CN114643083A - Monolithic polytrifluorochloroethylene bipolar membrane containing metal phthalocyanine derivative water dissociation catalyst and preparation method thereof - Google Patents
Monolithic polytrifluorochloroethylene bipolar membrane containing metal phthalocyanine derivative water dissociation catalyst and preparation method thereof Download PDFInfo
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- CN114643083A CN114643083A CN202210241576.1A CN202210241576A CN114643083A CN 114643083 A CN114643083 A CN 114643083A CN 202210241576 A CN202210241576 A CN 202210241576A CN 114643083 A CN114643083 A CN 114643083A
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- membrane
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- polytrifluorochloroethylene
- bipolar membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 134
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 92
- -1 polytrifluorochloroethylene Polymers 0.000 title claims abstract description 83
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 238000010494 dissociation reaction Methods 0.000 title claims abstract description 41
- 230000005593 dissociations Effects 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 239000003153 chemical reaction reagent Substances 0.000 claims description 47
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 44
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 239000002585 base Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 33
- 238000006277 sulfonation reaction Methods 0.000 claims description 31
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 28
- 239000012295 chemical reaction liquid Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000007306 functionalization reaction Methods 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 17
- 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 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 229920000578 graft copolymer Polymers 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 150000003440 styrenes Chemical class 0.000 claims description 14
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 238000005349 anion exchange Methods 0.000 claims description 11
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920001577 copolymer Polymers 0.000 claims description 9
- 238000005342 ion exchange Methods 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000031709 bromination Effects 0.000 claims description 8
- 238000005893 bromination reaction Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 7
- 238000005341 cation exchange Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003011 anion exchange membrane Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- VAPKHDZBJXRVNG-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene;1-ethenyl-4-methylbenzene Chemical group CC1=CC=C(C=C)C=C1.CC1=CC=CC(C=C)=C1 VAPKHDZBJXRVNG-UHFFFAOYSA-N 0.000 claims description 5
- BLXAGSNYHSQSRC-UHFFFAOYSA-M sodium;2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=CC=C1S([O-])(=O)=O BLXAGSNYHSQSRC-UHFFFAOYSA-M 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- ISNICOKBNZOJQG-UHFFFAOYSA-N 1,1,2,3,3-pentamethylguanidine Chemical compound CN=C(N(C)C)N(C)C ISNICOKBNZOJQG-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 4
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 4
- PTBPTNCGZUOCBK-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole Chemical compound CC1=NC(C)=C(C)N1 PTBPTNCGZUOCBK-UHFFFAOYSA-N 0.000 claims description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YREGSYXZCXZETF-UHFFFAOYSA-N 1,1,2,3-tetramethyl-3-propylguanidine Chemical compound CCCN(C)C(=NC)N(C)C YREGSYXZCXZETF-UHFFFAOYSA-N 0.000 claims description 3
- YTIPFUNXZCIVBV-UHFFFAOYSA-N 1-butyl-1,2,3,3-tetramethylguanidine Chemical compound CCCCN(C)C(=NC)N(C)C YTIPFUNXZCIVBV-UHFFFAOYSA-N 0.000 claims description 3
- MHKPHXSKQHOBRI-UHFFFAOYSA-N 1-ethenyl-2,3,4-trimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1C MHKPHXSKQHOBRI-UHFFFAOYSA-N 0.000 claims description 3
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 claims description 3
- GRBVDQFVTXVIPH-UHFFFAOYSA-N 1-ethyl-1,2,3,3-tetramethylguanidine Chemical compound CCN(C)C(=NC)N(C)C GRBVDQFVTXVIPH-UHFFFAOYSA-N 0.000 claims description 3
- OGMLFMYWHSCAHY-UHFFFAOYSA-N 1-hexyl-1,2,3,3-tetramethylguanidine Chemical compound CCCCCCN(C)C(=NC)N(C)C OGMLFMYWHSCAHY-UHFFFAOYSA-N 0.000 claims description 3
- DLDSJUDCGZNBNR-UHFFFAOYSA-N 2-(2,2-dimethylpropyl)-1h-imidazole Chemical compound CC(C)(C)CC1=NC=CN1 DLDSJUDCGZNBNR-UHFFFAOYSA-N 0.000 claims description 3
- JYBLQBKTEAJZGV-UHFFFAOYSA-N 2-butyl-4,5-dimethyl-1h-imidazole Chemical compound CCCCC1=NC(C)=C(C)N1 JYBLQBKTEAJZGV-UHFFFAOYSA-N 0.000 claims description 3
- GNCJRTJOPHONBZ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1h-imidazole Chemical compound CC1(C)NC=NC1(C)C GNCJRTJOPHONBZ-UHFFFAOYSA-N 0.000 claims description 3
- INXRCHGDJLSMII-UHFFFAOYSA-N 4,5-dimethyl-2-propyl-1h-imidazole Chemical compound CCCC1=NC(C)=C(C)N1 INXRCHGDJLSMII-UHFFFAOYSA-N 0.000 claims description 3
- PMZXJPLGCUVUDN-UHFFFAOYSA-N 4-ethenyl-1,2-dimethylbenzene Chemical compound CC1=CC=C(C=C)C=C1C PMZXJPLGCUVUDN-UHFFFAOYSA-N 0.000 claims description 3
- MJDYBKUPGFFNRO-UHFFFAOYSA-N 5-ethenyl-1,2,3-trimethylbenzene Chemical compound CC1=CC(C=C)=CC(C)=C1C MJDYBKUPGFFNRO-UHFFFAOYSA-N 0.000 claims description 3
- XOGTZOOQQBDUSI-UHFFFAOYSA-M Mesna Chemical compound [Na+].[O-]S(=O)(=O)CCS XOGTZOOQQBDUSI-UHFFFAOYSA-M 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 claims description 2
- UFMLLTODLZCTMW-UHFFFAOYSA-N 1-ethenyl-2,3,4,5,6-pentamethylbenzene Chemical compound CC1=C(C)C(C)=C(C=C)C(C)=C1C UFMLLTODLZCTMW-UHFFFAOYSA-N 0.000 claims description 2
- CDVJOHHCJGQSJH-UHFFFAOYSA-N 1-ethenyl-2,3,4,5-tetramethylbenzene Chemical compound CC1=CC(C=C)=C(C)C(C)=C1C CDVJOHHCJGQSJH-UHFFFAOYSA-N 0.000 claims description 2
- BEAZTUKYVBCHQY-UHFFFAOYSA-N 2-ethenyl-1,3,4,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1C BEAZTUKYVBCHQY-UHFFFAOYSA-N 0.000 claims description 2
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940087596 sodium phenolsulfonate Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims 2
- 210000004379 membrane Anatomy 0.000 description 98
- 210000002469 basement membrane Anatomy 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 125000005997 bromomethyl group Chemical group 0.000 description 14
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 229940077388 benzenesulfonate Drugs 0.000 description 10
- 229940031827 phenolate sodium Drugs 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- XJGIDGNLXAJIOA-UHFFFAOYSA-N 2,11,20,29,37,38,39,40-octazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(36),2,4,6,8,10(40),11,13,15,17,19,21(38),22,24,26,28,30,32,34-nonadecaen-37-amine Chemical compound Nn1c2nc3nc(nc4[nH]c(nc5nc(nc1c1ccccc21)c1ccccc51)c1ccccc41)c1ccccc31 XJGIDGNLXAJIOA-UHFFFAOYSA-N 0.000 description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- COVXBJIKNGVTNV-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;1,1-difluoroethene Chemical group FC(F)=C.FC(F)=C(F)Cl COVXBJIKNGVTNV-UHFFFAOYSA-N 0.000 description 2
- UCFZBOCMNGFLQX-UHFFFAOYSA-N [Co]N Chemical compound [Co]N UCFZBOCMNGFLQX-UHFFFAOYSA-N 0.000 description 2
- ZYBNERJTDVKVJJ-UHFFFAOYSA-N [Fe]N Chemical compound [Fe]N ZYBNERJTDVKVJJ-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000131 polyvinylidene Polymers 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ATTRMYMZQWIZOR-RRKCRQDMSA-N 4-amino-1-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-6-methyl-1,3,5-triazin-2-one Chemical compound CC1=NC(N)=NC(=O)N1[C@@H]1O[C@H](CO)[C@@H](O)C1 ATTRMYMZQWIZOR-RRKCRQDMSA-N 0.000 description 1
- 101710141544 Allatotropin-related peptide Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a monolithic polytrifluorochloroethylene bipolar membrane containing metal phthalocyanine derivative water dissociation catalyst and a preparation method thereof, belonging to the field of electrically driven membranes.
Description
Technical Field
The invention relates to a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst and a preparation method thereof, belonging to the technical field of electrically driven membranes.
Background
The bipolar membrane is a composite membrane material compounded by an anion exchange membrane, a cation exchange membrane and an intermediate catalyst layer. Under the action of an electric field, water molecules in the middle layer of the bipolar membrane are subjected to water dissociation to generate hydrogen ions and hydroxyl, so that the purpose of acid and alkali production is achieved. The theoretical potential of acid and alkali produced by the water dissociation of the bipolar membrane is 0.828V, and the theoretical voltage of acid and alkali produced by the electrolysis of water is 2.057V. In addition, the water dissociation rate of the bipolar membrane intermediate layer is about 5000 ten thousand times faster than that in the ordinary case. Therefore, the bipolar membrane technology has the characteristics of low energy consumption, high efficiency, no pollution of products and the like, and is widely applied to various fields of acid and alkali production and recovery, ocean chemical industry, pollution treatment, organic synthesis and the like.
Aromatic carbon skeletons such as polyaryletherketone and the like are commonly used bipolar membrane substrate materials at present, and quaternary ammonium functional groups are common functional groups of anion exchange membranes in bipolar membranes. However, the carbon-oxygen bond in the aromatic carbon skeleton is easily degraded by the attack of hydroxyl, and because of the attack of hydroxyl, the quaternary ammonium functional group is destroyed due to hoffman reaction, affinity substitution reaction and the like, so that the acid-base concentration generated by the bipolar membrane electrodialysis is generally low. Therefore, the control of the acid-base concentration is crucial to the application of acid-base generated by the bipolar membrane. On the other hand, the existing bipolar membrane is formed by compounding an anion exchange membrane, a cation exchange membrane and an intermediate catalyst layer, and due to the difference of physicochemical properties of different layers, the bipolar membrane is easy to peel off in the use process, so that the service life of the bipolar membrane is further shortened.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst and a preparation method thereof.
The technical scheme of the invention is as follows:
one of the purposes of the invention is to provide a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst, wherein one side of the bipolar membrane is introduced with a sulfonic acid group, and the other side of the bipolar membrane is introduced with a quaternary ammonium group;
the structural formula of the cation exchange membrane in the bipolar membrane is as follows: the structural formula of the cation exchange membrane in the bipolar membrane is as follows:
the anion exchange membrane has the structural formula:
the structural formula of the intermediate interfacial catalyst is as follows:
wherein n is the polymerization degree of the main chain of the polytrifluorochloroethylene basal membrane, m is the polymerization degree of the polybromomethylstyrene side chain, and n and m are integers which are not zero.
The invention also aims to provide a preparation method of the monolithic polytrifluorochloroethylene bipolar membrane containing the metal phthalocyanine derivative water dissociation catalyst, which comprises the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer: dissolving polychlorotrifluoroethylene in an organic solvent I, introducing nitrogen to remove oxygen, heating, mixing according to the molar ratio of polychlorotrifluoroethylene, a methyl styrene monomer, CuBr and bipyridine or pentamethyl diethylenetriamine being 1 (20-100): 1:2, reacting for 5-40 h at constant temperature under the protection of nitrogen, pouring the reaction liquid into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a grafted combination; leaching the precipitate with alcohol water for multiple times, soaking in running water for 24h, filtering, and drying to obtain polychlorotrifluoroethylene grafted polymethyl styrene graft polymer (PCTFE-g-PMST);
s2, bromination: dissolving the polychlorotrifluoroethylene grafted polymethyl styrene graft polymer prepared in the step S1 in an organic solvent II, adding a brominating agent and an initiator, boiling and refluxing for 4-6 h under the conditions of heating and stirring, stopping heating and stirring after full reaction, precipitating white floccules in anhydrous methanol or isopropanol, washing to remove impurities, and drying to obtain a bromomethylated polymer (PCTFE-g-BrPMST);
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the solution on a clean glass plate after the polymer is completely dissolved, and drying to prepare a polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene base membrane prepared in the step S3 in a reactor, respectively soaking two side surfaces of the base membrane in a sulfonation reagent and a negative membrane functional reaction reagent, introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at the temperature of 20-70 ℃ for reacting for 40-60 hours;
s5, preparing a bipolar membrane: after the negative film functionalization reaction is finished, continuing the sulfonation reaction at 20-90 ℃, and keeping the sulfonation reaction time for 50-72 h longer than the negative film functionalization reaction time; and (2) introducing sulfonic acid groups through sulfonation reaction, removing reaction liquid on one side of the cathode membrane, changing the reaction liquid into intermediate interface layer catalyst reaction liquid and cathode membrane functional reagent mixed solution for continuous reaction, introducing anion exchange groups and sulfonic acid groups into two sides of the base membrane respectively, introducing metal phthalocyanine derivatives and anion exchange groups into a thin layer between the two sides, and removing residual reaction liquid in the base membrane after the reaction is finished to obtain the monolithic polytrifluorochloroethylene bipolar membrane containing the metal phthalocyanine derivative water dissociation catalyst.
Further, in the step S1, the methylstyrene monomer is any one of 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2, 4-dimethylstyrene, 3, 4-dimethylstyrene, 2,3, 4-trimethylstyrene, 3,4, 5-trimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,4, 5-tetramethylstyrene, 2,3,4, 6-tetramethylstyrene, and 2,3,4,5, 6-pentamethylstyrene monomer.
Further, in the step S1, the organic solvent i is any one or a combination of two of N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any ratio.
Further, in the step S2, the organic solvent ii is any one or a combination of two of 1, 2-dichloroethane, chlorobenzene and carbon tetrachloride in any proportion.
Further, the solvent of the sulfonation reagent in the step S4 is any one of sodium phenolsulfonate, sodium hydroxybenzenesulfonate, sodium hydroxysulfonate, sodium 2-hydroxysulfonate, sodium 3-hydroxysulfonate, sodium 4-hydroxysulfonate, sodium mercaptoethylsulfonate or sodium mercaptopropylsulfonate, and the solution of the sulfonation reagent is one of distilled water, THF, DMF, DMAc, NMP and DMSO or a mixture of two of them in any proportion.
Further, in step S4, the solvent of the reaction reagent for negative membrane functionalization is any one of trimethylamine, triethylamine, dimethylimidazole, trimethylimidazole, methylethylimidazole, dimethylpropylimidazole, dimethylbutylimidazole, tetramethylimidazole, trimethylethylimidazole, methylethylimidazole, pentamethylguanidine, tetramethylethylguanidine, tetramethylpropylguanidine, tetramethylbutylguanidine, tetramethylhexylguanidine, or N-methylmorpholine, and the solution of the reaction reagent for negative membrane functionalization is one of distilled water, THF, DMF, DMAc, NMP, and DMSO or a combination of two of them at any ratio.
Further, the intermediate interface layer catalyst reaction liquid is an alcohol/water solution containing a metal phthalocyanine derivative.
Further, the phthalocyanine is any one of hydroxyl substituent phthalocyanine, amino substituent phthalocyanine, phthalocyanine containing transition metal hydroxyl substituent or phthalocyanine containing transition metal amino substituent.
Further, the metal phthalocyanine derivative central ion may be any one of inorganic metal ions.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst, which comprises the steps of polymerizing by ATRP, brominating polytrifluorochloroethylene grafted methyl styrene polymer by NBS to control the molecular weight of side chains of polymethyl styrene, obtaining bromomethylation polymer after bromination, further forming a base membrane material, introducing sulfonic acid groups and anion exchange groups by utilizing the reaction of bromomethyl and corresponding reagents, forming the monolithic bipolar membrane simultaneously provided with anion and cation exchange membrane layers, omitting a membrane forming process in the preparation process of the traditional bipolar membrane, and avoiding the use of carcinogenic substance chloromethyl ether.
(2) According to the invention, the bromomethyl of the side chain of the bipolar membrane reacts with the metal phthalocyanine derivative, so that the polytrifluorochloroethylene side chain is bonded with the metal phthalocyanine derivative to be used as a bipolar membrane middle layer water dissociation catalyst, the prepared bipolar membrane has low resistance and low transmembrane voltage, and the water dissociation catalyst is not easy to run off.
(3) The monolithic bipolar membrane prepared by the method provided by the invention has the advantages that the problems of bubbling, cracking and the like which are easily caused in the using process of the sandwich bipolar membrane can be avoided even if the monolithic bipolar membrane is used for a long time.
Detailed Description
The invention is further described in connection with the preferred embodiments, and the endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to such ranges or values; for numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified;
the experimental procedures in the following examples are conventional unless otherwise specified.
In the following examples, poly (vinylidene fluoride-chlorotrifluoroethylene) was used as the polychlorotrifluoroethylene, and the resulting polychlorotrifluoroethylene-grafted polymethylstyrene copolymer was a poly (vinylidene fluoride-chlorotrifluoroethylene) -grafted polymethylstyrene copolymer.
Example 1
A monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst, wherein one side of the bipolar membrane is introduced with sulfonic acid groups, and the other side of the bipolar membrane is introduced with quaternary ammonium groups; the structural formula of the cation exchange membrane in the bipolar membrane is as follows:
the anion exchange membrane has the structural formula:
the structural formula of the intermediate interfacial catalyst is as follows:
wherein n is the polymerization degree of the main chain of the polytrifluorochloroethylene basal membrane, m is the polymerization degree of the polybromomethylstyrene side chain, and n and m are integers which are not zero.
Example 2
A monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst, comprising the steps of:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer (PCTFE-g-PMST): weighing 20g of polychlorotrifluoroethylene, dissolving in 200mL of N-methylpyrrolidone, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 144.1g of 4-methylstyrene, 8.72g of CuBr and 9.52g of bipyridine into a reaction system, reacting at constant temperature for 40 hours under the protection of nitrogen, pouring the reaction solution into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a graft conjugate; leaching the precipitate with alcohol water for multiple times, then soaking the precipitate in running water for 24 hours to remove copper ions and bipyridine, filtering and drying the precipitate, putting the precipitate into a Soxhlet extractor to be extracted with toluene for 10 hours to completely remove homopolymer polystyrene, and putting the precipitate into a vacuum drying oven at 80 ℃ to be dried for 24 hours to prepare the polytrifluorochloroethylene grafted polymethylstyrene graft polymer, wherein the reaction formula is as follows:
s2, bromination: weighing 10g of polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, dissolving in 150mL of chlorobenzene, adding 9.04g N-bromosuccinimide as a brominating agent and 0.9g of dicumyl peroxide as an initiator, boiling and refluxing for 6h under the conditions of 130 ℃ and stirring, gradually changing the solution into orange red along with the reaction, continuing to react for a period of time after the orange red fades, stopping heating and stirring, precipitating white floccule in anhydrous methanol or isopropanol, extracting the white floccule in a Soxhlet extractor with acetone for 20h to remove impurities, and drying to obtain the bromomethylation polymer, wherein the reaction formula is as follows:
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the bromomethylated polymer on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene basement membrane prepared in the step S3 in a reactor, and respectively soaking two side surfaces of the basement membrane in a sulfonation reagent and a negative membrane functional reaction reagent, wherein the solvent of the sulfonation reagent is sodium p-phenolate sodium benzenesulfonate, and the solution is a mixed solution of distilled water and DMF (sodium p-phenolate sodium benzenesulfonate: H)2The mass ratio of O to DMF is 1:8:2), the solvent of the negative membrane functionalization reaction reagent is trimethylamine, and the solution is a mixed solution of distilled water and DMF (trimethylamine: H)2The mass ratio of O to DMF is 1:9:1), and the basement membrane separates the two reagents; introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at 70 ℃ for reaction;
s5, preparing a bipolar membrane: after the cathode membrane functionalization reaction is finished for 50 hours, continuing the sulfonation reaction at 90 ℃, maintaining the sulfonation reaction for 65 hours, introducing sulfonic acid groups into the sulfonation reaction, removing reaction liquid on one side of the cathode membrane, changing the reaction liquid into amino phthalocyanine iron alcohol/water solution, continuing the reaction for 10 hours, introducing anion exchange groups into bromomethyl on the outer layer of the cathode basement membrane and a cathode membrane functionalization reagent, introducing phthalocyanine into the bromomethyl on the inner layer of the cathode basement membrane and amino phthalocyanine iron through reaction, introducing a water dissociation catalyst into a cathode interface layer and an anode interface layer, and removing residual reaction liquid in the basement membrane after the reaction is finished to obtain the single-chip type polytrifluorochloroethylene bipolar membrane containing the phthalocyanine derivative water dissociation catalytic groups, wherein the ion exchange capacity of the anode is 1-2.5mmol/g, the ion exchange capacity of the cathode is 0.8-3.2mmol/g, and the specific reaction formula is as follows:
example 3
A preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst comprises the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer (PCTFE-g-PMST): weighing 20g of polychlorotrifluoroethylene, dissolving in 200mL of dimethyl sulfoxide, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 180.1g of 2-methylstyrene, 8.72g of CuBr and 21.13g of pentamethyldiethylenetriamine into a reaction system, reacting for 5 hours at constant temperature under the protection of nitrogen, pouring the reaction solution into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a graft conjugate; leaching the precipitate with alcohol water for multiple times, then soaking the precipitate in running water for 24 hours to remove copper ions and pentamethyldiethylenetriamine, filtering and drying the precipitate, putting the precipitate into a Soxhlet extractor, extracting the precipitate with toluene for 10 hours to completely remove homopolymer polystyrene, and putting the precipitate into a vacuum drying oven at 80 ℃ to dry the precipitate for 24 hours to prepare the polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, wherein the reaction formula is as follows:
s2, bromination: weighing 10g of polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, dissolving in 160mL of 1, 2-dichloroethane, adding 10.84g N-bromosuccinimide as a brominating agent and 1.08g of dicumyl peroxide as an initiator, boiling and refluxing for 5h under the conditions of 130 ℃ and stirring, gradually changing the solution into orange red along with the reaction, continuing the reaction for a period of time after the orange red fades, stopping heating and stirring, precipitating white floccules in anhydrous methanol or isopropanol, extracting the white floccules in a Soxhlet extractor with acetone for 20h to remove impurities, and drying to obtain the bromomethylated polymer, wherein the reaction formula is shown in example 1:
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the solution on a clean glass plate after the polymer is completely dissolved, and drying to prepare a polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene basement membrane prepared in the step S3 in a reactor, and respectively soaking two side surfaces of the basement membrane in a sulfonation reagent and a negative membrane functional reaction reagent, wherein the solvent of the sulfonation reagent is sodium p-phenolate sodium benzenesulfonate, and the solution is a mixed solution of distilled water and THF (sodium p-phenolate sodium benzenesulfonate: H)2THF is in a mass ratio of 1:7:3), the solvent of the quaternization reagent is dimethylimidazole, and the solution is a mixed solution of distilled water and THF (dimethylimidazole: H)2THF in a mass ratio of 1:8:2), and the base membrane separates the two reagents; introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at 20 ℃ for reaction;
s5, preparing a bipolar membrane: after the cathode membrane functionalization reaction is finished for 60 hours, continuing the sulfonation reaction at 20 ℃ for 72 hours; removing reaction liquid on one side of the cathode membrane, changing the reaction liquid into amino iron phthalocyanine alcohol/water solution, continuing to react for 8 hours, introducing an anion exchange group into bromomethyl on the outer layer of the cathode basement membrane and a cathode membrane functional reagent, introducing phthalocyanine into the bromomethyl on the inner layer of the cathode basement membrane and the amino iron phthalocyanine by reaction, introducing a water dissociation catalyst into a cathode interface layer and an anode interface layer, and removing residual reaction liquid in the basement membrane after the reaction is finished to obtain the monolithic polytrifluorochloroethylene bipolar membrane containing the phthalocyanine derivative water dissociation catalytic group, wherein the specific reaction formula is as follows:
example 4
A preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst comprises the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer (PCTFE-g-PMST): weighing 20g of polychlorotrifluoroethylene, dissolving in 200mL of N, N-dimethylformamide, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 172.9g of 3-methyl styrene, 8.72g of CuBr and 21.13g of pentamethyl diethylenetriamine into a reaction system, reacting for 24 hours at constant temperature under the protection of nitrogen, pouring the reaction solution into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a grafting combination; leaching the precipitate with alcohol water for multiple times, then soaking the precipitate in running water for 24 hours to remove copper ions and pentamethyldiethylenetriamine, filtering and drying the precipitate, placing the precipitate in a Soxhlet extractor to extract the precipitate for 10 hours with toluene to completely remove homopolymer polystyrene, and placing the precipitate in a vacuum drying oven at 80 ℃ to dry the precipitate for 24 hours to prepare the polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, wherein the reaction formula is as shown in example 2;
s2, bromination: weighing 10g of polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, dissolving in 160mL of carbon tetrachloride, adding 10.04g N-bromosuccinimide as a brominating agent and 1.0g of dicumyl peroxide as an initiator, boiling and refluxing for 4h under the conditions of 130 ℃ and stirring, gradually changing the solution into orange red along with the reaction, continuing to react for a period of time after the orange red fades, stopping heating and stirring, precipitating white floccule in anhydrous methanol or isopropanol, extracting the white floccule in a Soxhlet extractor with acetone for 20h to remove impurities, and drying to obtain the bromomethylation polymer, wherein the reaction formula is shown in example 1:
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the solution on a clean glass plate after the polymer is completely dissolved, and drying to prepare a polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene basement membrane prepared in the step S3 in a reactor, and respectively soaking two side surfaces of the basement membrane in a sulfonation reagent and a negative membrane functional reaction reagent, wherein the solvent of the sulfonation reagent is sodium p-phenolate sodium benzenesulfonate, and the solution is a mixed solution of distilled water and DMAc (sodium p-phenolate sodium benzenesulfonate: H)2The mass ratio of O to DMAc is 1:7:3), the solvent of the negative membrane functionalization reaction reagent is trimethyl imidazole, and the solution is a mixed solution of distilled water and DMAc (trimethyl imidazole: H)2DMAc is in a mass ratio of 1:8:2), and the base membrane separates the two reagents; introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at 50 ℃ for reaction;
s5, preparing a bipolar membrane: after the negative film functionalization reaction is finished for 40 hours, continuing the sulfonation reaction at 80 ℃ for 50 hours; removing reaction liquid on one side of the negative film, changing the reaction liquid into amino phthalocyanine copper alcohol/water solution, continuously reacting for 10 hours, introducing quaternary ammonium groups into a bromomethyl group on the outer layer of the negative basement film and a quaternizing agent, introducing phthalocyanine by reacting the bromomethyl group on the inner layer of the negative basement film with the amino phthalocyanine copper, introducing a water dissociation catalyst into the negative interface layer and the positive interface layer, and removing residual reaction liquid in the basement film after the reaction is finished to obtain the monolithic polytrifluorochloroethylene bipolar film containing the metal phthalocyanine derivative water dissociation catalyst, wherein the specific reaction formula is as follows:
example 5
A preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst comprises the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer (PCTFE-g-PMST): weighing 20g of polychlorotrifluoroethylene, dissolving in 200mL of N, N-dimethylacetamide, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 172.9g of 3-methylstyrene, 8.72g of CuBr and 21.13g of pentamethyldiethylenetriamine into a reaction system, reacting for 36 hours at constant temperature under the protection of nitrogen, pouring the reaction solution into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a graft conjugate; leaching the precipitate with alcohol water for multiple times, then soaking the precipitate in running water for 24 hours to remove copper ions and pentamethyldiethylenetriamine, filtering and drying the precipitate, placing the precipitate in a Soxhlet extractor to extract the precipitate for 10 hours with toluene to completely remove homopolymer polystyrene, and placing the precipitate in a vacuum drying oven at 80 ℃ to dry the precipitate for 24 hours to prepare the polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, wherein the reaction formula is as shown in example 2;
s2, bromination: weighing 10g of polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, dissolving the polychlorotrifluoroethylene grafted polymethylstyrene graft polymer in 150mL of mixed solvent of carbon tetrachloride and chlorobenzene, adding 10.04g N-bromosuccinimide as a brominating agent and 1.0g of dicumyl peroxide as an initiator, boiling and refluxing for 6h under the conditions of 130 ℃ and stirring, gradually changing the solution into orange red along with the reaction, continuing to react for a period of time after the orange red fades, stopping heating and stirring, precipitating white floccule in anhydrous methanol or isopropanol, extracting the white floccule in a Soxhlet extractor with acetone for 20h to remove impurities, and drying to obtain the bromomethylated polymer, wherein the reaction formula is shown in example 1:
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the bromomethylated polymer on a clean glass plate after the polymer is completely dissolved, and drying to prepare the polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene base membrane prepared in the step S3 in a reactor, and respectively soaking two side surfaces of the base membrane in a sulfonation reagent and a negative membrane functional reaction reagent, wherein the solvent of the sulfonation reagent is sodium p-phenolate sodium benzenesulfonate, and the solution is a mixed solution of distilled water and NMP (sodium p-phenolate sodium benzenesulfonate: H)2The mass ratio of O to NMP is 1:7:3), the solvent of the negative membrane functionalization reaction reagent is pentamethylguanidine, and the solution is a mixed solution of distilled water and NMP (pentamethylguanidine: H)2The mass ratio of O to NMP is 1:8:2), and the base membrane separates the two reagents; after nitrogen is introduced to remove air in the reactorSealing the reactor, and placing the reactor in a constant-temperature water bath kettle at 60 ℃ for reaction;
s5, preparing a bipolar membrane: after the negative film functionalization reaction is finished for 40h, continuing the sulfonation reaction at 50 ℃ for 50 h; removing reaction liquid on one side of a quaternary anion membrane, changing the reaction liquid into amino phthalocyanine copper alcohol/water solution, continuing to react for 8 hours, introducing an anion exchange group into bromomethyl on the outer layer of a cathode basement membrane and a cathode membrane functional reaction reagent, introducing phthalocyanine into the bromomethyl on the inner layer of the cathode basement membrane and the amino phthalocyanine copper through reaction, introducing a water dissociation catalyst into a cathode interface layer and an anode interface layer, removing residual reaction liquid in the basement membrane after the reaction is finished, and obtaining the monolithic polytrifluorochloroethylene bipolar membrane containing the metal phthalocyanine derivative water dissociation catalyst, wherein the specific reaction formula is as follows:
example 6
A preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst comprises the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer (PCTFE-g-PMST): weighing 20g of polychlorotrifluoroethylene, dissolving in 200mL of N-methylpyrrolidone, introducing nitrogen to remove oxygen, heating to 110 ℃, adding 144.1g of 2-methylstyrene, 8.72g of CuBr and 9.52g of bipyridine into a reaction system, reacting for 20 hours at constant temperature under the protection of nitrogen, pouring the reaction solution into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a graft conjugate; leaching the precipitate with alcohol water for multiple times, then soaking the precipitate in running water for 24 hours to remove copper ions and bipyridine, filtering and drying the precipitate, placing the precipitate in a Soxhlet extractor to be extracted with toluene for 10 hours to completely remove homopolymer polystyrene, and placing the precipitate in a vacuum drying oven at 80 ℃ to be dried for 24 hours to prepare the polytrifluorochloroethylene grafted polymethylstyrene graft polymer, wherein the reaction formula is shown in example 1:
s2, bromination: weighing 10g of polychlorotrifluoroethylene grafted polymethylstyrene graft polymer, dissolving in 150mL of a mixed solvent of 1, 2-dichloroethane and chlorobenzene, adding 10.04g N-bromosuccinimide as a brominating agent and 1.0g of dicumyl peroxide as an initiator, boiling and refluxing for 4h under the conditions of 130 ℃ and stirring, gradually changing the solution into orange red along with the reaction, continuing to react for a period of time after the orange red fades, stopping heating and stirring, precipitating white floccule in anhydrous methanol or isopropanol, putting the white floccule into a Soxhlet extractor, extracting with acetone for 20h to remove impurities, and drying to obtain the bromomethylated polymer, wherein the reaction formula is shown in example 1:
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the solution on a clean glass plate after the polymer is completely dissolved, and drying to prepare a polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of the base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene basement membrane prepared in the step S3 in a reactor, and respectively soaking two side surfaces of the basement membrane in a sulfonation reagent and a negative membrane functional reaction reagent, wherein the solvent of the sulfonation reagent is sodium p-phenolate sodium benzenesulfonate, and the solution is a mixed solution of distilled water and DMSO (sodium p-phenolate sodium benzenesulfonate: H)2DMSO is 1:7:3 in mass ratio, the solvent of the negative membrane functionalization reaction reagent is N-methylmorpholine, and the solution is a mixed solution of distilled water and DMSO (N-methylmorpholine: H)2DMSO is 1:8:2) by mass, and the base membrane separates the two reagents; introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at 60 ℃ for reaction; the bromomethyl on the positive basal membrane reacts with a sulfonation reagent to introduce sulfonic acid groups, and the bromomethyl on the negative basal membrane reacts with a negative membrane functionalization reaction reagent to introduce anion exchange groups, namely quaternary ammonium groups;
s5, preparing a bipolar membrane: after the negative membrane functionalization reaction is finished for 10 hours, continuing the sulfonation reaction at 45 ℃ until 20 hours are finished; removing reaction liquid on one side of a negative film, changing the reaction liquid into amino cobalt phthalocyanine alcohol/water solution, continuing to react for 8 hours, introducing an anion exchange group into bromomethyl on the outer layer of the negative basement membrane and a negative film functionalized reaction reagent, introducing phthalocyanine into the bromomethyl on the inner layer of the negative basement membrane through reaction with the amino cobalt phthalocyanine, introducing a water dissociation catalyst into a negative interface layer and a positive interface layer, and removing residual reaction liquid in the basement membrane after the reaction is finished to obtain the monolithic polytrifluorochloroethylene bipolar membrane containing the metal phthalocyanine derivative water dissociation catalyst, wherein the specific reaction formula is as follows:
in addition to the above embodiments, the methylstyrene monomer in step S1 in the present invention may be any one of 2, 4-dimethylstyrene, 3, 4-dimethylstyrene, 2,3, 4-trimethylstyrene, and 3,4, 5-trimethylstyrene monomer; the organic solvent I can also be the combination of two of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion; the solvent of the sulfonation reagent in the step S4 can be any one of sodium hydroxybenzenesulfonate, sodium hydroxysulfonate, 2-sodium hydroxysulfonate, 3-sodium hydroxysulfonate, 4-sodium hydroxysulfonate, sodium mercaptoethylsulfonate or sodium mercaptopropylsulfonate; the solvent of the quaternization reagent can be any one of triethylamine, methyl ethyl imidazole, dimethyl propyl imidazole, dimethyl butyl imidazole, tetramethyl imidazole, trimethyl ethyl imidazole, methyl ethyl imidazole, tetramethyl ethyl guanidine, tetramethyl propyl guanidine, tetramethyl butyl guanidine and tetramethyl hexyl guanidine; the phthalocyanine can also be any one of hydroxyl substituent phthalocyanine, amino substituent phthalocyanine and transition metal-containing hydroxyl substituent phthalocyanine.
The above-mentioned embodiments are only preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present patent.
Claims (10)
1. A monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst, characterized in that: introducing a sulfonic acid group into one surface of the bipolar membrane, and introducing a quaternary ammonium group into the other surface of the bipolar membrane; the structural formula of the cation exchange membrane in the bipolar membrane is as follows:
the anion exchange membrane has the structural formula:
the structural formula of the intermediate interfacial catalyst is as follows:
wherein n is the polymerization degree of the main chain of the polytrifluorochloroethylene base membrane, m is the polymerization degree of the polybromomethylstyrene side chain, and n and m are integers which are not zero.
2. A preparation method of a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst is characterized by comprising the following steps:
s1, preparing a polychlorotrifluoroethylene grafted polymethyl styrene copolymer: dissolving polychlorotrifluoroethylene in an organic solvent I, introducing nitrogen to remove oxygen, heating, mixing according to the molar ratio of polychlorotrifluoroethylene, a methyl styrene monomer, CuBr and bipyridine or pentamethyl diethylenetriamine being 1 (20-100): 1:2, reacting for 5-40 h at constant temperature under the protection of nitrogen, pouring the reaction liquid into an alcohol-water mixed solvent with the volume ratio of 1:1, and precipitating to obtain a grafted combination; leaching the precipitate with alcohol water for multiple times, soaking in running water for 24h, filtering, and drying to obtain the polychlorotrifluoroethylene grafted polymethyl styrene graft polymer;
s2, bromination: dissolving the polychlorotrifluoroethylene grafted polymethyl styrene polymer prepared in the step S1 in an organic solvent II, adding a brominating agent and an initiator, boiling and refluxing for 4-6 h under the conditions of heating and stirring, stopping heating and stirring after full reaction, precipitating white floccules in anhydrous methanol or isopropanol, washing to remove impurities, and drying to obtain a bromomethylation polymer;
s3, preparing a base film: dissolving the bromomethylated polymer prepared in the step S2 in N-dimethyl pyrrolidone, casting the solution on a clean glass plate after the polymer is completely dissolved, and drying to prepare a polychlorotrifluoroethylene grafted bromomethylated styrene base film;
s4, introducing ion exchange groups on two sides of a base membrane: placing the polychlorotrifluoroethylene grafted bromomethylated styrene base membrane prepared in the step S3 in a reactor, respectively soaking two side surfaces of the base membrane in a sulfonation reagent and a negative membrane functional reaction reagent, introducing nitrogen to remove air in the reactor, sealing the reactor, and placing the reactor in a constant-temperature water bath kettle at the temperature of 20-70 ℃ for reacting for 40-60 hours;
s5, preparing a bipolar membrane: after the negative film functionalization reaction is finished, continuing the sulfonation reaction at 20-90 ℃, and keeping the sulfonation reaction time for 50-72 h longer than the negative film functionalization reaction time; and (2) introducing sulfonic acid groups through sulfonation reaction, removing reaction liquid on one side of the cathode membrane, changing the reaction liquid into intermediate interface layer catalyst reaction liquid and cathode membrane functional reagent mixed solution for continuous reaction, introducing anion exchange groups and sulfonic acid groups into two sides of the base membrane respectively, introducing metal phthalocyanine derivatives and anion exchange groups into a thin layer between the two sides, and removing residual reaction liquid in the base membrane after the reaction is finished to obtain the monolithic polytrifluorochloroethylene bipolar membrane containing the metal phthalocyanine derivative water dissociation catalyst.
3. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: in step S1, the methylstyrene monomer is any one of 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 2, 4-dimethylstyrene, 3, 4-dimethylstyrene, 2,3, 4-trimethylstyrene, 3,4, 5-trimethylstyrene, 2,4, 6-trimethylstyrene, 2,3,4, 5-tetramethylstyrene, 2,3,4, 6-tetramethylstyrene, and 2,3,4,5, 6-pentamethylstyrene monomer.
4. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: in the step S1, the organic solvent I is any one or a combination of two of N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and N, N-dimethylformamide in any proportion.
5. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: and in the step S2, the organic solvent II is any one or a combination of two of 1, 2-dichloroethane, chlorobenzene and carbon tetrachloride in any proportion.
6. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: the solvent of the sulfonation reagent in the step S4 is any one of sodium phenolsulfonate, sodium hydroxybenzenesulfonate, sodium hydroxysulfonate, sodium 2-hydroxysulfonate, sodium 3-hydroxysulfonate, sodium 4-hydroxysulfonate, sodium mercaptoethylsulfonate or sodium mercaptopropylsulfonate, and the solution of the sulfonation reagent is one of distilled water, THF, DMF, DMAc, NMP and DMSO or a mixture of two of them in any proportion.
7. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: the solvent of the negative membrane functionalization reactant in the step S4 is any one of trimethylamine, triethylamine, dimethylimidazole, trimethylimidazole, methylethylimidazole, dimethylpropylimidazole, dimethylbutylimidazole, tetramethylimidazole, trimethylethylimidazole, methylethylimidazole, pentamethylguanidine, tetramethylethylguanidine, tetramethylpropylguanidine, tetramethylbutylguanidine, tetramethylhexylguanidine, or N-methylmorpholine, and the solution of the negative membrane functionalization reactant in the quaternary step S4 is one or a combination of two of distilled water, THF, DMF, DMAc, NMP, and DMSO in any proportion.
8. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst according to claim 2, wherein: the intermediate interface layer catalyst reaction liquid is an alcohol/water solution containing a metal phthalocyanine derivative.
9. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst of claim 8, wherein: the phthalocyanine is any one of hydroxyl substituent phthalocyanine, amino substituent phthalocyanine, phthalocyanine containing transition metal hydroxyl substituent or phthalocyanine containing transition metal amino substituent.
10. The method for preparing a monolithic polytrifluorochloroethylene bipolar membrane containing a metal phthalocyanine derivative water dissociation catalyst as claimed in claim 9, wherein: the metal phthalocyanine derivative central ion can be any one of inorganic metal ions.
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