CN105642127B - 一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法 - Google Patents
一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法 Download PDFInfo
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- CN105642127B CN105642127B CN201610019907.1A CN201610019907A CN105642127B CN 105642127 B CN105642127 B CN 105642127B CN 201610019907 A CN201610019907 A CN 201610019907A CN 105642127 B CN105642127 B CN 105642127B
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- Prior art keywords
- tetramethoxy
- polyvinylidene fluoride
- anthraquinone
- pvdf
- naphthalenes
- Prior art date
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Links
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 56
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 56
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 31
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000012528 membrane Substances 0.000 title claims abstract description 25
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 23
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000002790 naphthalenes Chemical class 0.000 claims abstract description 34
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 30
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 7
- 230000017858 demethylation Effects 0.000 claims abstract description 7
- 238000010520 demethylation reaction Methods 0.000 claims abstract description 7
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000001119 stannous chloride Substances 0.000 claims abstract description 7
- 235000011150 stannous chloride Nutrition 0.000 claims abstract description 7
- SWNROPPWBFHVCS-UHFFFAOYSA-N 1,4,5,8-tetramethoxynaphthalene Chemical class C1=CC(OC)=C2C(OC)=CC=C(OC)C2=C1OC SWNROPPWBFHVCS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 62
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 54
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000005457 ice water Substances 0.000 claims description 24
- RQNVIKXOOKXAJQ-UHFFFAOYSA-N naphthazarin Chemical compound O=C1C=CC(=O)C2=C1C(O)=CC=C2O RQNVIKXOOKXAJQ-UHFFFAOYSA-N 0.000 claims description 23
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- 238000004440 column chromatography Methods 0.000 claims description 20
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 17
- -1 dimethyl sulfate ester Chemical class 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- FBYIJIHPWCXRHH-UHFFFAOYSA-N 1,4,5,8-tetramethoxynaphthalene-2-carbaldehyde Chemical compound O=CC1=CC(OC)=C2C(OC)=CC=C(OC)C2=C1OC FBYIJIHPWCXRHH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 11
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 229960000359 chromic chloride Drugs 0.000 claims description 10
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 10
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000010898 silica gel chromatography Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 229910019213 POCl3 Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000011435 rock Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 3
- 239000011777 magnesium Substances 0.000 claims 3
- 229910052749 magnesium Inorganic materials 0.000 claims 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims 1
- 229930192627 Naphthoquinone Natural products 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 150000002791 naphthoquinones Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 150000008378 aryl ethers Chemical class 0.000 abstract 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 8
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
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- 238000011953 bioanalysis Methods 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- LQJVOKWHGUAUHK-UHFFFAOYSA-L disodium 5-amino-4-hydroxy-3-phenyldiazenylnaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].OC1=C2C(N)=CC(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=C1N=NC1=CC=CC=C1 LQJVOKWHGUAUHK-UHFFFAOYSA-L 0.000 description 3
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- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
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- 150000004053 quinones Chemical class 0.000 description 2
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- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-M 9,10-dioxoanthracene-1-sulfonate Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] JAJIPIAHCFBEPI-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- HQTJYTVKYNLWBJ-UHFFFAOYSA-N silane trimethyl-lambda3-chlorane Chemical compound [SiH4].CCl(C)C HQTJYTVKYNLWBJ-UHFFFAOYSA-N 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
- C08F12/22—Oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
本发明属于聚偏氟乙烯超滤膜的制备领域,具体涉及一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法。该制备方法具体为:(1)2‑(1‑羟基‑3‑丁烯)‑1,4,5,8‑四甲氧基萘的合成;(2)聚偏氟乙烯‑芳香醚类共聚物的合成:选用聚偏氟乙烯为引发剂,2‑(1‑羟基‑3‑丁烯)‑1,4,5,8‑四甲氧基萘为单体,N,N‑二甲基甲酰胺为溶剂,氯化亚铜/Me6TREN为催化体系,经原子自由基聚合法合成聚偏氟乙烯‑芳香醚类共聚物;(3)利用脱甲基氧化法将聚偏氟乙烯‑芳香醚类共聚物还原成醌;(4)将步骤(3)的聚合物和N,N‑二甲基甲酰胺制成铸膜液,刮制成膜。本发明在聚偏氟乙烯膜上所固定的蒽醌分子牢固、不会脱落。
Description
技术领域
本发明属于聚偏氟乙烯超滤膜的制备领域,具体涉及一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法。
背景技术
聚偏氟乙烯高分子材料具有机械强度高,化学稳定性良好、耐紫外辐照、室温下不被酸、碱、强氧化剂和卤素腐蚀等优点,以聚偏氟乙烯为原料制备的膜材料在环境工程领域应用广泛。但是聚偏氟乙烯表面疏水性较强,表面能比较低等缺点将影响膜的寿命。为进一步优化聚偏氟乙烯膜的性能,研究人员进行了一系列改性研究。申请号为2010102559483的中国专利申请公开了一种聚偏氟乙烯改性膜的制备方法,通过在铸膜液中添加致孔剂和聚丙烯腈来共混改性聚偏氟乙烯膜;申请号为2011100222338的中国专利申请利用水相原子转移自由基聚合的方法在聚偏氟乙烯膜表面上接枝有功能性聚合物,使聚偏氟乙烯膜表功能化,所得的膜具有良好的亲水性和抗污能力;申请号为2014106980874的中国专利申请通过静电纺丝的方法制备了聚偏氟乙烯/改性蒙脱土复合纤维膜材料,所制备的膜材料具有优良疏水吸油性能,可用于海上或水面溢油的处理、含油废水的处理。上述改性研究对优化膜性能、增加膜的使用寿命有一定意义,但是其应用原理仍然是基于物理分离,即将污染物质转移和富集,并未实现污染物质的降解,仍有危害环境的可能。研究开发一种既能够净化污水,又能够降解污染物质的膜具有重要的意义。
高浓度含氮的生活污水、工业废水和农田地表水径流汇入湖泊、水库、河流和海湾水域,造成水体中的某些藻类过度繁殖,严重恶化水质,破坏水体生态平衡。生物法是解决上述水体污染问题的最常用方法,但是受生物反硝化过程中电子传输速率的限制,生物法处理效果不稳定、处理效率低。经研究发现氧化还原介体可加快生物反硝化过程中的电子传输速率,提高生物法的处理效率。蒽醌类化合物是氧化还原介体中的一种,目前已有大量报道证实蒽醌类化合物能有效促进含氮废水的降解。已有的报道中多将蒽醌类化合物直接投入使用,这将造成氧化还原介体的流失,引发二次污染。为解决上述问题,研究人员对蒽醌类化合物的固定进行了一系列的研究。文献《固定化氧化还原介体强化酸性红B生物脱色作用研究》采用海藻酸钙固定1,5-二氯蒽,并应用于偶氮染料酸性红B的脱色中,发现固定化的1,5-二氯蒽能促进偶氮染料酸性红B的脱色,但是1,5-二氯蒽只是通过物理作用力束缚在载体上,容易从载体上解析下来。文献《固定化氧化还原介体加速亚硝酸盐生物反硝化作用》利用循环伏安法固定蒽醌磺酸钠( AQS /PPy /ACF),结果表明固定后的蒽醌磺酸钠能够明显加速亚硝酸盐生物反硝化过程,但是采用循环伏安法固定蒽醌磺酸钠的前提是制备聚吡咯膜,其制备过程受很多参数控制,非常复杂。如果将氧化还原介体固定于膜上,能有效解决氧化还原介体固定的问题,提高高浓度含氮污水的处理效率。
发明内容
本发明的目的在于针对现有技术的不足,提供一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法。该发明以化学合成和化学改性的方法将氧化还原介体固定于聚偏氟乙烯上,解决了现有的物理固定方法中出现的醌类物质易从载体上脱落流失,造成水体二次污染等问题;所制得的蒽醌功能化聚偏氟乙烯超滤膜在含氮污水处理领域具有良好的应用前景。
为实现上述目的,本发明采用如下技术方案:
一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法,包括以下步骤:
(1)2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成;
(2)聚偏氟乙烯-芳香醚类共聚物的合成:选用聚偏氟乙烯为引发剂,2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘为单体,N,N-二甲基甲酰胺为溶剂,氯化亚铜/Me6TREN为催化体系,经原子自由基聚合法合成聚偏氟乙烯-芳香醚类共聚物;
(3)利用脱甲基氧化法将聚偏氟乙烯-芳香醚类共聚物脱甲氧基还原成醌;
(4)将步骤(3)的聚合物和N,N-二甲基甲酰胺制成铸膜液,刮制成膜。
步骤(1)中2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成包括以下步骤:
①1,4,5,8-四甲氧基萘的合成:将萘茜、催化量四丁基溴化铵、四氢呋喃加入到圆底烧瓶中,搅拌至溶解,然后添加连二亚硫酸钠水溶液和硫酸二甲酯溶液,搅拌至溶液均匀;将圆底烧瓶移至冰水浴中,反应1h,缓慢滴加NaOH水溶液,滴加完毕后移除冰水浴,在室温下反应30min,匀速搅拌18h至反应完全,反应液经乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收乙酸乙酯,柱层析分离得1,4,5,8-四甲氧基萘;
②1,4,5,8-四甲氧基萘-2-甲醛的合成:在两口反应瓶中加入N,N-二甲基乙酰胺,将两口反应瓶置于冰水浴中,依次缓慢滴加三氯氧磷溶液和0.063 mol/L 1,4,5,8-四甲氧基萘的三氯甲烷溶液,滴加完毕后移除冰水浴,加热回流反应5 h;然后加冰水停止反应,反应液经氯仿萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收氯仿,柱层析分离得1,4,5,8-四甲氧基萘-2-甲醛;
③2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:氩气保护下,在干燥的两口反应瓶中依次加入分子筛、无水四氢呋喃、无水三氯化铬和锰粉,搅拌至颜色变成黑色后加入烯丙基溴,加入1,4,5,8-四甲氧基萘-2-甲醛和三甲基氯硅烷,反应3h,加饱和碳酸氢钠淬灭反应,反应液经硅藻土、乙醚洗涤,乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压回收浓缩残留物,用四氢呋喃溶解,加10%盐酸水解,在室温下搅拌10min,用乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压浓缩,柱层析得2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘。
步骤①中萘茜、四氢呋喃、连二亚硫酸钠、硫酸二甲酯、氢氧化钠的质量配比为:1.2-2: 70-80:50-60:100-120:100-150。
步骤②中N,N-二甲基乙酰胺、三氯氧磷、1,4,5,8-四甲氧基萘的三氯甲烷溶液的体积配比为:2 -3:2-5:10-25。
步骤③中无水四氢呋喃、无水三氯化铬、1,4,5,8-四甲氧基萘-2-甲醛、三甲基氯硅烷、烯丙基溴、锰粉的质量配比为:10-30:10-30:30-60:30-80:30-80:600-800。
步骤①、步骤②、步骤③中柱层析时所用的洗脱剂均为体积比为4:1的石油醚和丙酮混合溶剂。
步骤(2)具体为:在双层玻璃反应器(如图3所示)中依次添加聚偏氟乙烯、N,N-二甲基甲酰胺溶液,搅拌至溶液均匀后,添加Me6TREN和2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘,通氩气除氧30min,添加氯化亚铜,除氧1h,密封,将双层玻璃反应器置于冰水浴中,磁力搅拌下紫外辐照反应至预定的时间,待反应结束后用1:1的乙醇/水溶液沉析过滤,用氯仿重复多次抽提,得聚偏氟乙烯-芳香醚类共聚物,真空干燥备用;原料配比为:2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘、聚偏氟乙烯、N,N-二甲基甲酰胺、催化体系的质量配比为:30-60:5-12:400-550:0.1-1。
步骤2)中所述双层玻璃反应器的外层上设有进水口和出水口,与恒温循环水浴槽相连,以保持反应温度恒定;内层设有进气口、抽真空口及进料口,使反应在氮气氛围下进行;顶端采用石英玻璃加盖,以减少紫外辐照过程中玻璃对紫外光的吸收;所用紫外灯的波长为365nm,功率为1000W。
步骤(3)具体为:在两口反应瓶中滴加聚偏氟乙烯-芳香醚类共聚物的乙氰溶液,室温搅拌下滴加硝酸铈铵的水溶液,反应1h,减压回收乙氰,用氯仿萃取,水洗,饱和食盐水洗,无水硫酸镁干燥1.5 h,减压回收氯仿,硅胶柱层析分离得2-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌和6-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌的混合物,真空干燥后备用;所述的硅胶柱层析时所用的洗脱剂为体积比为3:1的石油醚和丙酮混合溶剂。
步骤(4)中:N,N-二甲基甲酰胺和步骤(3)的聚合物的质量配比为:15-20:80-85。
上述制备过程主要分为四步:①本发明利用NHK反应在萘茜上引入双键侧链,利于高分子材料与蒽醌类物质的ATRP聚合反应的发生;②利用ATRP 法合成接枝PVDF-芳香醚类共聚物,使聚偏氟乙烯功能化;③利用脱甲基氧化法制备醌,使聚偏氟乙烯蒽醌功能化;④利用相转化法,将制备的蒽醌功能化聚偏氟乙烯材料刮制成膜。
本发明的有益效果在于:
(1)单纯的蒽醌类化合物无法进行原子自由基聚合,本发明利用NHK反应在萘茜上引入双键侧链,利于高分子材料与蒽醌类物质的ATRP聚合反应的发生;在聚偏氟乙烯膜上所固定的蒽醌分子牢固、不会脱落;
(2)应用膜作为氧化还原介体的固定载体,可以适应各种膜处理设备,利于本发明的推广和应用;
(3)本发明能有效促进高浓度含氮废水的降解,特别是印染废水的降解。
附图说明
图1为2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成路线图;
图2为聚偏氟乙烯-芳香醚类共聚物的合成路线图;
图3为双层玻璃反应器;
图4为所制膜片的红外光谱图;
图5为蒽醌功能化聚偏氟乙烯超滤膜的循环使用效果图;从图中可以看出,本发明的超滤膜性能稳定,可循环多次使用。
具体实施方式
本发明用下列实施例来进一步说明本发明,但本发明的保护范围并不限于下列实施例。
实施例1
一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法,包括以下步骤:
(1)2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:
①1,4,5,8-四甲氧基萘的合成:将萘茜、催化量四丁基溴化铵、四氢呋喃加入到圆底烧瓶中,搅拌至溶解,然后添加连二亚硫酸钠水溶液和硫酸二甲酯溶液,搅拌至溶液均匀;将圆底烧瓶移至冰水浴中,反应1h,缓慢滴加NaOH水溶液,滴加完毕后移除冰水浴,在室温下反应30min,匀速搅拌18h至反应完全,反应液经乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收乙酸乙酯,柱层析分离得1,4,5,8-四甲氧基萘;1 H NMR (400MHz,DMSO):δ 6.44 (d,4 H),3.37 (s,12 H, CH3)。
萘茜、四氢呋喃、连二亚硫酸钠、硫酸二甲酯、氢氧化钠的质量配比为:1.5:75:55:110:125;
②1,4,5,8-四甲氧基萘-2-甲醛的合成:在两口反应瓶中加入N,N-二甲基乙酰胺,将两口反应瓶置于冰水浴中,依次缓慢滴加三氯氧磷和0.063 mol/L1,4,5,8-四甲氧基萘的三氯甲烷溶液,滴加完毕后移除冰水浴,加热回流反应5 h;然后加冰水停止反应,反应液经氯仿萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收氯仿,柱层析分离得1,4,5,8-四甲氧基萘-2-甲醛;1 H NMR (400 MHz,DMSO):δ 6.49-6.51 (m,3 H),3.40 (s,9 H,CH3),3.43 (s,3 H, CH3), 10.11(s,1H,CHO)。
N,N-二甲基乙酰胺、三氯氧磷、1,4,5,8-四甲氧基萘的三氯甲烷溶液的体积配比为:2.5:3:15;
③2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:氩气保护下,在干燥的两口反应瓶中依次加入分子筛、无水四氢呋喃、无水三氯化铬和锰粉,搅拌至颜色变成黑色后加入烯丙基溴,加入1,4,5,8-四甲氧基萘-2-甲醛和三甲基氯硅烷,反应3h,加饱和碳酸氢钠淬灭反应,反应液经硅藻土、乙醚洗涤,乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压回收浓缩残留物,用四氢呋喃溶解,加10%盐酸水解,在室温下搅拌10min,用乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压浓缩,柱层析得2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘;1 H NMR (400 MHz,DMSO):δ 6.47-6.51 (m,3 H),3.37 (s,9 H, CH3),3.43 (s,3 H,CH3), 8.45(s,1H,OH),4.83(t,1H,CH),2.39(m,2H,CH2),4.92(d,2H,CH2),5.76(m,1H,CH)。
无水四氢呋喃、无水三氯化铬、1,4,5,8-四甲氧基萘-2-甲醛、三甲基氯硅烷、烯丙基溴、锰粉的质量配比为:20:20:50:60:50:700。
(2)聚偏氟乙烯-芳香醚类共聚物的合成:在双层玻璃反应器中依次添加聚偏氟乙烯、N,N-二甲基甲酰胺溶液,搅拌至溶液均匀后,添加Me6TREN和2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘,通氩气除氧30min,添加氯化亚铜,除氧1h,密封,将双层玻璃反应器置于冰水浴中,磁力搅拌下紫外辐照反应至预定的时间,待反应结束后用1:1的乙醇/水溶液沉析过滤,用氯仿重复多次抽提,得聚偏氟乙烯-芳香醚类共聚物,真空干燥备用;原料配比为:2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘、聚偏氟乙烯、N,N-二甲基甲酰胺、催化体系的质量配比为:45:7:500:0.5;
(3)利用脱甲基氧化法将聚偏氟乙烯-芳香醚类共聚物制成醌:
在两口反应瓶中滴加聚偏氟乙烯-芳香醚类共聚物的乙氰溶液,室温搅拌下滴加硝酸铈铵的水溶液,反应1h,减压回收乙氰,用氯仿萃取,水洗,饱和食盐水洗,无水硫酸镁干燥1.5 h,减压回收氯仿,硅胶柱层析分离得2-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌和6-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌的混合物,真空干燥后备用;所述的硅胶柱层析时所用的洗脱剂为体积比为3:1的石油醚和丙酮混合溶剂;
(4)将步骤(3)的聚合物和N,N-二甲基甲酰胺按质量配比17:82制成铸膜液,刮制成膜。
实施例2
一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法,包括以下步骤:
(1)2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:
①1,4,5,8-四甲氧基萘的合成:将萘茜、催化量四丁基溴化铵、四氢呋喃加入到圆底烧瓶中,搅拌至溶解,然后添加连二亚硫酸钠水溶液和硫酸二甲酯溶液,搅拌至溶液均匀;将圆底烧瓶移至冰水浴中,反应1h,缓慢滴加NaOH水溶液,滴加完毕后移除冰水浴,在室温下反应30min,匀速搅拌18h至反应完全,反应液经乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收乙酸乙酯,柱层析分离得1,4,5,8-四甲氧基萘;萘茜、四氢呋喃、连二亚硫酸钠、硫酸二甲酯、氢氧化钠的质量配比为:1.2: 80:50:120:150;
②1,4,5,8-四甲氧基萘-2-甲醛的合成:在两口反应瓶中加入N,N-二甲基乙酰胺,将两口反应瓶置于冰水浴中,依次缓慢滴加三氯氧磷和0.063 mol/L 1,4,5,8-四甲氧基萘的三氯甲烷溶液,滴加完毕后移除冰水浴,加热回流反应5 h;然后加冰水停止反应,反应液经氯仿萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收氯仿,柱层析分离得1,4,5,8-四甲氧基萘-2-甲醛;
N,N-二甲基乙酰胺、三氯氧磷、1,4,5,8-四甲氧基萘的三氯甲烷溶液的体积配比为:2:5:10;
③2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:氩气保护下,在干燥的两口反应瓶中依次加入分子筛、无水四氢呋喃、无水三氯化铬和锰粉,搅拌至颜色变成黑色后加入烯丙基溴,加入1,4,5,8-四甲氧基萘-2-甲醛和三甲基氯硅烷,反应3h,加饱和碳酸氢钠淬灭反应,反应液经硅藻土、乙醚洗涤,乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压回收浓缩残留物,用四氢呋喃溶解,加10%盐酸水解,在室温下搅拌10min,用乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压浓缩,柱层析得2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘;
无水四氢呋喃、无水三氯化铬、1,4,5,8-四甲氧基萘-2-甲醛、三甲基氯硅烷、烯丙基溴、锰粉的质量配比为:10: 30:30:80:30: 800。
(2)聚偏氟乙烯-芳香醚类共聚物的合成:在双层玻璃反应器中依次添加聚偏氟乙烯、N,N-二甲基甲酰胺溶液,搅拌至溶液均匀后,添加Me6TREN和2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘,通氩气除氧30min,添加氯化亚铜,除氧1h,密封,将双层玻璃反应器置于冰水浴中,磁力搅拌下紫外辐照反应至预定的时间,待反应结束后用1:1的乙醇/水溶液沉析过滤,用氯仿重复多次抽提,得聚偏氟乙烯-芳香醚类共聚物,真空干燥备用;原料配比为:2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘、聚偏氟乙烯、N,N-二甲基甲酰胺、催化体系的质量配比为:30:12:400:1;
(3)利用脱甲基氧化法将聚偏氟乙烯-芳香醚类共聚物制成醌:
在两口反应瓶中滴加聚偏氟乙烯-芳香醚类共聚物的乙氰溶液,室温搅拌下滴加硝酸铈铵的水溶液,反应1h,减压回收乙氰,用氯仿萃取,水洗,饱和食盐水洗,无水硫酸镁干燥1.5 h,减压回收氯仿,硅胶柱层析分离得2-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌和6-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌的混合物,真空干燥后备用;所述的硅胶柱层析时所用的洗脱剂为体积比为3:1的石油醚和丙酮混合溶剂;
(4)将步骤(3)的聚合物和N,N-二甲基甲酰胺按质量配比15:85制成铸膜液,刮制成膜。
实施例3
一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法,包括以下步骤:
(1)2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:
①1,4,5,8-四甲氧基萘的合成:将萘茜、催化量四丁基溴化铵、四氢呋喃加入到圆底烧瓶中,搅拌至溶解,然后添加连二亚硫酸钠水溶液和硫酸二甲酯溶液,搅拌至溶液均匀;将圆底烧瓶移至冰水浴中,反应1h,缓慢滴加NaOH水溶液,滴加完毕后移除冰水浴,在室温下反应30min,匀速搅拌18h至反应完全,反应液经乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收乙酸乙酯,柱层析分离得1,4,5,8-四甲氧基萘;萘茜、四氢呋喃、连二亚硫酸钠、硫酸二甲酯、氢氧化钠的质量配比为:2:70:60:100:100;
②1,4,5,8-四甲氧基萘-2-甲醛的合成:在两口反应瓶中加入N,N-二甲基乙酰胺,将两口反应瓶置于冰水浴中,依次缓慢滴加三氯氧磷溶液0.063mol/L1,4,5,8-四甲氧基萘的三氯甲烷溶液,滴加完毕后移除冰水浴,加热回流反应5 h;然后加冰水停止反应,反应液经氯仿萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收氯仿,柱层析分离得1,4,5,8-四甲氧基萘-2-甲醛;
N,N-二甲基乙酰胺、三氯氧磷、1,4,5,8-四甲氧基萘的三氯甲烷溶液的体积配比为:3:2:25;
③2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:氩气保护下,在干燥的两口反应瓶中依次加入分子筛、无水四氢呋喃、无水三氯化铬和锰粉,搅拌至颜色变成黑色,加入1,4,5,8-四甲氧基萘-2-甲醛和三甲基氯硅烷,反应3h,加饱和碳酸氢钠淬灭反应,反应液经硅藻土、乙醚洗涤,乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压回收浓缩残留物,用四氢呋喃溶解,加10%盐酸水解,在室温下搅拌10min,用乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压浓缩,柱层析得2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘;
无水四氢呋喃、无水三氯化铬、1,4,5,8-四甲氧基萘-2-甲醛、三甲基氯硅烷、烯丙基溴、锰粉的质量配比为:30:10:60:30:80:800。
(2)聚偏氟乙烯-芳香醚类共聚物的合成:在双层玻璃反应器中依次添加聚偏氟乙烯、N,N-二甲基甲酰胺溶液,搅拌至溶液均匀后,添加Me6TREN和2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘,通氩气除氧30min,添加氯化亚铜,除氧1h,密封,将双层玻璃反应器置于冰水浴中,磁力搅拌下紫外辐照反应至预定的时间,待反应结束后用1:1的乙醇/水溶液沉析过滤,用氯仿重复多次抽提,得聚偏氟乙烯-芳香醚类共聚物,真空干燥备用;原料配比为:2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘、聚偏氟乙烯、N,N-二甲基甲酰胺、催化体系的质量配比为:60:5:550:0.1;
(3)利用脱甲基氧化法将聚偏氟乙烯-芳香醚类共聚物制成醌:
在两口反应瓶中滴加聚偏氟乙烯-芳香醚类共聚物的乙氰溶液,室温搅拌下滴加硝酸铈铵的水溶液,反应1h,减压回收乙氰,用氯仿萃取,水洗,饱和食盐水洗,无水硫酸镁干燥1.5 h,减压回收氯仿,硅胶柱层析分离得2-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌和6-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌的混合物,真空干燥后备用;所述的硅胶柱层析时所用的洗脱剂为体积比为3:1的石油醚和丙酮混合溶剂;
(4)将步骤(3)的聚合物和N,N-二甲基甲酰胺按质量配比20:80制成铸膜液,刮制成膜。
应用实施例1
表1 在含氮废水降解中的应用数据
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (10)
1.一种蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:包括以下步骤:
(1)2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成;
(2)聚偏氟乙烯-芳香醚类共聚物的合成:选用聚偏氟乙烯为引发剂,2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘为单体,N,N-二甲基甲酰胺为溶剂,氯化亚铜/Me6TREN为催化体系,经原子自由基聚合法合成聚偏氟乙烯-芳香醚类共聚物;
(3)利用脱甲基氧化法将聚偏氟乙烯-芳香醚类共聚物脱甲氧基还原成醌;
(4)将步骤(3)的聚合物和N,N-二甲基甲酰胺制成铸膜液,刮制成膜。
2.根据权利要求1所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤(1)中2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成包括以下步骤:
①1,4,5,8-四甲氧基萘的合成:将萘茜、催化量四丁基溴化铵、四氢呋喃加入到圆底烧瓶中,搅拌至溶解,然后添加连二亚硫酸钠水溶液和硫酸二甲酯溶液,搅拌至溶液均匀;将圆底烧瓶移至冰水浴中,反应1h,缓慢滴加NaOH水溶液,滴加完毕后移除冰水浴,在室温下反应30min,匀速搅拌18h至反应完全,反应液经乙酸乙酯萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收乙酸乙酯,柱层析分离得1,4,5,8-四甲氧基萘;
②1,4,5,8-四甲氧基萘-2-甲醛的合成:在两口反应瓶中加入N,N-二甲基乙酰胺,将两口反应瓶置于冰水浴中,依次缓慢滴加三氯氧磷和0.063mol/L 1,4,5,8-四甲氧基萘的三氯甲烷溶液,滴加完毕后移除冰水浴,加热回流反应5 h;然后加冰水停止反应,反应液经氯仿萃取、饱和食盐水洗涤、无水硫酸镁干燥,过滤,减压回收氯仿,柱层析分离得1,4,5,8-四甲氧基萘-2-甲醛;
③2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘的合成:氩气保护下,在干燥的两口反应瓶中依次加入分子筛、无水四氢呋喃、无水三氯化铬和锰粉,搅拌至颜色变成黑色后加入烯丙基溴,搅拌至颜色变成黑色,加入1,4,5,8-四甲氧基萘-2-甲醛和三甲基氯硅烷,反应3h,加饱和碳酸氢钠淬灭反应,反应液经硅藻土、乙醚洗涤,乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压回收浓缩残留物,用四氢呋喃溶解,加10%盐酸水解,在室温下搅拌10min,用乙醚萃取,饱和食盐水洗涤,无水硫酸镁干燥,减压浓缩,柱层析得2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘。
3.根据权利要求2所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤①中萘茜、四氢呋喃、连二亚硫酸钠、硫酸二甲酯、氢氧化钠的质量配比为:1.2-2: 70-80:50-60:100-120:100-150。
4.根据权利要求2所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤②中N,N-二甲基乙酰胺、三氯氧磷、1,4,5,8-四甲氧基萘的三氯甲烷溶液的体积配比为:2-3:2-5:10-25。
5.根据权利要求2所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤③中无水四氢呋喃、无水三氯化铬、1,4,5,8-四甲氧基萘-2-甲醛、三甲基氯硅烷、烯丙基溴、锰粉的质量配比为:10-30:10-30:30-60:30-80:30-80:600-800。
6.根据权利要求2-5任一项所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤①、步骤②、步骤③中柱层析时所用的洗脱剂均为体积比为4:1的石油醚和丙酮混合溶剂。
7.根据权利要求1所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤(2)中:2-(1-羟基-3-丁烯)-1,4,5,8-四甲氧基萘、聚偏氟乙烯、N,N-二甲基甲酰胺、催化体系的质量配比为:30-60:5-12:400-550:0.1-1。
8.根据权利要求1所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤(3)具体为:在两口反应瓶中滴加聚偏氟乙烯-芳香醚类共聚物的乙氰溶液,室温搅拌下滴加硝酸铈铵的水溶液,反应1h,减压回收乙氰,用氯仿萃取,水洗,饱和食盐水洗,无水硫酸镁干燥1.5 h,减压回收氯仿,硅胶柱层析分离得2-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌和6-(1-羟基-3-丁烯)-5,8-二甲氧基-1,4-萘醌的混合物,真空干燥后备用。
9.根据权利要求8所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:所述的硅胶柱层析时所用的洗脱剂为体积比为3:1的石油醚和丙酮混合溶剂。
10.根据权利要求1所述的蒽醌功能化聚偏氟乙烯超滤膜的制备方法,其特征在于:步骤(4)中:N,N-二甲基甲酰胺和步骤(3)的聚合物的质量配比为:15-20:80-85。
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