppm respectively correspond to hydrogen atoms on an aliphatic chain, which indicates that the carboxyl-containing polyether sulfone is successfully synthesized.
TABLE 1
| Numbering | Theoretical degree of sulfonation (%) | Actual degree of sulfonation (%) | Ion exchange capacity (mmol/g) |
| Preparation example 1 | 80 | 78 | 1.42 |
| Preparation example 2 | 100 | 96 | 1.69 |
| Preparation example 3 | 120 | 116 | 1.96 |
| Preparation example 4 | 80 | 76 | 1.39 |
| Preparation example 5 | 80 | 73 | 1.35 |
Example 1
This example illustrates a reverse osmosis membrane and method of making the same according to the present invention
1.0g of the carboxyl group-containing polyethersulfone D1 (C-SPAES) prepared in preparation example 1 after drying was dissolved in 98.95g of a total amount of a mixed solvent composed of formic acid, ethylene glycol monomethyl ether and deionized water (wherein the weight ratio of formic acid, ethylene glycol monomethyl ether and deionized water was 7: 2: 1), and 0.05g of polyvinyl alcohol (number average molecular weight: 95000, available from Bailingwei science and technology Co., Ltd.) was added to prepare a coating dilute solution. A bisphenol A type polysulfone ultrafiltration membrane (purchased from Zhejiang Meiyi membrane science and technology Co., Ltd., PS20, 140 micrometers in thickness, the same below) is fixed on a glass plate, the prepared C-SPAES coating liquid is uniformly brushed on the surface of the ultrafiltration membrane, heat treatment is carried out for 10 minutes at 60 ℃, after a solvent is volatilized to be dry, heating is carried out for 30 minutes at 80 ℃, and the C-SPAES composite reverse osmosis membrane with the thickness of a cross-linking type supporting layer of 140 micrometers and the thickness of a separation layer of 100 nanometers is obtained.
The reverse osmosis membrane was subjected to measurement of changes in the concentration of sodium chloride in the initial 2000ppm sodium chloride aqueous solution and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
Example 2
1.0g of the dried carboxyl group-containing polyethersulfone D2 (C-SPAES) prepared in preparation example 2 was dissolved in 98.9g of a total amount of a mixed solvent composed of formic acid, ethylene glycol dimethyl ether and deionized water (wherein the weight ratio of formic acid, ethylene glycol dimethyl ether and deionized water was 7: 2: 1), and 0.1g of polyethylene glycol (number average molecular weight: 95000, available from Bailingwei scientific Co., Ltd.) was added to prepare a coating solution. Fixing a bisphenol A type polysulfone ultrafiltration membrane on a glass plate, uniformly brushing the prepared C-SPAES coating liquid on the surface of the ultrafiltration membrane, carrying out heat treatment at 60 ℃ for 10 minutes, heating at 80 ℃ for 30 minutes after the solvent is volatilized, and obtaining the C-SPAES composite reverse osmosis membrane with the thickness of a cross-linking type supporting layer of 140 micrometers and the thickness of a separation layer of 300 nanometers.
The reverse osmosis membrane was subjected to measurement of changes in the concentration of sodium chloride in the initial 2000ppm sodium chloride aqueous solution and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
Example 3
1.0g of the dried carboxyl group-containing polyethersulfone D3 (C-SPAES) prepared in preparation example 3 was dissolved in 98.85g of a total amount of a mixed solvent composed of formic acid, ethylene glycol monomethyl ether and acetone (wherein the weight ratio of formic acid, ethylene glycol monomethyl ether and acetone was 7: 2: 1), and 0.15g of ethylene glycol was added to prepare a coating solution. Fixing a bisphenol A type polysulfone ultrafiltration membrane on a glass plate, uniformly brushing the prepared C-SPAES coating liquid on the surface of the ultrafiltration membrane, carrying out heat treatment at 60 ℃ for 10 minutes, heating at 80 ℃ for 30 minutes after the solvent is volatilized, and obtaining the C-SPAES composite reverse osmosis membrane with the thickness of a cross-linking type supporting layer of 140 micrometers and the thickness of a separation layer of 200 nanometers.
The reverse osmosis membrane was subjected to measurement of changes in the initial concentration of 2000ppm sodium chloride in the original aqueous solution of sodium chloride and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
Example 4
1.0g of the dried carboxyl group-containing polyethersulfone D4 (C-SPAES) prepared in preparation example 4 was dissolved in 98.8g of a mixed solvent composed of acetic acid, ethylene glycol monomethyl ether and deionized water (wherein the weight ratio of acetic acid, ethylene glycol monomethyl ether and deionized water was 7: 2: 1), and 0.2g of butanediol was added to prepare a coating solution. Fixing a bisphenol A type polysulfone ultrafiltration membrane on a glass plate, uniformly brushing the prepared C-SPAES coating liquid on the surface of the ultrafiltration membrane, carrying out heat treatment at 60 ℃ for 10 minutes, heating at 80 ℃ for 30 minutes after the solvent is volatilized, and obtaining the C-SPAES composite reverse osmosis membrane with the thickness of a cross-linking type supporting layer of 140 micrometers and the thickness of a separation layer of 500 nanometers.
The reverse osmosis membrane was subjected to measurement of changes in the concentration of sodium chloride in the initial 2000ppm sodium chloride aqueous solution and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
Example 5
1.0g of the dried carboxyl group-containing polyethersulfone D5 (C-SPAES) prepared in preparation example 5 was dissolved in 98.8g of a total amount of a mixed solvent composed of acetic acid, ethylene glycol dimethyl ether and acetone (wherein the weight ratio of acetic acid, ethylene glycol dimethyl ether and acetone was 8: 1: 1), and 0.05g of glycerol was added to prepare a coating solution. Fixing a bisphenol A type polysulfone ultrafiltration membrane on a glass plate, uniformly brushing the prepared C-SPAES coating liquid on the surface of the ultrafiltration membrane, carrying out heat treatment at 60 ℃ for 10 minutes, heating at 100 ℃ for 30 minutes after the solvent is volatilized, and obtaining the C-SPAES composite reverse osmosis membrane with the thickness of the cross-linking type supporting layer being 140 micrometers and the thickness of the separation layer being 100 nanometers.
The reverse osmosis membrane was subjected to measurement of changes in the initial concentration of 2000ppm sodium chloride in the original aqueous solution of sodium chloride and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
Comparative example 1
The preparation method is the same as that of example 1, except that after polyvinyl alcohol serving as a cross-linking agent is added into the prepared C-SPAES coating dilute solution, esterification reaction is not carried out under the heating condition, and the C-SPAES composite reverse osmosis membrane with the supporting layer being 140 micrometers in thickness and the separation layer being 100 nanometers in thickness is obtained.
The reverse osmosis membrane was subjected to measurement of changes in the initial concentration of 2000ppm sodium chloride in the original aqueous solution of sodium chloride and the permeate within 1 hour at 2.0MPa and 25 ℃ to calculate the salt rejection, and the results are shown in Table 2. The reverse osmosis membrane was immersed in 2000ppm sodium hypochlorite aqueous solution for 24 hours, then washed with water, and the water flux and the salt rejection rate to NaCl were measured by the above test methods, and the results are shown in table 2.
TABLE 2
From the above results, it can be seen that, in the reverse osmosis membranes provided by the present invention, as compared with comparative example 1 in which the esterification reaction is not performed under heating conditions, examples 1 to 5 show that the salt rejection of the reverse osmosis membrane provided by the present invention, i.e., the reverse osmosis membrane after cross-linking, is significantly improved and has strong oxidation resistance, and thus, the reverse osmosis membrane provided by the present invention has high salt rejection and also shows good oxidation resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (17)
1. A reverse osmosis membrane comprises a supporting layer and a separation layer which are stacked together, and is characterized in that the separation layer is a cross-linked network structure layer which is obtained by esterification reaction of carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups under a heating condition, wherein the cross-linking agent with at least two hydroxyl groups is polyvinyl alcohol and/or polyethylene glycol;
the compound is shown in a formula (I),
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand.
2. The reverse osmosis membrane of claim 1, wherein R1-R8、R11-R24Is hydrogen, R9Is C1-C3Alkylene of (A), R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
3. A reverse osmosis membrane according to claim 1 or 2,
R1-R8is hydrogen, R9Is ethylene, R10Is methyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is ethyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is propyl, R11-R24Is hydrogen.
4. A reverse osmosis membrane according to claim 1 or claim 2 wherein the support layer has a thickness of 40-200 microns and the separation layer has a thickness of 100-500 nm.
5. A reverse osmosis membrane according to claim 4 wherein the support layer has a thickness of 40-150 microns and the separation layer has a thickness of 100-300 nanometers.
6. A reverse osmosis membrane according to claim 1 or 2 wherein the carboxyl-containing polyethersulfone and the cross-linking agent are used in a weight ratio of 1 to 100: 1.
7. a reverse osmosis membrane according to claim 6 wherein the amount of carboxy-containing polyethersulfone and cross-linking agent is present in a weight ratio of 1-50: 1.
8. a method for preparing a reverse osmosis membrane, comprising the steps of:
(1) dissolving dried carboxyl-containing polyether sulfone with a structure shown in a formula (I) and a cross-linking agent with at least two hydroxyl groups in a solvent to prepare a coating solution, wherein the cross-linking agent with at least two hydroxyl groups is polyvinyl alcohol and/or polyethylene glycol;
(2) coating the coating liquid on a support layer, and carrying out an esterification reaction on the carboxyl-containing polyether sulfone and the cross-linking agent with at least two hydroxyl groups under a heating condition to obtain a separation layer on the support layer;
the compound is shown in a formula (I),
wherein R is1-R8、R11-R24Each independently is hydrogen or C1-C5Alkyl of R9Is absent or is C1-C5Alkylene of (A), R10Is hydrogen or C1-C5Alkyl group of (a), m: n = 0.1-10: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 1-10 ten thousand.
9. The method of claim 8, wherein R1-R8、R11-R24Is hydrogen, R9Is C1-C3OfAlkyl radical, R10Is C1-C3Alkyl group of (a), m: n = 0.4-4: 1, the number average molecular weight of the carboxyl-containing polyether sulfone is 5-8 ten thousand.
10. The production method according to claim 8 or 9,
R1-R8is hydrogen, R9Is ethylene, R10Is methyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is ethyl, R11-R24Is hydrogen; or,
R1-R8is hydrogen, R9Is ethylene, R10Is propyl, R11-R24Is hydrogen.
11. The preparation method according to claim 8 or 9, wherein the thickness of the support layer is 40-200 μm, and the amount of the coating liquid is such that the thickness of the separation layer is 100-500 nm.
12. The method as claimed in claim 11, wherein the thickness of the support layer is 40-150 μm, and the coating liquid is used in an amount such that the thickness of the separation layer is 100-300 nm.
13. The preparation method according to claim 8 or 9, wherein the amount of the carboxyl group-containing polyethersulfone is 0.5 to 10 wt% and the amount of the cross-linking agent is 0.01 to 1 wt%, based on the total weight of the coating solution; the weight ratio of the carboxyl-containing polyether sulfone to the cross-linking agent is 1-100: 1.
14. the preparation method according to claim 13, wherein the amount of the carboxyl group-containing polyethersulfone is 0.5-5 wt% and the amount of the cross-linking agent is 0.01-0.5 wt%, based on the total weight of the coating solution; the weight ratio of the carboxyl-containing polyether sulfone to the cross-linking agent is 1-50: 1.
15. the production method according to claim 8 or 9, wherein the solvent is any one or more of formic acid, acetic acid, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, acetone, and deionized water.
16. The production method according to claim 8 or 9, wherein the heating conditions include: the temperature is 20-120 deg.C, and the time is 5-50 minutes.
17. A reverse osmosis membrane produced by the method of any one of claims 8-16.
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| CN103071405A (en) * | 2013-01-31 | 2013-05-01 | 北京碧水源膜科技有限公司 | Reverse osmosis membrane and preparation method thereof |
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