CN103079685B - 用于纳滤的非对称膜 - Google Patents
用于纳滤的非对称膜 Download PDFInfo
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- CN103079685B CN103079685B CN201180040390.XA CN201180040390A CN103079685B CN 103079685 B CN103079685 B CN 103079685B CN 201180040390 A CN201180040390 A CN 201180040390A CN 103079685 B CN103079685 B CN 103079685B
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- solvent
- casting solution
- polybenzimidazoles
- film
- acid
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- 238000001728 nano-filtration Methods 0.000 title claims abstract description 43
- 239000012528 membrane Substances 0.000 title claims description 56
- 239000002904 solvent Substances 0.000 claims abstract description 96
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 238000005266 casting Methods 0.000 claims description 71
- 239000004693 Polybenzimidazole Substances 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 230000003750 conditioning effect Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 17
- 235000019198 oils Nutrition 0.000 claims description 17
- -1 aryl sulfonic acid Chemical compound 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 150000001350 alkyl halides Chemical class 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- BXXWFOGWXLJPPA-UHFFFAOYSA-N 2,3-dibromobutane Chemical compound CC(Br)C(C)Br BXXWFOGWXLJPPA-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002480 mineral oil Substances 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- AONKGGMHQHWMSM-UHFFFAOYSA-N 1,1,1-tribromopropane Chemical compound CCC(Br)(Br)Br AONKGGMHQHWMSM-UHFFFAOYSA-N 0.000 claims description 2
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 claims description 2
- CCUWGJDGLACFQT-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluoropentanedioic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(O)=O CCUWGJDGLACFQT-UHFFFAOYSA-N 0.000 claims description 2
- FJWGRXKOBIVTFA-UHFFFAOYSA-N 2,3-dibromobutanedioic acid Chemical compound OC(=O)C(Br)C(Br)C(O)=O FJWGRXKOBIVTFA-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical class OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- NHDLVKOYPQPGNT-UHFFFAOYSA-N benzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1 NHDLVKOYPQPGNT-UHFFFAOYSA-N 0.000 claims description 2
- CVSJGSMRCDOMMW-UHFFFAOYSA-N benzene;carbonic acid Chemical compound OC(O)=O.OC(O)=O.OC(O)=O.OC(O)=O.OC(O)=O.C1=CC=CC=C1 CVSJGSMRCDOMMW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010696 ester oil Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- FITZJYAVATZPMJ-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid Chemical class C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 FITZJYAVATZPMJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane 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
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 230000006872 improvement Effects 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 76
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 230000004907 flux Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 125000001118 alkylidene group Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000012465 retentate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- GXELTROTKVKZBQ-UHFFFAOYSA-N n,n-dibenzylhydroxylamine Chemical compound C=1C=CC=CC=1CN(O)CC1=CC=CC=C1 GXELTROTKVKZBQ-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003053 piperidines Chemical class 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
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Classifications
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Abstract
公开了用于有机溶剂纳滤的改进的致密皮层非对称膜及其制备的方法和应用。膜由聚苯并咪唑通过相转化形成,并且随后通过加入交联剂进行交联。这使得所述膜稳定并且允许甚至在通过相转化形成的所述膜的溶剂中以及在强酸性和强碱性的溶剂中保持所述膜的溶剂纳滤。
Description
技术领域
本发明涉及用于纳滤的非对称膜,尤其是涉及溶解在有机溶剂中的溶质的纳滤,且尤其是溶解在强碱性有机溶剂环境和强酸性有机溶剂环境中的溶质的纳滤的非对称膜。
背景技术
膜方法在分离科学领域中是众所周知,并可以应用到在液相和气相中一系列不同分子量物质的分离(例如参见“MembraneTechnologyandApplications”2ndEdition,R.W.Baker,JohnWiley和SonsLtd,ISBN0-470-85445-6)。
纳滤是使用孔隙一般在0.5~5nm范围内且具有截留分子量在200~2000道尔顿区域中的膜的膜方法。膜的截留分子量通常被定义为:当分子用膜进行纳滤时分子的分子量表现出90%的截留率。纳滤已被广泛用于水性流体的过滤,但是由于缺少合适的溶剂稳定的膜,它并没有被广泛地应用于有机溶剂中的溶质分离。尽管这样,但事实是有机溶剂纳滤(OSN)在制造业中具有包括溶剂交换、催化剂的回收和再循环、纯化和浓缩的许多潜在应用。美国专利5174899、5215667、5288818、5298669和5395979公开了在有机介质中从有机金属性化合物和/或羰基金属的溶液中分离有机金属性化合物和/或羰基金属。英国专利GB2373743描述了OSN在溶剂交换中的应用;英国专利GB2369311描述了OSN在相转化剂的再循环中的应用;以及欧洲专利EP1590361描述了OSN在寡核苷酸的合成过程中分离合成纤维的应用。然而,迄今为止没有描述OSN在强碱性有机溶剂环境和强酸性有机溶剂环境中应用的报道。
聚酰亚胺已被广泛地用于形成在分离方法中,尤其是气体分离,且也用于液体分离中使用的膜。US5264166和US6180008描述了致密皮层非对称聚酰亚胺膜的生产方法。使用相转化技术产生由直径小于5nm的孔径表征的非对称膜的超薄顶层,这些膜被制备为在载体基底上的平板膜。在形成之后,用溶解在溶剂中的非挥发性调节剂处理所述膜。所述调节剂保持从有机溶剂中纳滤低分子量溶质的性能并允许在干燥状态下处理、存放和加工所述膜。在美国专利5360530、5494566和5651877中描述这些膜在润滑油的滤液中回收溶剂的应用。GB2437519报道了通过聚酰亚胺溶液的相转化,随后对得到的聚酰亚胺膜进行交联,然后用溶解在溶剂中的非挥发性调节剂进行处理而形成的膜。然而,通过相转化形成的致密皮层聚酰亚胺膜并不是在所有的溶剂中稳定,即使是根据GB2437519进行了交联。尤其是,它们在强碱性有机环境或强酸性有机环境中不稳定。
已经广泛报道了聚苯并咪唑膜在气体分离和水性流体处理中的应用。US3699038、US3720607、US3841492、US4448687和US4693824报道了由铸膜液(dopesolution)通过相转化形成的致密皮层聚苯并咪唑膜。US3737402报道了由铸膜液通过相转化,随后在至少135℃的温度下退火以改进膜的反渗透性能而形成的聚苯并咪唑膜。US4693825报道了由含有作为添加剂的苯甲醇的铸膜液生产聚苯并咪唑膜。
已报道,聚苯并咪唑(PBI)膜的交联改进它们的耐化学性。US6986844、US4734466、US4666996和US4020142都公开了交联PBI的方法。然而,已知这些方法导致膜的脆度急剧增加,使得这些膜难以制造和使用。
发明内容
本发明提供了尤其适合在有机溶剂中使用的非对称聚苯并咪唑纳滤膜。
在第一方面中,本发明提供了用于包含溶剂和溶解的溶质进料流溶液的纳滤并在环境温度下表现出优先截留溶质的膜,所述膜包含浸渍有调节剂的致密皮层非对称聚苯并咪唑膜。
在具体的实施方式中,聚苯并咪唑被交联以改进所述膜的耐化学性。
在进一步的方面,本发明提供了如本文所定义的聚苯并咪唑膜在进料流的纳滤中的应用,其中,所述进料流包含强酸性溶剂或强碱性溶剂,和/或所述进料流包含一种或多种存在于所述溶剂中的强酸性或强碱性的化合物。
在另一方面,本发明提供了一种通过纳滤从进料流中分离溶解的溶质的方法,所述进料流包含强酸性溶剂或强碱性溶剂,和/或所述进料流包含了一种或多种存在于所述溶剂中的强酸性或强碱性的化合物;其中,所述方法包括使进料通过本文所定义的聚苯并咪唑膜。
在另一方面,本发明提供了一种形成用于溶剂纳滤的致密皮层非对称聚苯并咪唑膜的方法,所述方法包括以下步骤:
(a)制备聚苯并咪唑的铸膜液,所述聚苯并咪唑的铸膜液包括:
(i)聚苯并咪唑聚合物和(ii)所述聚苯并咪唑的与水混溶的溶剂体系;
(b)在载体基底上浇铸所述铸膜液的薄膜;
(c)使所述铸膜液进行一段蒸发期间的蒸发,然后将浇铸在基底上的薄膜浸入凝固介质(coagulatingmedium)中;
(d)可选地用包含一种或多种用于聚苯并咪唑的交联剂的溶剂处理所得到的非对称膜;
(e)用包含调节剂的洗涤浴或浴处理非对称膜。
在进一步的方面,本发明提供了通过如本文所定义方法的任意一种可获得的膜。
在进一步的方面,本发明提供了通过如本文所定义方法的任意一种获得的膜。
在进一步的方面,本发明提供了通过如本文所定义方法的任意一种直接获得的膜。
本发明的膜可以用于有机溶剂中的纳滤操作。尤其,它们可以用于可溶解碱性聚苯并咪唑的溶剂中的纳滤操作。相对于在典型的粘稠溶剂例如二甲基乙酰胺(DMAc)中失去结构且溶解,并且在一些氯化溶剂,诸如二氯甲烷中表现出低或无通量的许多现有技术的不对称溶剂纳滤膜,这是有利的。而且,本发明的膜可以被用于进料流的纳滤,其中,所述溶剂是强酸性或强碱性的,或者其中,所述进料流含有强酸性或强碱性的组分。相对于在强酸性或强碱性的条件下失去结构且溶解的许多现有技术的非对称溶剂的纳滤膜,这是有利的。然而,本发明的膜在这些溶剂中是稳定的,从而提供可接受的通量和截留率。然而,本发明的膜的另一优点是:当处理水和有机溶剂的混合物时,它们可以表现出比已知的膜更高的通量。
附图说明
图1示出了30℃下在二甲基乙酰胺中测得的合成的聚苯并咪唑的固有粘度。
图2示出了各种聚苯并咪唑膜在30巴下对于包含作为溶剂的丙酮和作为溶质的聚苯乙烯低聚物的纳滤进料流的通量。
图3示出了由含有17wt%的聚苯并咪唑的铸膜液制备的各种聚苯并咪唑膜在30巴下对包含作为溶剂的丙酮和作为溶质的聚苯乙烯低聚物的纳滤进料流的通量和截留率数据。
图4(a)和图4(b)示出了由包含15wt%的聚苯并咪唑的铸膜液制备的各种聚苯并咪唑膜在30巴下对包含作为溶剂的丙酮和作为溶质的聚苯乙烯低聚物的纳滤进料流的通量和截留率数据。
图5示出了由15和17wt%的铸膜液制备的聚苯并咪唑膜对作为溶剂的DMAc的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在THF中的聚苯乙烯低聚物的进料溶液的纳滤。
图6示出了由15和17wt%的铸膜液中制备的聚苯并咪唑膜对作为溶剂的比例为4∶1的DMAc∶THF的混合物的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在THF中的聚苯乙烯低聚物的进料溶液的纳滤(y轴上的%R表示%截留率);
图7示出了由15和17wt%的铸膜液制备的聚苯并咪唑膜对作为溶剂的DMAc的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在二氯甲烷中的聚苯乙烯低聚物的进料溶液的纳滤。
图8示出了由15和17wt%的铸膜液制备的聚苯并咪唑膜对作为溶剂的比例为4∶1的DMAc∶THF的混合物的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在二氯甲烷中的聚苯乙烯低聚物的进料溶液的纳滤(y轴上的%R表示%截留率)。
图9示出了由17wt%的铸膜液制备的交联的聚苯并咪唑膜对作为溶剂的DMAc的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在THF和DMF中的聚苯乙烯低聚物的进料溶液的纳滤(y轴上的%R表示%截留率)。
图10示出了由17wt%的铸膜液中制备的交联的聚苯并咪唑膜对作为溶剂的DMAc的通量和截留分子量(MWCO)曲线。在30巴和30℃下进行包含溶解在DMF中的聚苯乙烯低聚物的进料溶液的纳滤。
具体实施方式
非对称膜对于本领域的技术人员来说是熟悉的,且非对称膜包括在相同材料的较厚的多孔亚结构上的致密的超薄顶“皮肤”层组成的实体,即致密皮层。典型地,非对称膜被负载在合适的多孔基底或载体材料上。
本发明的聚苯并咪唑膜可以从若干聚苯并咪唑的聚合物源中生产。在包括US3699038、US3720607、US3737402、US3841492、US4448687、US4693824和US4693825的现有技术中存在这些聚合物的同一性。对于本领域中的技术人员已知的是生产合适的聚苯并咪唑的方法,并包括那些在美国专利2895948、美国专利Re26065、US3313783、US3509108、US3555389、US3433772、US3408336、US3549603、US3708439、US4154919、US4312976、US5410012、US5554715和在JournalPolymerScience,第50卷,第511~539页(1961)中所描述的。
用于制备本发明的膜的聚苯并咪唑聚合物优选的类别具有如下所示的一般重复结构I:
其中,R是四价芳香核,所述四价芳香核通常被芳香核的相邻碳原子上配对的形成苯并咪唑环的氮原子对称取代,而且R1是选自脂肪族、脂环族和芳族自由基的二价取代基。
适宜地,在如上所示的一般重复结构I中的R基团具有以下所示的结构:
其中,Q是相邻环之间的直连键或亚烷基连接键,且*标明对于稠合咪唑环的N原子的附接点。
在实施方式中,Q是直连键。
在一般重复结构I中的R1取代基可包括(1)芳族环、(2)亚芳基、(3)亚烷基、(4)亚芳基-醚基和(5)杂环。芳香核的合适实例是苯基。亚芳基的合适实例是亚苯基。术语“亚烷基”包括(1~20C)亚烷基。在一实施方式中,亚烷基是(1~6C)亚烷基。亚芳基-醚基适合为通式III的基团。
其中,每个Z1或Z2基团是氢或烃基取代基((1~6C)烃基是合适的)。当R1是杂环时,它适合为饱和、不饱和或部分饱和的含有1、2、3或4个环原子选自氮、硫或氧的4~12个原子的单环或双环,环可以是碳或氮连接的,其中,-CH2-基团可以可选地被-C(O)-取代;且其中,环的氮原子或硫原子可选地被氧化以形成N-氧化物或S-氧化物。杂环的具体实例包括吡啶、吡嗪、呋喃、喹啉、噻吩或吡喃。
有利于制备本发明的膜的聚苯并咪唑聚合物的进一步优选的类别具有如下所示的一般重复结构II:
其中,Z是具有在芳香核的相邻碳原子上配对的形成苯并咪唑环的氮原子的芳香核。有利于本发明的进一步的聚苯并咪唑是具有结构I的聚合物与具有结构II的聚合物的混合物。
合适的Z是稠合苯环。
用于形成本发明的膜的优选的聚苯并咪唑是具有下面所示的通式的聚(2,2′-间亚苯基)-5,5′-双-苯并咪唑:
其中,n是整数。
合适地,n是10~5000的整数,更典型地为20~3000,且甚至更典型地为50~2000。
可以通过将所需的聚苯并咪唑聚合物与可选的增粘剂、可选的空隙抑制剂(voidsuppressor)和可选的不混溶基体的离散的颗粒一起溶解在溶剂中以提供粘稠的聚合物的铸膜液,在多孔载体铺展该溶液以形成薄膜,部分地蒸发该溶剂并在水中淬火该薄膜来制造本发明的膜。这通过相转化方法沉淀该聚合物并形成非对称膜。
本发明包括用于形成致密皮层非对称交联的聚苯并咪唑溶剂纳滤膜的方法,该方法包括以下步骤:
(a)制备聚苯并咪唑的铸膜液,该聚苯并咪唑的铸膜液的基本组成为:
(i)含量为所述铸膜液的5~30wt%的聚苯并咪唑聚合物,
(ii)所述聚苯并咪唑的与水混溶的溶剂体系,
(iii)可选地,含量小于所述铸膜液的5wt%的增粘剂,
(iv)可选地,含量小于所述铸膜液的10wt%的空隙抑制剂,
(v)可选地,含量小于所述铸膜液的5wt%的表面活性剂,
(vi)可选地,悬浮在所述铸膜液中含量小于所述铸膜液的20wt%的
离散的无机或有机基体;
(b)在载体基底上浇铸所述铸膜液的薄膜;
(c)使所述铸膜液蒸发经过一段蒸发期间,然后将在基底上浇铸的薄膜浸入凝固介质(coagulatingmedium)中;
(d)可选地,用包含一种或多种用于聚苯并咪唑的交联剂的溶剂处理所得的非对称膜;
(e)用调节剂处理非对称膜。
可选地,作为步骤(e)后的进一步的步骤(f),可干燥该膜。
通过在一种有机溶剂或有机溶剂的混合物中溶解聚苯并咪唑聚合物可制备聚苯并咪唑聚合物的铸膜液,该有机溶剂包括下列与水混溶的溶剂:也称为DMAc的N,N-二甲基乙酰胺、以下简称为NMP的N-甲基-2-吡咯烷酮、以下简称为THF的四氢呋喃、以下简称为DMF的N,N-二甲基甲酰胺、二甲亚砜、1,4-二氧六环、γ-丁内酯、水、醇、酮和甲酰胺。
溶液中聚苯并咪唑聚合物的重量百分比最广泛的意义上可以在5~30%的范围内,但12~20%的范围是优选的,而且14~18%的范围是更优选的。
诸如增粘剂的添加剂的含量可为所述聚苯并咪唑聚合物的铸膜液的至多10wt%,并且该增粘剂包括聚乙烯吡咯烷酮类、聚乙二醇类和聚氨酯类。此外,诸如空隙抑制剂的添加剂的含量可为所述聚苯并咪唑聚合物的铸膜液的至多5wt%,并且空隙抑制剂包括马来酸。诸如影响孔隙结构的表面活性剂,例如TritonX-100(可从Sigma-AldrichUK有限公司获得(辛基苯氧基-聚乙氧基乙醇)的添加剂的含量可为所述聚苯并咪唑聚合物的铸膜液的至多5wt%。
粉末状固体形式的有机或无机基体的含量可为所述聚合物铸膜液的至多20wt%。碳分子筛基体可以通过在美国专利6585802中所述的任何合适的材料的热解而制成。如在美国专利6755900所述的沸石类也可用作无机基体。也可使用诸如二氧化钛、氧化锌和二氧化硅的金属氧化物,例如可从EvonikDegussaAG公司(德国)购得的属于Aerosol和AdNano商标的材料。也可使用诸如铈、锆和镁的混合物的金属氧化物。优选的基体是直径小于1.0微米的颗粒,优选直径小于0.1微米,并且优选直径小于0.01微米。在某些情况下,在与铸膜液分开的溶液中,优选有机溶剂溶液中分散上述基体,随后将此溶液加入至含有该聚合物的铸膜液中可能是有利的。在优选的实施方式中,例如沸石或金属氧化物的无机基体的晶体或纳米粒子可在与铸膜液分开的溶液中生长到选定的尺寸,并随后将该分散体溶液加入至含有该聚合物的铸膜液中。此分开的溶液可以包括具有分散于连续液相中的纳米粒子的水或有机溶剂。在另一优选实施方式中,分散基体的溶剂可能是挥发性的,并且在膜浇铸之前可以通过蒸发从铸膜液中除去该溶剂。
一旦聚苯并咪唑聚合物溶解在所描述的溶剂体系中,且可选地将有机或无机基体添加至铸膜液中,以便良好地分散基体,从而被浇铸到合适的多孔载体或基底上。该载体可以采用不阻塞穿过膜的渗透物的通过且不与膜材料、浇铸溶液、凝胶化浴溶剂或使用中渗透过膜的溶剂发生反应的惰性多孔材料的形式。这样典型的惰性载体是金属网、烧结金属、多孔陶瓷、烧结玻璃、纸、多孔不溶的塑料以及纺布或无纺布材料。优选地,载体材料为无纺布聚合物材料,诸如聚酯、聚乙烯、聚丙烯、聚醚醚酮(PEEK)、聚苯硫醚(PPS)、乙烯-三氟氯乙烯(ECTFE)或碳纤维材料。
浇铸操作之后,可以在足以在聚苯并咪唑膜上产生致密的超薄顶部“皮肤”层的条件下蒸发部分溶剂。适用于此目的的典型的蒸发条件包括:小于100秒,优选少于30秒的持续时间暴露在空气中。在另一优选的实施方式中,在15~25℃下以小于30秒的持续时间对整个膜的表面吹空气。
凝固介质或淬火介质可由水、醇、酮或它们的混合物以及例如X-100(从Sigma-Aldrich公司(英国)有限公司购得(辛基苯氧基聚乙氧基乙醇))的表面活性剂的添加剂组成。影响凝固的条件对于本领域的技术人员是公知的。
可以根据以下技术洗涤形成非对称聚苯并咪唑膜。典型地,诸如包括但不限于甲醇、乙醇、异丙醇、丙酮、甲乙酮或它们的混合物的这些低分子量的醇类和酮类的水溶性有机化合物以及与水混合的共混物可用于从膜中除去残留的浇铸溶剂(例如DMAc)。可替代地,该膜可用水洗涤。在连续的溶剂交换法中,除去残留的浇铸溶剂可能需要连续的洗涤共混物。通过适当的溶剂交换法可以提高膜效率(溶质截留率)和渗透率。
在US4666996、US6986844、US4734466和US4020142中描述了用于处理聚苯并咪唑聚合物的合适的交联剂,并且这些文献均并入本文。合适的交联剂包括多官能卤代烷、二乙烯砜和多官能有机强酸。
多官能卤代烷包括那些含有至少两个卤取代基,并且具有通式:
其中,X是Br或Cl、n是1~11、a是1~10、b是0~4且c是0~6。双官能卤代烷优选的类别包含具有X-(CH2)n.CH2-X结构的直链的末端二取代的化合物,其中,X和n如上述所定义。最优选的双官能卤代烷是二溴丁烷(DBB)。卤代烷还可以含有三个或更多个卤取代基。具有三个或更多个卤取代基的示例性的卤代烷包括三溴丙烷、三氯丙烷、四溴季戊醇和四氯季戊醇。
进一步合适的交联剂包括具有以下通式的二乙烯砜:
其中,每个R1-R4相同或不同,并选自H或C1~C3的烷基。
适合于在本发明中使用的多官能有机强酸包括羧酸、磺酸、硫酸或磷酸。代表性实例为全氟戊二酸、苯六甲酸、苯五甲酸、1,2,3,4-苯四甲酸、1,2,3,5-苯四甲酸、1,2,4,5-苯四甲酸、1,3,5-苯三甲酸、二溴琥珀酸、聚丙烯酸、1,4,5,8-萘四甲酸、2,6-萘二磺酸、芳基磺酸、芳基亚磺酸、芳基亚膦酸、芳基膦酸。使用多官能有机强酸交联聚苯并咪唑的合适溶剂对于本领域技术人员是已知的,并且包括冰醋酸。
该交联剂可以溶解在溶剂中以形成交联溶液。该溶剂可以是选自酮、醚、醇、羧酸或溶解交联剂的任何溶剂的有机溶剂。在优选的实施方式中,在交联溶液中的溶剂也将使非对称膜溶胀以允许交联剂良好地渗透到膜中。
用于溶解卤代烷的溶剂不应与卤代烷反应且不应溶解未交联的PBI膜。优选的溶剂包括诸如丙酮、甲基异丁基酮(MIBK)、甲乙酮(MEK)和戊酮的酮;以及诸如异丙醚和丁醚的醚。
用于溶解二乙烯砜的溶剂还可选地包含强碱催化剂,所述强碱催化剂包括诸如氢氧化钠和氢氧化钾的碱金属氢氧化物(alcoholmetalhydroxide)、诸如甲醇钠、乙醇钠的具有1~6个烷基碳原子的碱金属醇盐(alcoholmetalalkoxide),以及诸如特别优选的苄基三甲基氢氧化铵的烷基芳基胺的氢氧化物(alkylarylaminehydroxide)。一般添加碱催化剂的量是基于被添加的二乙烯砜的总重量的5~150%。优选的范围是约25~50wt%。
交联剂在交联溶液中的浓度可相对于每体积溶液中待加入的聚苯并咪唑非对称膜的量进行调节,以控制发生交联的程度,从而交联剂中的反应基团与经处理的膜中的聚苯并咪唑胺的氢基团之间的比例在0.01~100的范围内,优选在0.01~10的范围内且还更优选在0.1~5的范围内。
用于交联的时间可在0.01~120小时之间、更优选在0.5~60小时之间变化。交联的温度可以在0℃和所用溶剂的沸点之间,优选为0~150℃之间、还更优选在50~120℃之间变化。
然后,通过使膜与溶解在溶剂中的调节剂接触以浸渍所述膜,来调节所述非对称膜。所述调节剂是低挥发性有机液体。所述调节剂是可选自合成油类(例如聚烯烃油、硅油、聚α烯烃油、聚异丁烯油、合成蜡异构油、酯油和烷基芳烃油)、矿物油(包括溶剂精制油和氢化矿物油和石油蜡异构油)、植物油脂类、高级醇类(诸如癸醇、十二烷醇、十七烷醇)、丙三醇类以及二醇类或它们的衍生物(诸如聚丙二醇类、聚乙二醇类、聚亚烷基二醇类或它们的衍生物)。用于溶解所述调节剂的合适溶剂包括醇、酮、芳烃、烃或它们的混合物。根据本发明的调节剂的使用允许在干燥状态下保持合适的孔隙结构,并产生具有改进的柔性和加工特性的平板膜。在使用之前,必须从所述膜中冲掉所述调节剂,即,当所述膜在干燥状态下时,本发明的调节剂用于保持所需的膜结构以维持性能特性,而当膜用于溶剂纳滤的目的时,调节剂不是功能膜的组分。这使得本发明的调节剂不同于成为功能膜一部分的试剂。
用调节剂处理之后,通常在环境条件下的空气中干燥所述膜以除去残留的溶剂。
热处理也可被用于增加溶质的膜截留率。调节步骤之后,可加热所述膜至150~300℃之间并保持1分钟~2小时。
本发明的膜可被用于纳滤操作,尤其在有机溶剂中的纳滤操作。术语“纳滤”是指透过膜施加压力梯度时,使溶剂通过,同时阻止大溶质分子通过的膜方法。这个可以依照本领域技术人员已知的公测度膜截留率Ri被定义,并定义为:
其中,CP,i=渗透物中物质i的浓度,渗透物是已通过膜的液体;而且CR,i=滞留物中物质i的浓度,滞留物是未通过膜的液体。将理解的是,如果Ri>0,那么膜选择地渗透物质i。本领域技术人员非常理解的是,纳滤是至少一种分子量在100~2000gmol-1范围内的溶质分子i相对至少一种溶剂被滞留在膜表面,从而Ri>0的方法。对于纳滤典型施加压力在5~50巴的范围内。
术语“溶剂”将会被一般技术读者很好地理解,并且包括具有分子量小于300道尔顿的有机液体或含水液体。应当理解的是,所述术语溶剂还包括溶剂的混合物。
作为非限制性例子,溶剂包括芳烃类、烷烃类、酮类、二醇类、氯化溶剂类、酯类、醚类、胺类、腈类、醛类、酚类、酰胺类、羧酸类、醇类、呋喃类、极性质子溶剂类和极性非质子溶剂类、水和它们的混合物。
作为非限制性例子,具体的溶剂的例子包括甲苯、二甲苯、苯、苯乙烯、苯甲醚、氯苯、二氯苯、氯仿、二氯甲烷、二氯乙烷、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲基醚酮(MEK)、甲基异丁基酮(MIBK)、丙酮、乙二醇、乙醇、甲醇、丙醇、丁醇、己烷、环己烷、二甲氧基乙烷、甲基叔丁基醚(MTBE)、二乙醚、己二腈、N,N-二甲基甲酰胺、二甲亚砜、N,N-二甲基乙酰胺、二氧六环、硝基甲烷、硝基苯、吡啶、二硫化碳、四氢呋喃、甲基四氢呋喃、N-甲基吡咯烷酮、乙腈、水和它们的混合物。
本发明的膜特别适合于溶剂是强酸性或强碱性的,或者进料流包含强酸性或强碱性组分的纳滤操作。
本文所用的术语“强酸性”是指pKa小于5的化合物。本文所用的术语“强碱性”是指pKa值大于9的化合物。强酸性或强碱性的化合物可以是溶剂和/或溶解在溶剂中的化合物。
作为非限制性例子,具体的强碱性的溶剂包括胺类,尤其是链烷醇胺类,烷基胺类,和多胺类(诸如烷基二胺类、烷基三胺类),哌啶及其衍生物(包括烷基化哌啶类),吡啶和烷基吡啶类(包括烷基吡啶类、二烷基吡啶类和三烷基吡啶类);所述胺类包括乙胺、乙二胺、二亚乙基三胺、三亚乙基四胺、甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、异丙胺、二异丙胺、正丙胺、二正丙胺、三正丙胺、二正丁胺、三正丁胺、环己胺、二环己胺、二甲基环己胺、五甲基二亚乙基三胺、五甲基二亚丙基三胺、四甲基二亚丙基三胺、苄基二甲胺、四甲基双(氨乙基)醚、N,N-二甲基-2(2-氨乙氧基)乙醇、3-氨基丙醇、N-乙基甲胺、2-乙氧基乙胺、N,N-二乙基羟胺、N-乙基-N-(1,2-二甲基丙基)胺、二异丙基甲胺、2-乙基己胺、二甲基丁胺、3-甲氧基丙胺、3-(2-乙基己氧基)-1-丙胺、甲氨基丙胺、二甲氨基丙胺、甲氧基丙胺、3-乙氧基丙胺、N,N-二异丙基乙胺、二甲基异丙胺、双-2-乙基己胺、二乙基甲胺、N-甲基异丙胺、二苄基羟胺、乙醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺、N-甲基二乙醇胺、甲基乙醇胺、2-(2-氨乙氧基)乙醇、聚乙二醇胺、丙醇胺、吗啉、N-甲基吗啉、N-乙基吗啉、N-甲基吗啉氧化物、氨丙基吗啉、喹啉以及诸如甲醇钠、乙醇钠的具有1~6个烷基碳原子数的碱金属醇盐的溶液,以及诸如特别优选的苄基三甲基氢氧化铵的烷基芳基胺的氢氧化物。
作为非限制性的实例,具体的强酸性溶剂包括羧酸类和它们的衍生物,包括三氟乙酸和乙酸。
溶剂可以被理解为溶剂、酸性溶剂或碱性溶剂以及它们的混合物。
术语“溶质”将被一般技术读者很好地理解,并且包括存在于包含溶剂和至少一种溶质的液体溶液中的有机分子,使得在液体中溶质的重量分数低于溶剂的重量分数,并且,所述溶质的分子量至少比所述溶剂的分子量高20gmol-1。
本发明的膜可以根据本领域的技术人员已知的任何设计进行配置,诸如螺旋缠绕型、板框式、壳管式或它们的衍生设计。
下面的实施例阐明本发明。
在实施例1~4中,使用具有4个横流单元的实验室规模的横流纳滤单元。从平板切下有效面积为14cm2的膜盘(disc)并将其置入4个串联的横流单元中。将<1wt%的测试溶质组成的进料溶液填充至5L的进料罐中,并通过使用隔膜泵(Hydra-Cell,Wanner,USA)在1.5Lmin-1的流速下再循环。使用位于压力表的下游的反压调节器产生池内压力。横穿4个单元的压降测量为小于0.5巴。通过热交换器使再循环的液体保持在30℃。在启动期间,不施加任何压力且废弃初始渗透物的情况下,通过再循环纯溶剂1小时除去调节剂。在操作期间,从每个横流单元的各自取样口收集渗透物样品,并且从所述进料罐获取滞留物样品。所述膜的预调节是必要的,以便降低压缩的影响来得到稳态的通量和截留率。从以下等式来计算溶剂通量Nv:
其中,V=从来自特定的横流单元的渗透物流收集的液体样品的体积,t=收集液体样品用的时间,A=膜面积。
在聚苯乙烯溶质的纳滤期间,使用由苯乙烯低聚物的同系物组成的进料溶液来得到MWCO曲线。所述苯乙烯低聚物混合物含有1g的PS580和PS1050的混合物(购自PolymerLabs公司,英国)和0.1g的α-甲基苯乙烯二聚体(购自SigmaAldrich公司,英国)。在这个浓度下,所述苯乙烯低聚物完全溶解在测试的溶剂中。
实施例1
聚苯并咪唑聚合物合成如下。
在室温下,在1L的三颈圆底烧瓶中称量625gm的多磷酸(PPA),随后固定烧瓶到装配有油浴的架空搅拌组件。将油加热至155℃,在大约125℃时在恒定流量的干燥氮气下开始添加四胺。该添加是非常缓慢的且以持续超过15分钟的方式添加。四胺的添加完成后,将温度进一步升高至170℃并保持恒定,以45分钟流入二酸添加物。该反应在170℃下继续搅拌4小时。4小时后,将反应温度进一步升高至210℃并持续2.5小时,随后在230℃下持续2小时。在反应结束时,将细的连续纤维的形式的粘性聚合物溶液倒入到大大过量的水中。
将未加工的PBI纤维碾压成细碎片并用碳酸氢钠溶液进一步处理以中和磷酸。将混合物中的细的短纤维碾压以制成细粉末。进一步用水随后用丙酮洗涤聚合物的细粉末,并在真空烘箱中干燥过夜。通过将聚合物溶解在热二甲基乙酰胺(DMAc)中,然后通过在大大过量的水中离心和沉淀来进一步纯化干燥的聚合物。将沉淀的聚合物用水洗涤3次并碾压成细粉末。将聚合物的细粉末浸泡到丙酮来代替吸收在聚合物中的水,随后在120℃下在真空烘箱中干燥过夜。
合成的聚合物的表征如下:
通过用于分子量测定的GPC表征合成的PBI,如下表1所示:
表1
编号 | %产率 | Mw | Mn | 多分散性(Mw/Mn) | IV(dl.g-1)** |
批次1* | 93 | 324889 | 190578 | 1.7 | 1.08 |
通过在30℃下利用DMAc作为溶剂的稀溶液方法测定聚合物的固有粘度,并在图1中示出。
从聚苯并咪唑聚合物制备膜如下:
使用制备的聚合物形成膜。表2中给出了铸膜液组合物。起始的聚合物的高分子量限制了该聚合物的铸膜液的浓度为15~17重量%。将称量的DMAc加入烧瓶中并首先加热至80℃,一旦溶剂的温度达到所需的温度,将纯化的聚合物加入到烧瓶中。在高温下的聚合物的溶解产生无任何残留物的高粘性聚合物溶液。待聚合物完全溶解后,解除加热以冷却铸膜液。一旦铸膜液被冷却,将其转移到50毫升离心管中以7000rpm离心铸膜液30分钟。使铸膜液静置过夜以消除任何气泡。在表2中也给出膜浇铸条件的细节。
表2
用于指定膜的编码如下所示,即15PBI-1/0-0-UX-0
使用自动薄膜涂敷器(BraiveInstruments)上的可调浇铸刀将铸膜液在聚丙烯基底材料上浇铸250μm厚的薄膜。在控制的时间间隔内,使溶剂从薄膜的表面蒸发,之后在室温下将薄膜平行于表面浸入到的沉淀水浴(precipitationwaterbath)。该膜随后被浸入异丙醇的溶剂交换浴中以除去残留的DMAc和水。之后,将膜浸入到IPA/聚乙二醇400(40/60,v/v%)的浴中以防止变干。然后在空气中干燥该膜以除去过量的溶剂。
然后在横流纳滤中测试该膜的通量和截留率。图2~图8示出了这些测试的数据。
实施例2
如上述的实施例1一样形成膜,并随后进行如下交联。
在60℃的温度下,将膜浸入到甲基异丁基酮和交联剂(二溴丁烷)浴中12小时。然后将膜从交联浴中取出,并用IPA洗涤该膜以除去任何残留的交联剂。之后,将膜浸入到IPA/聚乙二醇400(40/60,v/v%)的浴中以防止变干。然后在空气中干燥该膜以除去过量的溶剂。用PVC带将经干燥的膜固定到玻璃板上并在100℃下在烘箱中加热1小时。
然后,如上所述测试这些交联的膜的通量和截留率。在图9和图10示出了这些测试的数据。
实施例3
按照实施例3制备交联的聚苯并咪唑膜并将交联的聚苯并咪唑膜浸入到一乙醇胺和三氟乙酸的未稀释溶液中,并保持在30℃。监测膜的稳定性4周以上。未观察到的膜的外观或性质的改变。
实施例4
按照实施例2制备交联的聚苯并咪唑膜。这些膜用于测试包含溶解在1gL-1的丁基二乙二醇∶一乙醇胺∶水(60∶20∶20)的混合物中的由TOKYOOHKAKOGYOEUROPEB.V提供的目录号TFR970的光刻胶材料的溶液的纳滤。该膜表现出对光刻胶(PR)的积极的截留率,如在下面的表3中所示:
表3:在BDG∶MEA∶水中用于PR分离的交联PBI膜的性能评估
*过滤24小时后,基于标准PS截留率分析的膜的MWCO。
Claims (26)
1.一种形成用于溶剂纳滤的交联的致密皮层非对称聚苯并咪唑膜的方法,包括以下步骤:
(a)制备聚苯并咪唑的铸膜液,所述聚苯并咪唑的铸膜液包括:
(i)聚苯并咪唑聚合物和(ii)所述聚苯并咪唑的与水混溶的溶剂体系;
(b)在载体基底上浇铸所述铸膜液的薄膜;
(c)使所述铸膜液进行一段蒸发期间的蒸发,然后将浇铸在基底上的所述薄膜浸入凝固介质中;
(d)用包含多官能卤代烷、二乙烯砜、多官能有机强酸中的一种或多种的溶剂处理所得到的非对称膜;
(e)用调节剂处理所述非对称膜,
其中,在步骤(a)中的聚苯并咪唑的铸膜液包含14~18wt%的聚苯并咪唑聚合物,且步骤(d)在50~120℃的温度下进行。
2.根据权利要求1所述的方法,其中,多官能卤代烷是双官能卤代烷、三官能卤代烷。
3.根据权利要求1或2所述的方法,所述方法进一步包括(f)干燥所述膜。
4.根据权利要求1所述的方法,其中,所述方法进一步包括将所述膜加热至约150℃或更高的温度的步骤。
5.根据权利要求4所述的方法,其中,在多达3小时将所述膜加热至约150℃或更高的温度。
6.根据权利要求1所述的方法,其中,聚苯并咪唑具有以下通式:
7.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液包含选自水、醇、酮和甲酰胺中的一种或多种溶剂。
8.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液包含选自N-甲基-2-吡咯烷酮、四氢呋喃、N,N-二甲基甲酰胺、二甲亚砜、N,N-二甲基乙酰胺、1,4-二氧六环和γ-丁内酯中的一种或多种溶剂。
9.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液还包含所述铸膜液的至多10wt%的增粘剂。
10.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液还包含以所述铸膜液的至多10wt%的量加入至所述聚苯并咪唑的铸膜液的增粘剂,所述增粘剂选自聚乙烯吡咯烷酮类、聚乙二醇类和聚氨酯类。
11.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液还包含以所述聚苯并咪唑的铸膜液的至多5wt%的量使用的空隙抑制剂。
12.根据权利要求1所述的方法,其中,所述聚苯并咪唑的铸膜液还包含以所述铸膜液的至多20wt%的量分散在所述聚苯并咪唑的铸膜液中的离散的有机基体或无机基体。
13.根据权利要求11所述的方法,其中,离散的基体的平均粒度小于0.1微米。
14.根据权利要求12或13所述的方法,其中,离散的基体首先分散于溶剂中,并随后添加到所述铸膜液中。
15.根据权利要求14所述的方法,其中,用于分散所述离散的基体的所述溶剂通过蒸发从所述聚苯并咪唑的铸膜液中除去。
16.根据权利要求1所述的方法,其中,所述交联剂选自二溴丁烷、三溴丙烷、三氯丙烷、四溴季戊醇、四氯季戊醇、全氟戊二酸、苯六甲酸、苯五甲酸、1,2,3,4-苯四甲酸、1,2,3,5-苯四甲酸、1,2,4,5-苯四甲酸、1,3,5-苯三甲酸、二溴琥珀酸、聚丙烯酸、1,4,5,8-萘四甲酸、2,6-萘二磺酸、芳基磺酸、芳基亚磺酸、芳基亚膦酸和芳基膦酸中。
17.根据权利要求1所述的方法,其中,所述交联剂溶解在选自酮、醚、羧酸和醇的溶剂中。
18.根据权利要求1、16或17所述的方法,其中,调节用于处理所述聚苯并咪唑膜的交联剂的量,以使所述交联剂中的反应基团与被处理的膜中的聚苯并咪唑胺的氢基团在0.01~100的范围内。
19.根据权利要求1、16或17所述的方法,其中,调节用于处理所述聚苯并咪唑膜的交联剂的量,以使所述交联剂中的反应基团与被处理的膜中的聚苯并咪唑胺的氢基团在0.1~10的范围内。
20.根据权利要求1、16或17所述的方法,其中,用于交联的时间在0.1~120小时之间。
21.根据权利要求1所述的方法,其中,所述调节剂是非挥发性液体。
22.根据权利要求21所述的方法,其中,所述调节剂是选自合成油类、矿物油类、植物油脂类、高级醇类、丙三醇类和二醇类中的一种或多种。
23.根据权利要求22所述的方法,其中,所述调节剂是选自聚烯烃油、硅油、聚α烯烃油、聚异丁烯油、合成蜡异构油、酯油、烷基芳烃油、溶剂精制油、氢化矿物油、石油蜡异构油、癸醇、十二烷醇、十七烷醇、聚丙二醇类、聚乙二醇类、聚亚烷基二醇类中的一种或多种。
24.根据权利要求1所述的方法,其中,所得到的膜配置为螺旋缠绕型、板框式、壳管式或它们衍生设计。
25.一种通过前述权利要求中任意一项所述的方法得到的膜。
26.一种根据权利要求25所述的膜在包含有机溶剂和溶解的溶质的进料流溶液的纳滤中的应用,其中,所述进料流包含至少一种强碱性溶剂或强酸性溶剂。
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US10328396B2 (en) | 2019-06-25 |
AU2011281326A1 (en) | 2013-02-21 |
CA2805780A1 (en) | 2012-01-26 |
KR102101707B1 (ko) | 2020-04-20 |
KR20140085372A (ko) | 2014-07-07 |
EA201390135A1 (ru) | 2013-10-30 |
EP2595733A1 (en) | 2013-05-29 |
EP2595733B1 (en) | 2021-04-14 |
BR112013001380B8 (pt) | 2022-08-02 |
WO2012010886A1 (en) | 2012-01-26 |
CA2805780C (en) | 2021-08-10 |
UA115963C2 (uk) | 2018-01-25 |
JP2013532578A (ja) | 2013-08-19 |
MY171822A (en) | 2019-10-31 |
AU2011281326B2 (en) | 2015-03-26 |
GB201012080D0 (en) | 2010-09-01 |
CL2013000167A1 (es) | 2013-12-06 |
BR112013001380A2 (pt) | 2016-05-17 |
US20170165614A1 (en) | 2017-06-15 |
BR112013001380B1 (pt) | 2021-01-12 |
SG187556A1 (en) | 2013-03-28 |
MX2013000770A (es) | 2013-07-05 |
EA027868B1 (ru) | 2017-09-29 |
IL224282B (en) | 2018-01-31 |
JP6055406B2 (ja) | 2016-12-27 |
CN103079685A (zh) | 2013-05-01 |
ES2870873T3 (es) | 2021-10-27 |
US20130118983A1 (en) | 2013-05-16 |
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