CN109473605A - 聚酰亚胺多孔隔膜的制备方法 - Google Patents
聚酰亚胺多孔隔膜的制备方法 Download PDFInfo
- Publication number
- CN109473605A CN109473605A CN201811164384.5A CN201811164384A CN109473605A CN 109473605 A CN109473605 A CN 109473605A CN 201811164384 A CN201811164384 A CN 201811164384A CN 109473605 A CN109473605 A CN 109473605A
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- China
- Prior art keywords
- preparation
- diaphragm
- solvent
- polyimide foraminous
- polyamic acid
- Prior art date
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 37
- 229920001721 polyimide Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 24
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 125000001246 bromo group Chemical group Br* 0.000 claims description 9
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- -1 Carboxylic acid dianhydride Chemical class 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LSTRKXWIZZZYAS-UHFFFAOYSA-N 2-bromoacetyl bromide Chemical group BrCC(Br)=O LSTRKXWIZZZYAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- XTTLUUBHRXWFSZ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene Chemical compound ClC1=C(Cl)C=C2C=C(Cl)C(Cl)=CC2=C1 XTTLUUBHRXWFSZ-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- SYZRZLUNWVNNNV-UHFFFAOYSA-N 2-bromoacetyl chloride Chemical compound ClC(=O)CBr SYZRZLUNWVNNNV-UHFFFAOYSA-N 0.000 claims description 2
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 claims description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 claims description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical class NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 claims description 2
- JCUYNPHEESTECG-UHFFFAOYSA-N 3-amino-6-(4-aminophenyl)benzene-1,2-disulfonic acid Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(S(O)(=O)=O)=C1S(O)(=O)=O JCUYNPHEESTECG-UHFFFAOYSA-N 0.000 claims description 2
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 claims description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 claims 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 claims 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 230000009435 amidation Effects 0.000 abstract description 2
- 238000007112 amidation reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229920006254 polymer film Polymers 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical class NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000002221 antipyretic Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical class C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002145 thermally induced phase separation Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
本发明涉及一种聚酰亚胺多孔隔膜的制备方法。该方法使用热不稳定聚合物为致孔剂,先将热不稳定聚合物与聚酰胺酸(PAA)在溶剂中反应形成共聚物,铺成聚合物薄膜,再在高温下热解除去热不稳定链段,并使聚酰胺酸亚酰胺化,得到聚酰亚胺多孔隔膜。本发明将致孔剂与聚酰胺酸通过化学反应实现分子级分散,致孔剂与聚酰胺酸的反应活性高,能够随意调节隔膜孔隙率。该隔膜可用于锂离子及锂硫电池领域。本发明制备方法简单、反应效率高、易于工业化生产,隔膜耐高温性能优异、机械性能好,能够提高电池的电化学性能和安全性。
Description
技术领域
本发明涉及一系列聚酰亚胺多孔隔膜的制备方法,属于高分子合成、储能及功能材料领 域。
背景技术
隔膜作为电池的关键组件,位于正极和负极之间,能够提供锂离子传输通道,同时防 止正负极间电子传输发生接触短路。在保证电池的正常工作的前提下,通过隔膜功能化提高 电池的电化学性能是一种行之有效的策略。如增强隔膜的机械强度及耐高温性能,提高电池 的安全性;提高隔膜的电解液浸润性促进锂离子传输,改善电池的电化学性能。此外,锂硫 电池中在隔膜上引入磺酸基团能够有效抑制多硫离子的穿梭,减少活性物质损失和负极的破 坏导致的电池性能恶化。
传统的锂电池隔膜主要是聚丙烯(PP)及聚乙烯(PE)隔膜。聚烯烃隔膜具有高的机械 强度、耐溶剂性等优点,但是其熔点较低(聚乙烯熔点约为130℃,聚丙烯约为160℃),当电池发生热失控时容易造成正负极接触短路引发安全事故。此外,在锂硫电池体系中,聚烯烃隔膜不能抑制多硫离子穿梭,导致电池容量的快速衰减。目前,常用的多孔隔膜制备方法主要有干法单向拉伸或双向隔膜,如商业化的聚丙烯(PP)隔膜;湿法(热致相分离法) 如商业化湿法聚乙烯(PE)隔膜;静电纺丝法,用于制备无纺纤维薄膜;以及文献中常见 的非溶剂诱导相分离法制备不对称隔膜等。热解致孔剂制备多孔隔膜的研究及应用在电池隔膜领域的报道较少。
聚酰亚胺具有优异的机械性能、耐高低温性能、化学稳定性好等特点,在航空航天、微 电子、纺织等领域具有广泛应用。使用聚酰亚胺制备电池隔膜能够提高电池的安全性,电解 液浸润性等性能。将聚酰亚胺功能化制备带磺酸基隔膜能够显著缓解锂硫电池体系中的多硫 离子穿梭效应,抑制电池的自放电行为。目前,聚酰亚胺隔膜的制备方法以静电纺丝法为主, 也有少量非溶剂诱导相分离法的报道,但是热解化学键接的致孔剂制备聚酰亚胺锂隔膜用于 锂离子电池、锂硫电池的报道极为鲜见。
本发明使用热不稳定聚合物作为致孔剂,通过化学反应使致孔剂与聚酰胺酸进行键合形 成共聚物,实现致孔剂与膜基材的分子级均匀分散,通过高温处理在热解致孔剂的同时使聚 酰胺酸亚酰胺化制备孔径分布均匀,性能优异的聚酰亚胺隔膜是一项极具创新性和商业化价 值的研究内容。
发明内容
本发明的目的是提供一种极具应用价值的聚酰亚胺多孔隔膜的制备方法,适用于锂离 子电池及锂硫电池领域。
为实现上述目的,本发明的聚酰亚胺多孔隔膜的制备方法包括如下步骤:
(1)热不稳定聚合物的制备:
将羟基封端的热不稳定低聚物进行减压干燥,除去溶剂和水,然后用溶剂溶解后,在搅 拌下分次加入溴化试剂和缚酸剂并反应,随后加入非质子极性溶剂析出沉淀并抽滤除去,并 用碳酸氢钠水溶液洗涤除去未反应溴化试剂,除溶剂并减压干燥,得到溴基封端的热不稳定 致孔剂A;
将羟基封端的热不稳定聚合物溴化合成溴基封端的聚合物,反应式如下:
步骤(1)中使用的热不稳定低聚物Polymer为聚丙二醇(PPG)或聚己内酯(PCL)、聚丙交酯(PLA)、聚碳酸亚丙酯(PPC)的二元醇;热不稳定低聚物的相对分子质量800-14000。
步骤(1)所述溴化试剂为溴乙酰溴或溴乙酰氯,其摩尔用量为热不稳定低聚物的2-20 倍;所述缚酸剂为4-二甲氨基吡啶、吡啶或三乙胺,其摩尔用量为热不稳定低聚物的1-5倍。
步骤(1)的反应为放热反应,反应温度应控制在室温附近,溴化试剂要分批加入并剧 烈搅拌,需要时可使用冰水浴降温。反应需要加入缚酸剂三乙胺除去生成的HBr,反应时间 在12-48小时。反应结束后需加入非质子极性溶剂四氢呋喃、丙酮等析出沉淀并过滤除去, 所得聚合物溶液经进一步纯化并干燥后得到热不稳定聚合物A。
所述的溶剂为氯仿、二氯甲烷或1,2-二氯乙烷,用量质量为热不稳定低聚物的5-20倍; 所述非质子极性溶剂为丙酮、N,N-二甲基甲酰胺或四氢呋喃,其体积用量为溶液的1-5倍。
所述碳酸氢钠水溶液的质量分数为1-10%,其摩尔用量为溶液的1-5倍,洗涤次数为3-8 次。
(2)聚酰胺酸前聚体的合成:
将二胺单体溶于有机溶剂,加入等摩尔量的二酐单体在机械搅拌下进行反应,反应数小 时后加入无水碳酸钾,继续反应数小时后,通过离心除去未反应的碳酸钾,得到聚酰胺酸溶 液B;
使用二酐单体与二胺单体在有机溶剂中反应,然后再加入碳酸钾反应制得聚酰胺酸钾盐, 反应式如下:
其中R1来自所使用的二酐单体的结构,R2来自所使用的二胺单体的结构。
步骤(2)中所述二胺单体为4,4'-二氨基二苯醚、4,4'-二氨基二苯甲酮、4,4'-硫基二苯 胺、4,4'-亚异丙基二苯胺、3,3'-二甲基联苯胺、3,3'-二甲氧基联苯胺、3,3'-二甲基-4,4'-二 氨基二苯甲酮、间苯二胺、对苯二胺、3,3’-磺酰基二苯胺、2,2’-双(4-氨基苯酚)、4,4’ -二氨基联苯、4,4'-亚甲基二苯胺、3,3'-二羧基联苯胺、2,4-二氨基甲苯、2,5-二氨基甲 苯、刚果红、4,4`-二氨基二苯乙烯-二磺酸、联苯胺双磺酸中的一种或几种。
步骤(2)中所述二酐单体为均苯四甲酸二酐、4,4'-氧双邻苯二甲酸酐,3,3',4,4'-二苯 甲酮四羧酸二酐、1,2',3,3'-二苯甲酮四羧酸二酐、2,6-二氯萘-1,4,5,8-四羧酸二酐、3,3',4,4'- 联苯四羧酸二酐、2,2',3,3'-联苯四羧酸二酐、1,4-双(三氟甲基)-2,3,5,6-苯四羧酸二酐、 2,7-二氯萘-1,4,5,8-四羧酸二酐、2,3,6,7-四氯萘-2,4,5,8-四羧酸二酐、菲-1,8,9,10-四羧酸 二酐、苯-1,2,3,4-四羧酸二酐和吡嗪-2,3,5,6-四羧酸二酐中的一种或几种。
步骤(2)所述有机溶剂为N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜或环丁砜 中的一种或几种,其质量用量为反应物的5-20倍,反应时间为1-48小时,反应温度为10-100℃。
步骤(2)所述碳酸钾的用量为二酐单体的0.1-2倍,反应时间为0.5-10小时,反应温度 为10-100℃。
(3)共聚物薄膜的制备:
向聚酰胺酸溶液B中加入溴基封端的热不稳定致孔剂A,快速搅拌反应至混合物溶液 变透明后,将反应液离心除泡,然后使用刮刀将溶液刮涂到玻璃板上,挥发掉溶剂得到共聚 物薄膜;
热不稳定聚合物A与聚酰胺酸B反应制备共聚物,并铺成聚合物薄膜,所涉及的反应 式如下:
步骤(3)中通过调节热不稳定聚合物A的添加量控制多孔膜的孔隙率,该共聚反应在室温下进行,反应时间0-3h。反应完成后的成膜操作为:将反应液离心除泡,然后使用 刮刀将溶液刮涂到玻璃板上,挥发掉溶剂得到共聚物薄膜,溶剂的挥发需要通过调节温度与气流速度进行控制。
步骤(3)所述溴基封端的热不稳定致孔剂A的质量用量为聚酰胺酸的1-5倍,反应时 间为5-200min。
步骤(3)所述刮刀厚度为100-1000μm;步骤(3)所述溶剂挥发温度为20-100℃;
(4)多孔聚酰亚胺隔膜的制备:
将制备好的薄膜进行高温热处理,使热不稳定聚合物分解成孔,同时聚酰胺酸发生反应 脱水转化成聚酰亚胺。
反应如下:
步骤(4)所得多孔聚酰亚胺隔膜的聚合物组成为一种聚酰亚胺或者两种聚酰亚胺共聚 或共混的形式存在的。
步骤(4)所述高温热处理的温度为100-350℃,热处理时间为1-20h。
与现有技术相比,本发明具有如下有益效果:本发明为原料反应活性高、产率高、重现 性好,易于放大进行工业化生产,孔径孔隙率易于调节,所的聚酰亚胺隔膜的功能化基团类 型及含量可任意调节,满足不同的性能需求,所得隔膜的机械性能优异,耐高温性好,孔隙 率高。
下面结合具体实施例子对本发明做进一步说明。
附图说明
图1为实施例1制备产物的核磁氢谱图;
图2为实施例2制备的共聚物及高温处理所得聚酰亚胺隔膜的照片;
图3为实施例2制备的共聚物及高温处理所得聚酰亚胺隔膜的氮气氛围下热重图;
图4为实施例2制备的聚酰亚胺隔膜的扫描电镜形貌图。
具体实施方式
为更好理解本发明的技术方案,通过以下具体实施例作进一步详细描述。
实施例1:热不稳定聚合物聚碳酸亚丙酯二元醇的溴基封端反应。
(1)羟基封端PPC(PPC-2OH)的合成
取85g高分子量PPC于三口圆底烧瓶中,在氮气氛围中于160℃进行机械搅拌,待温度 稳定在160℃时,加入15g 1,4丁二醇(BDO)进行醇解,反应2小时后停止加热,冷却到 室温,加入50mL氯仿使产物溶解,随后加入50mL去离子水洗涤,并通过分液漏斗分液, 除去未反应的BDO及小分子的PPC-2OH,重复洗涤5次以上,将纯化好的PPC-2OH的氯 仿溶液转移至表面皿中,使氯仿挥发除净,可得PPC-2OH产物,产率~60%。使用滴定法测 定羟基含量,根据羟值计算醇解所得PPC-2OH的相对分子质量
(2)溴封端PPC(PPC-2Br)的合成
于50mL单口圆底烧瓶中加入10g PPC-2OH,解热到80℃,使用油泵抽真空干燥2h后,加入10mL二氯甲烷使其溶解,随后加入羟基的2.2倍当量的三乙胺使搅拌均匀。将 PPC-2OH溶液进行冰浴使温度降至0℃左右,分次加入羟基10倍当量的溴乙酰溴进行溴化 反应,待溴乙酰溴完全加入后,撤去冰浴在室温下搅拌反应24h。随后加入20mL四氢呋喃, 使产物中杂质沉淀下来,通过抽滤除去沉淀并通过旋蒸除去溶剂。使用20mL氯仿溶解旋蒸 后产物,并配制5wt.%的NaHCO3溶液对产物进行洗涤,除去未反应的溴乙酰溴和HBr,于 分液漏斗中进行分液,经过5次洗涤后,再用去离子水洗涤2-3次除去有机相中不溶物。随 后使用旋蒸除去溶剂,将产物于45℃真空干燥箱中干燥24h,得到PPC-2Br,产率~50%。通 过核磁氢谱测试确定产物结构(图1)。具体反应流程如反应式1所示。
反应式1 PPC-Br的反应流程式
实施例2:均苯四甲酸二酐与4,4'-二氨基二苯醚为原料制备聚酰亚胺隔膜
于150mL的圆底烧瓶中加入10mmol的二胺单体4,4'-二氨基二苯醚及50mL N,N-二甲 基乙酰胺于室温、氮气氛围下机械搅拌至完全溶解,随后加入10mmol均苯四甲酸二酐于室温下反应10h,进行聚合,加入10mmol无水碳酸钾进行反应2h后,离心除去未反应固 体颗粒得到聚酰胺酸钾盐(PAA-K+)。具体反应流程如反应式2所示:
反应式2 PAA-K+的反应流程式
于50mL离心管中称取2g 7wt.%的PAA-K+溶液,加入0.15g PPC-2Br快速搅拌使混合均匀得透明溶液,于转速为10000r/min下离心1min,除去溶液中气泡后,使用200μm 的刮刀将溶液涂覆到玻璃板上,随后转移至调平后的加热台上挥发溶剂,得到均匀的共聚物 薄膜。所的薄膜的热重分析图将薄膜置入管式炉中于氮气氛围下进行程序升温,于120℃保温2h,180℃保温2h,240℃保温2h,280℃保温1h,300℃保温1h,进行PPC的热解以及 聚酰胺酸的亚酰胺化反应得到聚酰亚胺隔膜。PAA-K+与PPC-2Br反应交联薄膜及高温处理 所得聚酰亚胺的照片和N2下热重图如图2,图3所示。图4为制备的聚酰亚胺隔膜的扫描 电镜形貌图。具体反应流程如反应式3所示:
反应式3 PAA-g-PPC的反应流程式。
Claims (10)
1.一种聚酰亚胺多孔隔膜的制备方法,其特征在于包括如下步骤:
(1)热不稳定聚合物的制备:
将羟基封端的热不稳定低聚物进行减压干燥,除去溶剂和水,然后用溶剂溶解后,在搅拌下分次加入溴化试剂和缚酸剂并反应,随后加入非质子极性溶剂析出沉淀并抽滤除去,并用碳酸氢钠水溶液洗涤除去未反应溴化试剂,除溶剂并减压干燥,得到溴基封端的热不稳定致孔剂A;
(2)聚酰胺酸前聚体的合成:
将二胺单体溶于有机溶剂,加入等摩尔量的二酐单体在机械搅拌下进行反应,反应数小时后加入无水碳酸钾,继续反应数小时后,通过离心除去未反应的碳酸钾,得到聚酰胺酸溶液B;
(3)共聚物薄膜的制备:
向聚酰胺酸溶液B中加入溴基封端的热不稳定致孔剂A,快速搅拌反应至混合物溶液变透明后,将反应液离心除泡,然后使用刮刀将溶液刮涂到玻璃板上,挥发掉溶剂得到共聚物薄膜;
(4)多孔聚酰亚胺隔膜的制备:
将制备好的薄膜进行高温热处理,使热不稳定聚合物分解成孔,同时聚酰胺酸发生反应脱水转化成聚酰亚胺。
2.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(1)中所述的热不稳定低聚物为聚丙二醇、聚己内酯、聚丙交酯或聚碳酸亚丙酯的二元醇,热不稳定低聚物的相对分子质量 800-14000。
3.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(1)所述溴化试剂为溴乙酰溴或溴乙酰氯,其摩尔用量为热不稳定低聚物的2-20倍;所述缚酸剂为4-二甲氨基吡啶、吡啶或三乙胺,其摩尔用量为热不稳定低聚物的1-5倍。
4.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(2)中所述二胺单体为4,4'-二氨基二苯醚、4,4'- 二氨基二苯甲酮、4,4'- 硫基二苯胺、4,4'- 亚异丙基二苯胺、3,3'- 二甲基联苯胺、3,3'- 二甲氧基联苯胺、3,3'- 二甲基-4,4'- 二氨基二苯甲酮、间苯二胺、对苯二胺、3,3’- 磺酰基二苯胺、2,2’- 双(4- 氨基苯酚)、4,4’- 二氨基联苯、4,4'- 亚甲基二苯胺、3,3'- 二羧基联苯胺、2,4- 二氨基甲苯、2,5- 二氨基甲苯、刚果红、4,4`-二氨基二苯乙烯-二磺酸、联苯胺双磺酸中的一种或几种;
所述二酐单体为均苯四甲酸二酐、4,4'-氧双邻苯二甲酸酐,3,3',4,4'- 二苯甲酮四羧酸二酐、1,2',3,3'- 二苯甲酮四羧酸二酐、2,6- 二氯萘-1,4,5,8- 四羧酸二酐、3,3',4,4'- 联苯四羧酸二酐、2,2',3,3'- 联苯四羧酸二酐、1,4- 双( 三氟甲基)-2,3,5,6- 苯四羧酸二酐、2,7- 二氯萘-1,4,5,8- 四羧酸二酐、2,3,6,7- 四氯萘-2,4,5,8- 四羧酸二酐、菲-1,8,9,10- 四羧酸二酐、苯-1,2,3,4- 四羧酸二酐和吡嗪-2,3,5,6- 四羧酸二酐中的一种或几种。
5.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,所述的溶剂为氯仿、二氯甲烷或1,2-二氯乙烷,用量质量为热不稳定低聚物的5-20倍;所述非质子极性溶剂为丙酮、N,N-二甲基甲酰胺或四氢呋喃,其体积用量为溶液的1-5倍。
6.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,所述碳酸氢钠水溶液的质量分数为1-10%,其摩尔用量为溶液的1-5倍,洗涤次数为3-8次。
7.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(2)所述有机溶剂为N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜或环丁砜中的一种或几种,其质量用量为反应物的5-20倍,反应时间为1-48小时,反应温度为10-100℃。
8.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(2)所述碳酸钾的用量为二酐单体的0.1-2倍,反应时间为0.5-10小时, 反应温度为10-100℃。
9.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(3)所述
溴基封端的热不稳定致孔剂A的质量用量为聚酰胺酸的1-5倍,反应时间为5-200 min。
10.如权利要求1所述的聚酰亚胺多孔隔膜的制备方法,其特征在于,步骤(3)所述
刮刀厚度为100-1000 μm;步骤(3)所述溶剂挥发温度为20-100℃;步骤(4)所述高温热处理的温度为100-350℃,热处理时间为1-20 h。
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