CN111454434B - Metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate - Google Patents
Metalloporphyrin complex, preparation method thereof and preparation method of polycarbonate Download PDFInfo
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- CN111454434B CN111454434B CN202010411745.2A CN202010411745A CN111454434B CN 111454434 B CN111454434 B CN 111454434B CN 202010411745 A CN202010411745 A CN 202010411745A CN 111454434 B CN111454434 B CN 111454434B
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- 229920000515 polycarbonate Polymers 0.000 title claims description 63
- 239000004417 polycarbonate Substances 0.000 title claims description 63
- 238000002360 preparation method Methods 0.000 title description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 62
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 62
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 46
- 150000002118 epoxides Chemical class 0.000 claims abstract description 29
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 14
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims description 147
- -1 halide anions Chemical class 0.000 claims description 80
- 238000006116 polymerization reaction Methods 0.000 claims description 60
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical group CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims description 6
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 175
- 230000003197 catalytic effect Effects 0.000 abstract description 34
- 239000000047 product Substances 0.000 abstract description 31
- 125000005587 carbonate group Chemical group 0.000 abstract description 17
- 238000009826 distribution Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 6
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 150000005676 cyclic carbonates Chemical class 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 129
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 50
- 239000000243 solution Substances 0.000 description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- 229910052786 argon Inorganic materials 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- 238000003756 stirring Methods 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000005160 1H NMR spectroscopy Methods 0.000 description 25
- 238000005481 NMR spectroscopy Methods 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 24
- 230000006837 decompression Effects 0.000 description 24
- 238000005227 gel permeation chromatography Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 239000012043 crude product Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 230000005311 nuclear magnetism Effects 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- 238000007599 discharging Methods 0.000 description 12
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- 230000007935 neutral effect Effects 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229920000379 polypropylene carbonate Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WNGGWVAYNUANOX-UHFFFAOYSA-N [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 Chemical compound [N]1C2=CC=C1C=C(N1)C=C(O)C1=CC([N]1)=CC=C1C=C(N1)C=CC1=C2 WNGGWVAYNUANOX-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
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- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 description 1
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
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- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
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- 238000002523 gelfiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- BOFQSBUEWRVAHJ-UHFFFAOYSA-N methoxymethane;dihydrochloride Chemical compound Cl.Cl.COC BOFQSBUEWRVAHJ-UHFFFAOYSA-N 0.000 description 1
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- 238000004806 packaging method and process Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- JMOHQJVXBQAVNW-UHFFFAOYSA-M sodium;2,4-dinitrophenolate Chemical compound [Na+].[O-]C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O JMOHQJVXBQAVNW-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
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- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
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- 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
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/152—Side-groups comprising metal complexes
- C08G2261/1528—Side-groups comprising metal complexes of Al
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- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/40—Polymerisation processes
- C08G2261/41—Organometallic coupling reactions
- C08G2261/418—Ring opening metathesis polymerisation [ROMP]
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Abstract
The invention provides a metalloporphyrin complex with a structure shown in a formula (I) or a formula (II). The metalloporphyrin complex has an oligomeric main chain structure formed based on ring-opening metathesis polymerization, and meanwhile, the metalloporphyrin complex contains quaternary ammonium salt or quaternary phosphonium salt functional groups, and the difunctional metalloporphyrin complex with the oligomeric structure has the catalytic characteristics of multiple active centers and difunctional catalysts. In the copolymerization of carbon dioxide and epoxide, the complex has high catalytic activity and high selectivity, and no cocatalyst is needed. Experimental results show that the maximum conversion number (TOF) of the catalytic system can reach 18000h when the copolymerization of carbon dioxide and epoxide is catalyzed ‑1 The method comprises the steps of carrying out a first treatment on the surface of the Less than 10% of cyclic carbonate by-product in the copolymerization product; the carbonate unit content of the prepared polymer reaches 70% -90%, the number average molecular weight is 10,000-250,000 g/mol, and the molecular weight distribution is 1.20-1.35.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a metalloporphyrin complex, a preparation method thereof and a preparation method of polycarbonate.
Background
The conversion and immobilization of carbon dioxide into polymeric materials has become an important research direction in the field of carbon dioxide utilization, where CO 2 The method is most attractive in ring-opening copolymerization Reaction (ROCOP) with Propylene Oxide (PO), the carbon dioxide fixation amount in the Prepared Polypropylene Carbonate (PPC) can reach more than 40%, and the PPC has extremely high application value in the fields of disposable plastic packaging, agricultural mulching films and environment-friendly polyurethane raw materials. Inoue has first discovered CO since 1969 2 Since the ring-opening copolymerization with epoxides, a wide variety of heterogeneous and homogeneous catalytic systems have been developed in the art, all of which aim to increase catalytic activity and selectivity, while at the same time well controlling the polymer structure. Various heterogeneous catalysts including rare earth ternary catalysts have been applied to the industrialization of polycarbonate, but the catalytic activity and selectivity of heterogeneous catalysts are still far lower than those of homogeneous catalysts, and the homogeneous catalysts have definite catalyst structures, so that the molecular design and mechanism research are facilitated.
Early studies found goldThe catalyst has higher catalytic performance under the action of an externally added cocatalyst, so that the homogeneous catalyst is generally applied in a two-component system, and the two-component system consisting of salen or porphyrin complex of trivalent metal (cobalt, chromium and aluminum) and quaternary ammonium salt or macromolecular organic base is widely applied to catalyzing CO 2 Copolymerization with epoxide, research shows that the trivalent metal complex has an axial nucleophilic group which is a catalyst capable of catalyzing CO 2 Key factors for the copolymerization with epoxide. Wherein SalenCo/[ PPN ]][X]Is the most interesting two-component system, exhibiting good catalytic activity, polymer selectivity and stereochemical selectivity, however, the problems of lower catalyst activity and poor selectivity still prevent the further development of two-component systems. And long-time researches show that the substantial breakthrough of the catalyst performance cannot be realized by adjusting the substituent groups, the axial groups, the cocatalyst and the like of the catalyst ligand. In the subsequent research, a concept of a single-molecule difunctional catalyst is introduced, the core idea is that a cocatalyst component is bonded to a catalyst ligand, so that the catalyst can directionally activate the connected metal center and can also serve as a nucleophilic group to promote epoxy ring opening and chain growth, and the strategy verifies the effectiveness of the catalyst in a difunctional SalenCo and porphyrin aluminum system and shows good catalytic activity and selectivity.
In 2007, lee et al originally designed a novel bifunctional SalenCo complex containing a Lewis acid metal center and a quaternary ammonium salt in the same molecule [ J.Am.chem.Soc.,129 (26): 8082-8083.]. The complex still has excellent catalytic activity at high temperature and low concentration because of the interaction between the quaternary ammonium salt bonded to the ligand skeleton and the chain extension anion, so that the polymer chain extension segment always surrounds the metal center. On this basis, in 2008, lee bonded the polyammonium salt units to the ligands to synthesize new bifunctional complexes [ angelw.chem.int.ed., 47:7306-7309.]At lower catalyst concentrations ([ PO)]/[cat.]=100000/1), catalyze CO 2 The activity of the PO copolymerization is up to 22000h -1 And the catalyst can be recovered by silica gel filtration, and the catalytic activity is well maintained when the catalyst is recovered for use. In 2009, lu et al found MTBD functionalized SalenCo III X is joined in marriageThe compounds can also be used to prepare polypropylene carbonates with molecular weights exceeding 100kg/mol, carbonate unit contents>99%, furthermore at high reaction temperature (100 ℃) and low catalyst concentration ([ PO)]/[cat.]=10000/1) still maintains good catalytic performance [ j.am.chem.soc. ], 131 (32): 11509-11518.]. The design strategy of the difunctional catalyst obviously improves the performance, but the catalytic activity still cannot reach a satisfactory degree, and researches show that the bottleneck cannot be broken through simple catalyst modification or changing reaction conditions, and only the conventional new catalyst design thought is broken through, so that breakthrough is possible.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a metalloporphyrin complex, which does not need a catalytic auxiliary agent in the copolymerization reaction of carbon dioxide and epoxide, and has high catalytic activity and high selectivity.
Compared with the prior art, the invention provides a metalloporphyrin complex with a structure shown in a formula (I) or a formula (II). The metalloporphyrin complex has an oligomeric main chain structure formed based on ring-opening metathesis polymerization, and meanwhile, the metalloporphyrin complex contains quaternary ammonium salt or quaternary phosphonium salt functional groups. In the copolymerization of carbon dioxide with epoxide, the complex has high catalytic activity and high selectivity, and no cocatalyst is needed. Experimental results show that the highest conversion number (TOF) of the catalytic system can reach 18000h-1 when catalyzing the copolymerization reaction of carbon dioxide and epoxide; less than 10%, even less than 0.01% of cyclic carbonate by-product in the copolymerization product; the carbonate unit content of the prepared polymer reaches 70% -90%, the number average molecular weight is 10,000-250,000 g/mol, and the molecular weight distribution is 1.20-1.35.
Detailed Description
The invention provides a metalloporphyrin complex, a preparation method thereof and a preparation method of polycarbonate, and a person skilled in the art can refer to the content of the metalloporphyrin complex and the polycarbonate, and appropriately improve the technological parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.
The invention provides a metalloporphyrin complex with a structure of formula (I) or formula (II):
wherein x is an integer of 2 to 50; preferably an integer from 3 to 48; more preferably an integer of 5 to 45;
y is an integer of 1 to 25, preferably an integer of 2 to 23, more preferably an integer of 3 to 20,
the value of y is preferably 1 (1-10); more preferably 1 (1) to 8); specifically, the ratio may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7 or 1:8.
The said
Is a linking group; the linking group has the structure of formula (VII) or formula (VIII):
wherein: p is an integer of 1 to 10; preferably an integer of 1 to 8; may be 1,2,3,4,5,6,7 or 8.
The Ra is
The Rb is->
Said->
Or->
Is metalloporphyrin complex; said->
Is a difunctional metalloporphyrin complex having the structure of formula (III): said->
Is a metalloporphyrin complex having the structure of formula (VI):
wherein M is a metal element; preferably selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium; more preferably iron, cobalt or aluminum.
n is the degree of polymerization, n=1 to 10; and may be 1,2,3,4,5,6,7,8,9 or 10.
L is selected from one of quaternary ammonium salt functional groups and quaternary phosphonium salt functional groups; l is preferably one of a quaternary ammonium salt functional group having the structure of formula (IV) and a quaternary phosphonium salt functional group having the structure of formula (V):
wherein n, m and k are independently selected from integers from 1 to 6; and may be 1,2,3,4,5 or 6.
Y 1 - And Y 2 - Independently selected from halide anions, NO 3 - 、CH 3 COO - 、CCl 3 COO - 、CF 3 COO - 、ClO 4 - 、BF 4 - One or more of p-toluenesulfonic acid group, p-methylbenzoic acid group, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion and pentafluorophenol oxy anion.
X is independently selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 One or more of p-methylbenzoic acid group, p-methylbenzenesulfonic acid group, o-nitrophenoxy group, p-nitrophenoxy group, m-nitrophenoxy group, 2, 4-dinitrophenol oxy group, 3, 5-dinitrophenol oxy group, 2,4, 6-trinitrophenol oxy group, 3, 5-dichlorophenol oxy group, 3, 5-difluorophenol oxy group, 3, 5-di-trifluoromethyl phenol oxy group or pentafluorophenol oxy anion.
The R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R is 19 Independently selected from one of hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, aryl with benzene ring number of 1-3 or substituted aryl with benzene ring number of 1-3; wherein the aryl of C6-C30 is preferably aryl with benzene ring number of 1-3; the substituted C6-C30 aryl group is preferably a substituted aryl group having 1 to 3 benzene rings.
In the invention, the metalloporphyrin complex is specifically represented by formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106;
wherein x is an integer of 2 to 50; preferably an integer from 3 to 48; more preferably an integer of 5 to 45; y is an integer of 1 to 25, preferably an integer of 2 to 23, more preferably an integer of 3 to 20.
The metalloporphyrin complex provided by the invention has a structure shown in a formula (I) or a formula (II), has an oligomeric main chain structure formed based on ring-opening metathesis polymerization, contains quaternary ammonium salt or quaternary phosphonium salt functional groups, and is creatively designed into a difunctional metalloporphyrin complex with an oligomeric structure, and has the catalytic characteristics of multiple active centers and a difunctional catalyst.
The invention provides a preparation method of metalloporphyrin complex, which comprises the following steps:
polymerizing a compound shown in a formula (i-6) by using a GrubsIII catalyst to obtain a compound shown in a formula (i-9);
reacting a compound shown in a formula (i-9) with a metal salt compound to obtain a compound shown in a formula (i-11);
reacting a tertiary amine compound shown in the formula (I-11) to obtain a compound shown in the formula (I);
or (b)
Polymerizing a compound shown in a formula (i-6) and a compound shown in a formula (i-8) by using a GrubsIII catalyst to obtain a compound shown in a formula (i-10);
reacting a compound shown in a formula (i-10) with a metal salt compound to obtain a compound shown in a formula (i-12);
reacting a compound shown in a formula (i-12) with a tertiary phosphine compound to obtain a compound shown in a formula (II);
wherein x is an integer of 2 to 50; y is an integer of 1-25, z is an integer of 1-25, the value of y is 1 (1-10), and M is a metal element; n is the degree of polymerization, n=1 to 10; l is selected from one of quaternary ammonium salt functional groups and quaternary phosphonium salt functional groups;
x is independently selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 One or more of p-methylbenzoic acid group, p-methylbenzenesulfonic acid group, o-nitrophenoxy group, p-nitrophenoxy group, m-nitrophenoxy group, 2, 4-dinitrophenol oxy group, 3, 5-dinitrophenol oxy group, 2,4, 6-trinitrophenol oxy group, 3, 5-dichlorophenol oxy group, 3, 5-difluorophenol oxy group, 3, 5-di-trifluoromethyl phenol oxy group or pentafluorophenol oxy anion.
The R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R is 19 Independently selected from one of hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, aryl with benzene ring number of 1-3 or substituted aryl with benzene ring number of 1-3.
The invention provides a preparation method of metalloporphyrin complex, which comprises the steps of polymerizing a compound shown in a formula (i-6) under the condition of adopting GrubsIII catalyst to obtain a compound shown in a formula (i-9). The polymerization is a ring-opening metathesis polymerization.
Reacting a compound shown in a formula (i-9) with a metal salt compound to obtain a compound shown in a formula (i-11); the metal in the metal salt compound is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium. The molar ratio of the porphyrin complex component in the compound shown in the formula (i-9) to the molar ratio of the metal salt compound is 1 (1.0-1.2);
reacting a tertiary amine compound shown in the formula (I-11) to obtain a compound shown in the formula (I); the tertiary amine compound is one of trimethylamine, tributylamine and trihexylamine. The temperature of the reaction is 25-40 ℃; the reaction time is 0.5 h-1.5 h.
According to the present invention, the preparation method of the compound represented by the formula (i-6) specifically comprises:
Reacting a compound with a structure shown in a formula (i-1) with 5-norbornene-2-carboxylic acid under the action of a catalyst to obtain a compound shown in a formula (i-2); the temperature of the reaction is preferably 50-60 ℃; the reaction time is preferably 16 to 20 hours.
p is an integer of 1 to 10; y is a negative ion in a quaternary ammonium salt functional group or a negative ion in a quaternary phosphonium salt functional group.
The catalyst of the invention is preferably 4-dimethylaminopyridine; the feeding mole ratio of the compound with the structure shown in the formula (i-1) to 5-norbornene-2-acyl chloride is 1 (5-20);
reacting a compound with a structure shown in a formula (i-3) with dimethyl ether dichloride under the action of a catalyst to obtain a compound with a structure shown in a formula (i-4); the temperature of the reaction is 25-45 ℃; the reaction time is 20 min-40 min.
n is an integer of 1 to 6; y is a negative ion in a quaternary ammonium salt functional group or a negative ion in a quaternary phosphonium salt functional group. The mass ratio of the compound having the structure represented by the formula (i-3) to dimethyl ether is preferably (1 to 3): 1.
Reacting a compound with a structure shown in a formula (i-4), 4-hydroxybenzaldehyde and pyrrole under the action of propionic acid to obtain a compound with a structure shown in a formula (i-5); the feeding mole ratio of the fourth compound of the compound with the structure shown in the formula (i-4), 4-hydroxybenzaldehyde and pyrrole is 1:3:4; the temperature of the reaction is 160-165 ℃; the reaction time is 45 min-1 h.
Under the action of a catalyst, a compound with a structure shown in a formula (i-5) reacts with 5-norbornene-2-acyl chloride or a compound shown in a formula (i-2) to obtain a compound shown in a formula (i-6). Wherein the reaction temperature of the compound with the structure shown in the formula (i-5) and 5-norbornene-2-acyl chloride is 60-80 ℃; the reaction time is 40-48 h.
In the formula (i-6)
Is said linking group.
The catalyst of the invention is preferably anhydrous potassium carbonate; the feeding mole ratio of the compound with the structure shown in the formula (i-5) to the 5-norbornene-2-acyl chloride is 1 (5-20), or the feeding mole ratio of the compound with the structure shown in the formula (i-5) to the second compound is (5-20): 1.
The preparation method of the metalloporphyrin complex provided by the invention comprises the steps of polymerizing a compound shown in a formula (i-6) and a compound shown in a formula (i-8) under the condition of using a GrubsIII catalyst to obtain a compound shown in a formula (i-10). The temperature of the reaction is 40-50 ℃; the reaction time is 3-4 hours;
the molar ratio of the compound shown in the formula (i-6) to the compound shown in the formula (i-8) is 1 (0.1-10);
the compound represented by the formula (i-10) is reacted with a metal salt compound to obtain a compound represented by the formula (i-12). The molar ratio of the porphyrin complex component in the formula (i-10) to the tertiary amine or tertiary phosphine compound is 1 (30-45); the temperature of the reaction is 25-30 ℃; the reaction time is 4-6 h.
Reacting a compound shown in a formula (i-12) with a tertiary phosphine compound to obtain a compound shown in a formula (II); the tertiary phosphine compound is triphenylphosphine. The temperature of the reaction is 25-40 ℃; the reaction time is 0.5 h-1.5 h.
In the present invention, the compound represented by the formula (i-8) is prepared by the following method:
the compound having the structure represented by the formula (i-7) is reacted with 5-norbornene-2-yl chloride or the compound represented by the formula (i-2) to give the compound of the formula (i-8). The reaction temperature of the compound with the structure shown in the formula (i-7) and the 5-norbornene-2-acyl chloride is 60 to 80 ℃; the reaction time is 40-48 hours; the reaction temperature of the compound with the structure shown in the formula (i-7) and the compound shown in the formula (i-2) is 40-50 ℃; the reaction time is 3-4 h.
The feeding mole ratio of the compound with the structure shown in the formula (i-7) and the 5-norbornene-2-acyl chloride is 1 (5-20), or the feeding mole ratio of the compound with the structure shown in the formula (i-7) and the second compound is (5-20): 1.
The present invention is not limited to the preparation method of the formula (i-7), and those skilled in the art will be familiar with the method.
R in the formula (i-7) and the formula (i-8) shown in the invention 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R is 19 Independently selected from one of hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, aryl with benzene ring number of 1-3 or substituted aryl with benzene ring number of 1-3.
The invention provides a preparation method of polycarbonate, which comprises the following steps:
the metalloporphyrin complex according to any one of claims 1 to 7 or the metalloporphyrin complex prepared by the method according to any one of claims 8 to 9 is used as a catalyst, and carbon dioxide and epoxide are subjected to copolymerization reaction to obtain polycarbonate.
The difunctional metalloporphyrin complex is used as a catalyst, and under the condition of no addition of a cocatalyst, the carbon dioxide and the epoxide are subjected to copolymerization reaction to obtain the polycarbonate.
According to the invention, the molar ratio of metalloporphyrin complex to epoxide is preferably 1 (2000 to 500000); more preferably 1 (3000 to 400000);
the pressure of the carbon dioxide is preferably 0.1-8.0 MPa; more preferably 0.5 to 7.0MPa; most preferably 1 to 6.0MPa.
The temperature of the copolymerization reaction is preferably 0-150 ℃; more preferably from 10℃to 130 ℃; most preferably from 30℃to 120 ℃; the time of the copolymerization reaction is preferably 0.5 to 48 hours; more preferably 0.5 to 40 hours; most preferably 0.5 to 20 hours.
The epoxide comprises one or more of ethylene oxide, propylene oxide, 1, 2-epoxybutane, epoxycyclohexane, epoxycyclopentane, epoxychloropropane, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether and styrene alkylene oxide.
The invention provides a metalloporphyrin complex with a structure shown in a formula (I) or a formula (II). The metalloporphyrin complex has an oligomeric main chain structure formed based on ring-opening metathesis polymerization, and meanwhile, the metalloporphyrin complex contains quaternary ammonium salt or quaternary phosphonium salt functional groups. In the copolymerization of carbon dioxide with epoxide, the complex has high catalytic activity and high selectivity, and no cocatalyst is needed. Experimental results show that the maximum conversion number (TOF) of the catalytic system can reach 18000h when the copolymerization of carbon dioxide and epoxide is catalyzed -1 The method comprises the steps of carrying out a first treatment on the surface of the Less than 10%, even less than 0.01% of cyclic carbonate by-product in the copolymerization product; the carbonate unit content of the prepared polymer reaches 70% -90%, the number average molecular weight is 10,000-250,000 g/mol, and the molecular weight distribution is 1.20-1.35.
In order to further illustrate the present invention, the following describes in detail a metalloporphyrin complex, a method for preparing the same, and a method for preparing polycarbonate, provided by the present invention, with reference to examples.
Example 1
Step a 1) 5-norbornene-2-carboxylic acid (3.62 mmol,1 equiv) and methylene chloride (30 mL) were added to a dry one-necked flask (100 mL) and dissolved by stirring. To the reaction solution, dicyclohexylcarbodiimide (DCC, 3.62mmol,1 equiv.) was added, and a first compound (3.62 mmol,1 equiv.) having a structure represented by formula (12), 4-dimethylaminopyridine (catalyst equivalent). The system is stirred and dissolved under the protection of argon, and heated and refluxed for 16h. After the completion of the reaction, the reaction solution was diluted with methylene chloride and filtered, and the filtrate was dried over anhydrous magnesium sulfate, and the solvent was removed in vacuo, whereby an oily product was obtained. The crude product was purified by silica gel column chromatography (n-hexane/ethyl acetate=20/1, V/V) to obtain a second compound having a structure represented by formula (13) as a light oil. High resolution electrospray mass spectrometry analysis, analysis results [ C12H17ClO2]:228.09, found:228.1.
Step b 1), adding a third compound (18 g) having a structure represented by formula (14) and titanium tetrachloride (24 g) to dry dichloromethane (120 mL) under ice bath conditions, then adding dichlorodimethyl methyl ether (8 g) to a solution of the third compound in 30min, reacting the obtained mixed solution at 35 ℃ for 30min, pouring the obtained reaction solution into a large beaker filled with ice water, then extracting with dichloromethane, collecting an organic phase, and washing with saturated sodium bicarbonate solution to obtain a crude product, and purifying the crude product by silica gel column chromatography, wherein an eluent is dichloromethane/petroleum ether=2/1 (volume ratio), thereby obtaining a fourth compound having a structure represented by formula (15). High resolution electrospray mass spectrometry analysis, analysis results [ C13H17BrO ]:268.05, found:268.0.
Step c 1), 4-hydroxybenzaldehyde (18 mmol) and a fourth compound (54 mmol) having a structure represented by formula (15) were added to a three-necked flask (500 mL), propionic acid (240 mL) was added thereto at a molar ratio of 1:3, and the system was heated to 130℃and stirred for 0.5h. Pyrrole (72 mmol) was then added dropwise and after completion the temperature was raised to 165℃and the mixture was allowed to reflux in air for 1h. After the completion of the reaction, the reaction mixture was cooled to room temperature, 500mL of methanol was added to the reaction mixture, and the mixture was left in a refrigerator overnight. The crude violet solid product was collected by filtration, washed with methanol and hot water, and dried. The crude product mainly comprises tetraphenylporphyrin, monohydroxy porphyrin and polyhydroxy porphyrin, a silica gel chromatographic column is used for separating the product, an eluent is pure dichloromethane, a second component is collected, and the product is dried after rotary evaporation, so that a fifth compound with a structure shown in a formula (16) is obtained. High resolution electrospray mass spectrometry analysis, analysis results [ C62H63Br3N4O ]:1116.26, found:1116.30.
Step d 1) in a magnetically stirred round bottom flask (250 mL), the second compound (15.8 mmol,2.5 equiv.) of the structure represented by formula (13), anhydrous potassium carbonate (15.8 mmol,2.5 equiv.), N, N-dimethylformamide (DMF, 50 mL) was added, respectively, and dissolved with stirring. The fifth compound (6.33 mmol,1 equiv) having the structure shown in formula (16) was dissolved in dry N, N-dimethylformamide (DMF, 30 mL), and the system was slowly added at room temperature and dissolved with stirring for 30min. After the addition, the reaction temperature was raised to 60℃and stirring was continued for 48h, after which the solvent was removed in vacuo. Dichloromethane (200 mL) and water (200 mL) were added to the system, and the organic layer was separated. The aqueous phase was extracted with dichloromethane (2×50 mL), the organic phases were combined, dried over anhydrous magnesium sulfate and concentrated by filtration to give a violet crude product. Purification by column chromatography on silica gel (eluent n-hexane/ethyl acetate=20/1 followed by dichloromethane/n-hexane=1/1, V/V) afforded the sixth compound having the structure shown in formula (17). High resolution electrospray mass spectrometry analysis, analysis results [ C74H79Br3N4O3]:1308.37, found:1308.3.
Example 1 experimental procedure does not involve step e)
Step f 1), in an argon atmosphere glove box, the dried polymerization tube (15 mL) was equipped with a magnetic stirrer and a closedA sixth compound (150. Mu. Mol,50 equiv) having a structure represented by the formula (17) was dissolved in dry chloroform (5 mL) with a GrubsIII generation catalyst (3. Mu. Mol,1 equiv) added thereto in a molar ratio of polymerized monomer to catalyst of 50:1, and the solution was lyophilized three times to remove oxygen and the polymerization tube was closed. The reaction was stirred at 40℃for 3h. After the polymerization was completed, vinyl ether (3 mL) was added to quench, followed by dropwise addition of diethyl ether (30 mL) with stirring, the polymerized monomer was dissolved in diethyl ether, the target product of oligoporphyrin was precipitated out, and the solid product was collected by centrifugation and washed three times with diethyl ether. After vacuum drying, a ninth compound (x: y takes a value of 1:0) as shown in the formula (18) is obtained as a dark red solid target product. Gel permeation chromatography (GPC, CH 2 Cl 2 ):M n ＝11000，PDI＝1.29。
Step g 1) in an argon atmosphere glove box, the ninth compound (1 mmol) represented by the formula (18) was dissolved in dry dichloromethane (20 mL) with stirring, and then diethylaluminum chloride (1.05 mmol,1mol/L n-hexane solution) was added thereto, and the reaction solution was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was filtered using a sand core filter funnel covered with a layer of neutral alumina (200 to 300 mesh), and the neutral alumina was washed with a dry mixed solution of methylene chloride/methanol (10/1, V/V), and the filtrate was collected, concentrated and dried to obtain a tenth compound having a structure represented by formula (19).
Step h 1), tenth compound (1.5 mmol) having the structure shown in formula (19) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48h. After the reaction is finished, the solvent and tributylamine are removed in vacuum, and the difunctional metalloporphyrin complex Port (Al-01) shown in the formula (20) is obtained, wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 2
Step a) is not involved in the experimental procedure of example 2.
Step b 2) and step c 2) the experimental procedure was the same as in step b 1) and step c 1) in preparation example 1, respectively, to obtain a fourth compound having the structure represented by formula (15) and a fifth compound having the structure represented by formula (16).
Step d 2), under the protection of argon, 5-norbornene-2-carboxylic acid (12 mmol) was added into a 250mL three-necked flask equipped with dry tetrahydrofuran (150 mL), the system was placed in an ice-water bath at 0℃and oxalyl chloride (60 mmol) was added dropwise, after the completion of which N, N-dimethylformamide (DMF, 0.2 mL) was added, and after stirring for 30min, the temperature was restored and the reaction was stirred for 6h. After the reaction, the solvent and the excess oxalyl chloride are removed under reduced pressure to obtain a pale yellow oily 5-norbornene-2-acyl chloride product which is directly used for the next synthetic reaction.
A250 mL three-necked flask was charged with a fifth compound (6 mmol) having a structure represented by formula (16) under argon atmosphere, dichloromethane (100 mL) was dried, dissolved by magnetic stirring, and the purple reaction solution was cooled to 0 ℃. After the synthesized 5-norbornene-2-yl chloride (12 mmol) was dissolved in dry dichloromethane (10 mL), it was added dropwise to the reaction system, followed by addition of pyridine (2 mL) by syringe, and after stirring the reaction system for 30min, the reaction was resumed at room temperature with stirring for 24h. After the reaction was completed, the reaction mixture was washed with a dilute hydrochloric acid solution, and after removal of pyridine components, saturated NaHCO was used, respectively 3 Saturated NaCl, H 2 The organic layer was collected by washing with O three times and dried over anhydrous sodium sulfate. The violet filtrate was collected by filtration and concentrated to give the crude product. The first component was collected by separation and purification using silica gel column chromatography (dichloromethane/petroleum ether=1/1, V/V), to obtain a sixth compound having a structure represented by formula (21). High resolution electrospray mass spectrometry analysis, analysis results [ C70H71Br3N4O2 ]]:1236.31，found:1236.3。
Step e 2), under the protection of argon, 5-norbornene-2-carboxylic acid (12 mmol) was added into a 250mL three-necked flask containing dry tetrahydrofuran (150 mL), the system was placed in an ice-water bath at 0 ℃, oxalyl chloride (60 mmol) was added dropwise, N-dimethylformamide (DMF, 0.2 mL) was added after the completion, and after stirring for 30min, the temperature was restored to room temperature and the reaction was stirred for 6h. After the reaction, the solvent and the excess oxalyl chloride are removed under reduced pressure to obtain a pale yellow oily 5-norbornene-2-acyl chloride product which is directly used for the next synthetic reaction.
A seventh compound (6 mmol) having a structure represented by formula (22) was placed in a 250mL three-necked flask under argon atmosphere, dichloromethane (100 mL) was dried, dissolved by magnetic stirring, and the purple reaction solution was cooled to 0 ℃. After the synthesized 5-norbornene-2-yl chloride (12 mmol) was dissolved in dry dichloromethane (10 mL), it was added dropwise to the reaction system, followed by addition of pyridine (2 mL) by syringe, and after stirring the reaction system for 30min, the reaction was resumed at room temperature with stirring for 24h. After the reaction was completed, the reaction mixture was washed with a dilute hydrochloric acid solution, and after removal of pyridine components, saturated NaHCO was used, respectively 3 Saturated NaCl, H 2 The organic layer was collected by washing with O three times and dried over anhydrous sodium sulfate. The violet filtrate was collected by filtration and concentrated to give the crude product. The first component was collected by separation and purification using silica gel column chromatography (dichloromethane/petroleum ether=1/1, V/V), to obtain an eighth compound having a structure represented by formula (23). High resolution electrospray mass spectrometry analysis, analysis results [ C52H38N4O2 ]]:750.30，found:750.3。
Step f 2), in a glove box under argon atmosphere, the dried polymerization tube (15 mL) was equipped with a magnetic stirrer and a sealing cock, the sixth compound (75. Mu. Mol,25 equiv) having the structure represented by formula (21) and the eighth compound (75. Mu. Mol,25 equiv) having the structure represented by formula (23) were dissolved in dried chloroform (5 mL), grubsIII generation catalyst (3. Mu. Mol,1 equiv) was added, the molar ratio of the polymerization monomer to the catalyst was 50:1, and the solution was lyophilized for three times to remove oxygen, and the polymerization tube was sealed. At 40 DEG C The reaction was stirred for 3h. After the polymerization was completed, vinyl ether (3 mL) was added to quench, followed by dropwise addition of diethyl ether (30 mL) with stirring, the polymerized monomer was dissolved in diethyl ether, the target product of oligoporphyrin was precipitated out, and the solid product was collected by centrifugation and washed three times with diethyl ether. After vacuum drying, a ninth compound (x: y takes a value of 1:1) as shown in formula (24) is obtained as a dark red solid target product. Gel permeation chromatography (GPC, CH 2 Cl 2 ):M n ＝12400，PDI＝1.22。
Step g 2) in an argon atmosphere glove box, the ninth compound (1.0 mmol) represented by the formula (24) was dissolved in dry dichloromethane (20 mL), and after stirring, diethylaluminum chloride (1.05 mmol,1mol/L n-hexane solution) was added thereto, and the reaction solution was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was filtered using a sand core filter funnel covered with a layer of neutral alumina (200 to 300 mesh), and the neutral alumina was washed with a dry mixed solution of methylene chloride/methanol (10/1, V/V), and the filtrate was collected, concentrated and dried to obtain a tenth compound having a structure represented by formula (25).
Step h 2), tenth Compound (1.5 mmol) having the structure represented by the formula (25) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48 hours. After the reaction, removing the solvent and the redundant amine compound in vacuum to obtain a difunctional metalloporphyrin complex Por (Al-02) shown in a formula (26), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 3
Step a) was not involved in the experimental procedure of example 3.
Step b 3) and step c 3) the experimental procedure was the same as in step b 1) and step c 1) in preparation example 1, respectively, to obtain a fourth compound having a structure represented by formula (15) and a fifth compound having a structure represented by formula (16). Step d 3), step e 3) the experimental procedure was the same as step d 2), step e 2) in preparation example 2, respectively, to obtain a sixth compound having the structure shown by formula (21) and an eighth compound having the structure shown by formula (23).
Step f 3), in a glove box under argon atmosphere, the dried polymerization tube (15 mL) was equipped with a magnetic stirrer and a sealing cock, the sixth compound (50. Mu. Mol,16.66 equiv) having the structure represented by the formula (21) and the eighth compound (100. Mu. Mol,33.33 equiv) having the structure represented by the formula (23) were dissolved in dried chloroform (5 mL), grubsIII generation catalyst (3. Mu. Mol,1 equiv) was added, the molar ratio of the polymerization monomer to the catalyst was 50:1, and the solution was lyophilized for three times to remove oxygen, and the polymerization tube was sealed. The reaction was stirred at 40℃for 3h. After the polymerization was completed, vinyl ether (3 mL) was added to quench, followed by dropwise addition of diethyl ether (30 mL) with stirring, the polymerized monomer was dissolved in diethyl ether, the target product of oligoporphyrin was precipitated out, and the solid product was collected by centrifugation and washed three times with diethyl ether. After vacuum drying, a ninth compound (x: y takes a value of 1:2) as shown in formula (27) is obtained as a target product in the form of a dark red solid. The prepared oligomer was characterized by nuclear magnetic resonance hydrogen spectroscopy, GPC, MALDI-TOF-MS. Gel permeation chromatography (GPC, CH 2 Cl 2 ):M n ＝12300，PDI＝1.20。
Step g 3) in an argon atmosphere glove box, the ninth compound (1.0 mmol) represented by the formula (27) was dissolved in dry dichloromethane (20 mL), and after stirring, diethylaluminum chloride (1.05 mmol,1mol/L n-hexane solution) was added thereto, and the reaction solution was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was filtered using a sand core filter funnel covered with a layer of neutral alumina (200 to 300 mesh), and the neutral alumina was washed with a dry mixed solution of methylene chloride/methanol (10/1, V/V), and the filtrate was collected, concentrated and dried to obtain a tenth compound having a structure represented by formula (28).
Step h 3), tenth compound (1.5 mmol) having the structure shown in formula (28) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48h. After the reaction, removing the solvent and the redundant amine compound in vacuum to obtain a difunctional metalloporphyrin complex Por (Al-03) shown in a formula (29), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 4
Step a 4) 5-norbornene-2-carboxylic acid (3.62 mmol,1 equiv) and methylene chloride (30 mL) were added to a dry one-necked flask (100 mL) and dissolved by stirring. To the reaction solution, dicyclohexylcarbodiimide (DCC, 3.62mmol,1 equiv.) was added, and a first compound (3.62 mmol,1 equiv.) having a structure represented by formula (30), 4-dimethylaminopyridine (catalyst equivalent). The system is stirred and dissolved under the protection of argon, and heated and refluxed for 16h. After the completion of the reaction, the reaction solution was diluted with methylene chloride and filtered, and the filtrate was dried over anhydrous magnesium sulfate, and the solvent was removed in vacuo, whereby an oily product was obtained. The crude product was purified using silica gel column chromatography (n-hexane/ethyl acetate=20/1, V/V) to obtain a second compound having a structure represented by formula (31). High resolution electrospray mass spectrometry analysis, analysis results [ C16H25ClO2]:284.15, found:284.1.
Step b 4), adding a third compound (18 g) having a structure represented by formula (32) and titanium tetrachloride (24 g) to dry dichloromethane (120 mL) under ice water bath conditions, then adding dichlorodimethyl methyl ether (8 g) to a solution of the third compound in 30min, reacting the obtained mixed solution at 35 ℃ for 30min, pouring the obtained reaction solution into a large beaker filled with ice water, then extracting with dichloromethane, collecting an organic phase, and washing with saturated sodium bicarbonate solution to obtain a crude product, and purifying the crude product by silica gel column chromatography, wherein an eluent is dichloromethane/petroleum ether=2/1 (volume ratio), thereby obtaining a fourth compound having a structure represented by formula (33). High resolution electrospray mass spectrometry analysis, analysis results [ C15H21BrO ]:296.08, found:296.0.
Step c 4) in a three-necked flask (500 mL), 4-hydroxybenzaldehyde (18 mmol) and a fourth compound (54 mmol) having a structure represented by formula (33) were added, the molar ratio of the two aldehydes was 1:3, propionic acid (240 mL) was added, and the system was heated to 130℃and stirred for 0.5h. Pyrrole (72 mmol) was then added dropwise and after completion the temperature was raised to 165℃and the mixture was allowed to reflux in air for 1h. After the completion of the reaction, the reaction mixture was cooled to room temperature, 500mL of methanol was added to the reaction mixture, and the mixture was left in a refrigerator overnight. The crude violet solid product was collected by filtration, washed with methanol and hot water, and dried. The crude product mainly comprises tetraphenylporphyrin, monohydroxy porphyrin and polyhydroxy porphyrin, a silica gel chromatographic column is used for separating the product, an eluent is pure dichloromethane, a second component is collected, and the product is dried after rotary evaporation, so that a fifth compound with a structure shown in a formula (34) is obtained. High resolution electrospray mass spectrometry analysis, analysis results [ C68H75Br3n4O ]:1200.35, found:1200.3.
Step d 4) in a magnetically stirred round bottom flask (250 mL), the second compound (15.8 mmol,2.5 equiv.) of the structure represented by formula (31), anhydrous potassium carbonate (15.8 mmol,2.5 equiv.), N, N-dimethylformamide (DMF, 50 mL) was added, respectively, and dissolved with stirring. The fifth compound (6.33 mmol,1 equiv) having the structure shown in formula (34) was dissolved in dry N, N-dimethylformamide (DMF, 30 mL), and the system was slowly added at room temperature and dissolved with stirring for 30min. After the addition, the reaction temperature was raised to 60℃and stirring was continued for 48h, after which the solvent was removed in vacuo. Dichloromethane (200 mL) and water (200 mL) were added to the system, and the organic layer was separated. The aqueous phase was extracted with dichloromethane (2×50 mL), the organic phases were combined, dried over anhydrous magnesium sulfate and concentrated by filtration to give a violet crude product. Purification by column chromatography on silica gel (eluent n-hexane/ethyl acetate=20/1 followed by dichloromethane/n-hexane=1/1, V/V) afforded the sixth compound having the structure shown in formula (35). High resolution electrospray mass spectrometry analysis, analysis results [ C84H99Br3N4O3]:1448.53, found:1448.5.
Step e 4) in a magnetically stirred round bottom flask (250 mL), the second compound of the structure represented by formula (31) (15.8 mmol,2.5 equiv.) and anhydrous potassium carbonate (15.8 mmol,2.5 equiv.) were added, respectively, and N, N-dimethylformamide (DMF, 50 mL) were dissolved with stirring. The seventh compound (6.33 mmol,1 equiv) having the structure of formula (22) was dissolved in dry N, N-dimethylformamide (DMF, 30 mL), slowly added to the system at room temperature, and the stirring was continued for 30min. After the addition, the reaction temperature was raised to 60℃and stirring was continued for 48h, after which the solvent was removed in vacuo. Dichloromethane (200 mL) and water (200 mL) were added to the system, and the organic layer was separated. The aqueous phase was extracted with dichloromethane (2×50 mL), the organic phases were combined, dried over anhydrous magnesium sulfate and concentrated by filtration to give a violet crude product. Purification by column chromatography on silica gel (eluent n-hexane/ethyl acetate=20/1 followed by dichloromethane/n-hexane=1/1, V/V) afforded the eighth compound having the structure shown in formula (36). High resolution electrospray mass spectrometry analysis, analysis results [ C60H54N4O3]:878.42, found:878.4.
Step f 4), in a glove box under argon atmosphere, the dried polymerization tube (15 mL) was equipped with a magnetic stirrer and a sealing cock, the sixth compound (50. Mu. Mol,16.66 equiv) having the structure represented by the formula (35) and the eighth compound (100. Mu. Mol,33.33 equiv) having the structure represented by the formula (36) were dissolved in dried chloroform (5 mL), grubsIII generation catalyst (3. Mu. Mol,1 equiv) was added, the molar ratio of the polymerization monomer to the catalyst was 50:1, and the solution was lyophilized for three times to remove oxygen, and the polymerization tube was sealed. The reaction was stirred at 40℃for 3h. After the polymerization was completed, vinyl ether (3 mL) was added to quench, followed by dropwise addition of diethyl ether (30 mL) with stirring, the polymerized monomer was dissolved in diethyl ether, the target product of oligoporphyrin was precipitated out, and the solid product was collected by centrifugation and washed three times with diethyl ether. After vacuum drying, a ninth compound (x: y takes a value of 1:2) represented by the formula (37) was obtained. Gel permeation chromatography (GPCCH 2 Cl 2 ):M n ＝13200，PDI＝1.26。
Step g 4), in an argon atmosphere glove box, the ninth compound (1.0 mmol) represented by the formula (37) was dissolved in dry dichloromethane (20 mL), and after stirring, diethylaluminum chloride (1.05 mmol,1mol/L n-hexane solution) was added thereto, and the reaction solution was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was filtered using a sand core filter funnel covered with a layer of neutral alumina (200 to 300 mesh), and the neutral alumina was washed with a dry mixed solution of methylene chloride/methanol (10/1, V/V), and the filtrate was collected, concentrated and dried to obtain a tenth compound having a structure represented by formula (38).
Step h 4), tenth Compound (1.5 mmol) of the structure represented by the formula (38) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48h. After the reaction, removing the solvent and the redundant amine compound in vacuum to obtain a difunctional metalloporphyrin complex Por (Al-04) shown in a formula (39), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 5
The experimental procedures of step a 5), step b 5), step c 5), and step d 5) were the same as those of step a 4), step b 4), step c 4), and step d 4) in example 4, respectively, to obtain a second compound having a structure represented by formula (31), a fourth compound having a structure represented by formula (33), a fifth compound having a structure represented by formula (34), and a sixth compound having a structure represented by formula (35).
Step e 5) in a magnetically stirred round bottom flask (250 mL), the second compound of the structure represented by formula (31) (15.8 mmol,2.5 equiv.) and anhydrous potassium carbonate (15.8 mmol,2.5 equiv.) were added, respectively, and N, N-dimethylformamide (DMF, 50 mL) were dissolved with stirring. The seventh compound (6.33 mmol,1 equiv) having the structure shown in formula (40) was dissolved in dry N, N-dimethylformamide (DMF, 30 mL), slowly added to the system at room temperature, and stirring was continued for 30min. After the addition, the reaction temperature was raised to 60℃and stirring was continued for 48h, after which the solvent was removed in vacuo. Dichloromethane (200 mL) and water (200 mL) were added to the system, and the organic layer was separated. The aqueous phase was extracted with dichloromethane (2×50 mL), the organic phases were combined, dried over anhydrous magnesium sulfate and concentrated by filtration to give a violet crude product. Purification by column chromatography on silica gel (eluent n-hexane/ethyl acetate=20/1 followed by dichloromethane/n-hexane=1/1, V/V) afforded the eighth compound having the structure shown in formula (41). High resolution electrospray mass spectrometry analysis, analysis results [ C60H51Br3N4O3]:1112.15, found:1112.1.
Step f 5), in a glove box under argon atmosphere, the dried polymerization tube (15 mL) was equipped with a magnetic stirrer and a sealing cock, the sixth compound (50. Mu. Mol,16.66 equiv) having the structure represented by the formula (35) and the eighth compound (100. Mu. Mol,33.33 equiv) having the structure represented by the formula (41) were dissolved in dried chloroform (5 mL), grubsIII generation catalyst (3. Mu. Mol,1 equiv) was added, the molar ratio of the polymerization monomer to the catalyst was 50:1, and the solution was lyophilized for three times to remove oxygen, and the polymerization tube was sealed. The reaction was stirred at 40℃for 3h. After the polymerization was completed, vinyl ether (3 mL) was added to quench, followed by dropwise addition of diethyl ether (30 mL) with stirring, the polymerized monomer was dissolved in diethyl ether, the target product of oligoporphyrin was precipitated out, and the solid product was collected by centrifugation and washed three times with diethyl ether. After vacuum drying, a ninth compound (x: y has a value of 1:2) represented by the formula (42) was obtained. Gel permeation chromatography (GPC, CH 2 Cl 2 ):M n ＝14500，PDI＝1.28。
Step g 5) in an argon atmosphere glove box, the ninth compound (1.0 mmol) represented by the formula (42) was dissolved in dry dichloromethane (20 mL), and after stirring, diethylaluminum chloride (1.05 mmol,1mol/L n-hexane solution) was added thereto, and the reaction solution was stirred at room temperature for 3 hours. After the completion of the reaction, the reaction mixture was filtered using a sand core filter funnel covered with a layer of neutral alumina (200 to 300 mesh), and the neutral alumina was washed with a dry mixed solution of methylene chloride/methanol (10/1, V/V), and the filtrate was collected, concentrated and dried to obtain a tenth compound having a structure represented by formula (43).
Step h 4), tenth Compound (1.5 mmol) having the structure represented by the formula (43) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48 hours. After the reaction, removing the solvent and the redundant amine compound in vacuum to obtain a difunctional metalloporphyrin complex Por (Al-05) shown in a formula (44), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 6
Step a 6), step b 6), step c 6), and step d 6) the experimental procedure was the same as in step a 4), step b 4), step c 4), and step d 4) in example 4, respectively, to obtain a second compound having a structure represented by formula (31), a fourth compound having a structure represented by formula (33), a fifth compound having a structure represented by formula (34), and a sixth compound having a structure represented by formula (35); step e 6) and step f 6) the experimental procedures were the same as those of step e 5) and step f 5) in preparation example 5, respectively, to obtain an eighth compound having a structure represented by formula (41) and a ninth compound having a structure represented by formula (42).
Step g 6) A fifth compound (1.0 mmol) represented by the formula (42) was dissolved in 20mL of anhydrous DMF, cobalt acetate (180 mg) from which crystal water had been removed was added, and the reaction was stirred at room temperature for 12 hours. 0.042g of anhydrous lithium chloride was added, and oxygen was introduced to continue the reaction for 12 hours. The reaction was stopped, the solvent was removed under reduced pressure, and the residue was dissolved in 20mL of methylene chloride and washed three times with 70mL of saturated sodium bicarbonate solution and 70mL of saturated brine solution, respectively. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residue was dissolved in 20mL of methylene chloride, and 0.01g of silver tetrafluoroborate was added thereto and reacted in the dark for 24 hours. Insoluble matter was removed by filtration, and 0.20g of sodium 2, 4-dinitrophenol was added to the filtrate and reacted at room temperature for 2 hours. Inorganic salts were removed by filtration and the solvent was removed under reduced pressure. The crude product was recrystallized from methylene chloride and n-hexane to obtain a tenth compound having a structure represented by the formula (43).
Step h 6), tenth compound (1.5 mmol) having the structure shown in formula (43) and tributylamine (50 mmol) were added to a mixed solvent of 10mL of dried tetrahydrofuran and acetonitrile solution, and the mixture was refluxed for 48h. After the reaction, removing the solvent and the redundant amine compound in vacuum to obtain a difunctional metalloporphyrin complex Por (Co-01) shown in a formula (44), wherein the mass ratio of tetrahydrofuran to acetonitrile in the mixed solvent is 1:1.
After the metalloporphyrin complex is prepared, the metalloporphyrin complex is placed into an ampere bottle for vacuumizing and drying treatment, the metalloporphyrin complex is continuously vacuumized for 12 hours by using a vacuum oil pump at 50 ℃, high-purity argon is used for ventilation every 30 minutes in the process of pumping, and the vacuumized metalloporphyrin complex is placed into a glove box for storage.
Example 7
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps:
the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-01) in example 1 and 75mmol of dried propylene oxide were added to a 15ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 4MPa, and the temperature of the autoclave was controlled at 25℃to carry out polymerization for 3 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 7 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 98% and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalyst system is 1480h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 38000 and the molecular weight distribution was 1.25 as measured by GPC.
Example 8
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-01) in example 1 and 75mmol of dried propylene oxide were added to a 15ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the temperature of the autoclave was controlled at 50℃to carry out polymerization for 3 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 8 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 95% and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalyst system is 6800h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate prepared was 76000 and the molecular weight distribution was 1.24 as determined by GPC.
Example 9
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-02) in example 2 and 150mmol of dry propylene oxide were added to a 25ml autoclave after dehydration and deoxidation, and then the autoclave was taken out of the glove box and passed through a dioxygen having a pressure regulating function Carbon dioxide is filled into the high-pressure reaction kettle to enable the pressure in the high-pressure reaction kettle to reach 4MPa, and the temperature of the high-pressure reaction kettle is controlled at 70 ℃ for polymerization reaction for 1h. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 9 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 87% and the product selectivity was 99%; the catalytic activity (TOF value) of the catalyst system is calculated to be 8900h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 69000 and the molecular weight distribution was 1.29 as determined by GPC.
Example 10
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-03) in example 3 and 375mmol of dried propylene oxide were added to a 50ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 5MPa, and the polymerization was carried out at 110℃for 0.5 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. At 25 ℃ in a vacuum drying ovenThe unreacted propylene oxide was removed to obtain a polycarbonate.
By passing through 1 The polycarbonate prepared in example 10 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 78% and the product selectivity was 95%; the catalytic activity (TOF value) of the catalyst system is 15800h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 82000 and the molecular weight distribution was 1.31 as measured by GPC.
Example 11
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of aluminum porphyrin complex Poly (Al-03) in example 3 and 375mmol of dried propylene oxide were added to a 50ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 5MPa, and the temperature of the autoclave was controlled at 120℃to conduct polymerization for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate produced in example 11 was examined for H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 75% and the product selectivity was 97%; the catalytic activity (TOF value) of the catalyst system is 16800h -1 The method comprises the steps of carrying out a first treatment on the surface of the The preparation was determined by GPCThe polycarbonate had a number average molecular weight of 56000 and a molecular weight distribution of 1.24.
Example 12
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box. In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-03) in example 3 and 150mmol of dried propylene oxide were added to a 25ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 4MPa, and the polymerization was carried out at 50℃for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 12 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 95% and the product selectivity was 99%; the catalytic activity (TOF value) of the catalytic system is 8755h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 61000 and the molecular weight distribution was 1.25 as measured by GPC.
Example 13
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmo of the aluminum porphyrin complex Poly (Al-04) in example 4 and 375mmo of dried propylene oxide were added to a 50ml autoclave after dehydration and deoxidation, and then the autoclave was taken out of the glove box, and carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 3MPa, and the polymerization was carried out at 110℃for 0.5 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate obtained in example 13 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 86% and the product selectivity was 99%; the catalytic activity (TOF value) of the catalyst system is 13100h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 45000 as measured by GPC, and the molecular weight distribution was 1.24.
Example 14
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-05) of example 5 and 150mmol of dried propylene oxide were added to a 25ml autoclave after water removal and oxygen removal, and then the autoclave was taken out of the glove box, And filling carbon dioxide into the high-pressure reaction kettle through a carbon dioxide supply line with a pressure regulating function to enable the pressure in the high-pressure reaction kettle to reach 4MPa, and controlling the temperature of the high-pressure reaction kettle at 70 ℃ for polymerization reaction for 1h. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate obtained in example 14 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 73% and the product selectivity was 99%; the catalytic activity (TOF value) of the catalyst system is 8530h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 62000 and the molecular weight distribution was 1.27 as measured by GPC.
Example 15
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-05) in example 5 and 375mmol of dried propylene oxide were added to a 50ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 5MPa, and the polymerization was carried out at 120℃for 1 hour. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance is performedAnd (5) measuring. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate produced in example 15 was examined by H-NMR nuclear magnetism, which showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 92% and the product selectivity was 96%; the catalytic activity (TOF value) of the catalyst system is calculated to be 15770h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate thus obtained was 89000 and the molecular weight distribution was 1.23 as measured by GPC.
Example 16
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Al-05) in example 5 and 150mmol of dried propylene oxide were added to a 25ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 4MPa, and the polymerization was carried out at 25℃for 3 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate obtained in example 16 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 95% and the product selectivity was 99%; the catalytic activity (TOF value) of the catalyst system is 1800h -1 The method comprises the steps of carrying out a first treatment on the surface of the The preparation was determined by GPCThe polycarbonate had a number average molecular weight of 55000 and a molecular weight distribution of 1.23.
Example 17
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Co-01) in example 6 and 75mmol of dry epichlorohydrin were added to 15ml of a high-pressure reaction kettle after water removal and oxygen removal, the high-pressure reaction kettle was taken out of the glove box, carbon dioxide was then introduced into the high-pressure reaction kettle through a carbon dioxide supply line having a pressure regulating function, the pressure in the high-pressure reaction kettle was brought to 4MPa, and the temperature of the high-pressure reaction kettle was controlled at 10℃for polymerization for 8 hours. After the polymerization reaction is finished, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate obtained in example 17 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 99% and the product selectivity was 99.9%; the catalytic activity (TOF value) of the catalyst system is calculated to be 550h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate prepared was 73000 and the molecular weight distribution was 1.28 as determined by GPC.
Example 18
In the invention, the carbon dioxide and the epoxide are polymerized in the high-pressure reaction kettle, and the high-pressure reaction kettle is subjected to water removal and deoxidization treatment before the polymerization reaction, and the specific method comprises the following steps: the high-pressure reaction kettle is subjected to decompression and argon replacement treatment in a vacuum oven at 80 ℃, the operations of decompression and argon replacement are repeated once per hour, the operations are repeated three times in total, the purposes of removing water and deoxidizing the high-pressure reaction kettle are achieved, and then the high-pressure reaction kettle is placed in a glove box.
In a glove box, 0.015mmol of the aluminum porphyrin complex Poly (Co-01) in example 6 and 375mmol of dried propylene oxide were added to a 50ml autoclave after dehydration and deoxidation, the autoclave was taken out of the glove box, carbon dioxide was introduced into the autoclave through a carbon dioxide supply line having a pressure regulating function to bring the pressure in the autoclave to 5MPa, and the polymerization was carried out at 110℃for 3 hours. After the polymerization reaction is finished, cooling the high-pressure reaction kettle to 25 ℃, slowly discharging carbon dioxide in the high-pressure reaction kettle, and opening the reaction kettle for the first time to take 1 H-NMR nuclear magnetic resonance sample, nuclear magnetic resonance measurement is performed. The unreacted propylene oxide was removed in a vacuum oven at 25℃to give a polycarbonate.
By passing through 1 The polycarbonate prepared in example 18 was tested by H-NMR nuclear magnetism, which indicated that the polycarbonate had a carbonate unit content of 99% and a cyclic carbonate by-product content of less than 10%; the TOF value of the catalytic system is 18100h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 125000 and the molecular weight distribution was 1.22 as measured by GPC.
By passing through 1 The polycarbonate produced in example 18 was examined by H-NMR nuclear magnetism, and the result showed that the chemical structure selectivity (carbonate unit content) of the polycarbonate was 99% and the product selectivity was 97%; the catalytic activity (TOF value) of the catalyst system is 18100h -1 The method comprises the steps of carrying out a first treatment on the surface of the The number average molecular weight of the polycarbonate obtained was 125000 and the molecular weight distribution was 1.22 as measured by GPC.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (8)
1. A metalloporphyrin complex having the structure of formula (I) or formula (II):
wherein x is an integer of 2 to 50; y is an integer of 1-25, z is an integer of 1-25, and the value of y is 1 (1-10);
the said
Is a linking group; the linking group has the structure of formula (VII) or formula (VIII):
wherein: p is an integer of 1 to 10;
the Ra is a difunctional metalloporphyrin complex having a structure of formula (III); the Rb is a metalloporphyrin complex having a structure of formula (VI):
wherein M is a metal element; n is the degree of polymerization, n=1 to 10;
the L is one of a quaternary ammonium salt functional group with a structure of formula (IV) and a quaternary phosphonium salt functional group with a structure of formula (V):
wherein n, m and k are independently selected from integers from 1 to 6;
Y 1 - and Y 2 - Independently selected from halide anions, NO 3 - 、CH 3 COO - 、CCl 3 COO - 、CF 3 COO - 、ClO 4 - 、BF 4 - One or more of p-toluenesulfonic acid group, p-methylbenzoic acid group, o-nitrophenoxy anion, p-nitrophenoxy anion, m-nitrophenoxy anion, 2, 4-dinitrophenol oxy anion, 3, 5-dinitrophenol oxy anion, 2,4, 6-trinitrophenol oxy anion, 3, 5-dichlorophenol oxy anion, 3, 5-difluorophenol oxy anion, 3, 5-di-trifluoromethyl phenol oxy anion and pentafluorophenol oxy anion;
X is independently selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 One or more of p-methylbenzoic acid group, p-methylbenzenesulfonic acid group, o-nitrophenoxy group, p-nitrophenoxy group, m-nitrophenoxy group, 2, 4-dinitrophenol oxy group, 3, 5-dinitrophenol oxy group, 2,4, 6-trinitrophenol oxy group, 3, 5-dichlorophenol oxy group, 3, 5-difluorophenol oxy group, 3, 5-di-trifluoromethyl phenol oxy group or pentafluorophenol oxy anion;
the R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R is 19 Independently selected from one of hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, aryl with benzene ring number of 1-3 or substituted aryl with benzene ring number of 1-3.
2. The complex of claim 1, wherein M is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel, or ruthenium.
3. The complex of claim 1, wherein the metalloporphyrin complex is specifically of formula 101, formula 102, formula 103, formula 104, formula 105 or formula 106;
4. a method of preparing the metalloporphyrin complex of claim 1, comprising:
polymerizing a compound shown in a formula (i-6) by using a Grubbs III catalyst to obtain a compound shown in a formula (i-9);
Reacting a compound shown in a formula (i-9) with a metal salt compound to obtain a compound shown in a formula (i-11);
reacting a compound shown in a formula (I-11) with a tertiary amine compound to obtain a compound shown in the formula (I);
or (b)
Polymerizing a compound shown in a formula (i-6) and a compound shown in a formula (i-8) by using a Grubbs III catalyst to obtain a compound shown in a formula (i-10);
reacting a compound shown in a formula (i-10) with a metal salt compound to obtain a compound shown in a formula (i-12);
reacting a compound shown in a formula (i-12) with a tertiary phosphine compound to obtain a compound shown in a formula (II);
wherein x is an integer of 2 to 50; y is an integer of 1-25, z is an integer of 1-25, the value of y is 1 (1-10), and M is a metal element; n is the degree of polymerization, n=1 to 10;
x is independently selected from halogen, -NO 3 、CH 3 COO-、CCl 3 COO-、CF 3 COO-、ClO 4 -、BF 4 -、BPh 4 -、-CN、-N 3 One or more of p-methylbenzoic acid group, p-methylbenzenesulfonic acid group, o-nitrophenoxy group, p-nitrophenoxy group, m-nitrophenoxy group, 2, 4-dinitrophenol oxy group, 3, 5-dinitrophenol oxy group, 2,4, 6-trinitrophenol oxy group, 3, 5-dichlorophenol oxy group, 3, 5-difluorophenol oxy group, 3, 5-di-trifluoromethyl phenol oxy group or pentafluorophenol oxy anion;
y is a negative ion in a quaternary ammonium salt functional group or a negative ion in a quaternary phosphonium salt functional group;
The R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 、R 10 、R 11 、R 12 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 And R is 19 Independently selected from one of hydrogen, halogen, C1-C5 aliphatic group, substituted C1-C5 aliphatic group, aryl with benzene ring number of 1-3 or substituted aryl with benzene ring number of 1-3.
5. The method according to claim 4, wherein the tertiary amine compound is one of trimethylamine, tributylamine and trihexylamine; the tertiary phosphine compound is triphenylphosphine; the metal in the metal salt compound is selected from one of magnesium, aluminum, zinc, chromium, manganese, iron, cobalt, titanium, yttrium, nickel or ruthenium.
6. A method for producing a polycarbonate, comprising:
a metalloporphyrin complex according to any one of claims 1 to 3 or a metalloporphyrin complex prepared by the method according to any one of claims 4 to 5 is used as a catalyst, and carbon dioxide and epoxide are subjected to copolymerization reaction to obtain a polycarbonate.
7. The method according to claim 6, wherein the molar ratio of metalloporphyrin complex to epoxide is 1 (2000-500000); the pressure of the carbon dioxide is 0.1-8.0 MPa; the temperature of the copolymerization reaction is 0-150 ℃; the time of the copolymerization reaction is 0.5 to 48 hours.
8. The method according to claim 6, wherein the epoxide comprises one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, and styrene alkylene oxide.
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| CN103435623A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院长春应用化学研究所 | Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate |
| CN109988290A (en) * | 2019-04-22 | 2019-07-09 | 中国科学院长春应用化学研究所 | A kind of preparation method of oligomeric Metalloporphyrins and polycarbonate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103435623A (en) * | 2013-09-05 | 2013-12-11 | 中国科学院长春应用化学研究所 | Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate |
| CN109988290A (en) * | 2019-04-22 | 2019-07-09 | 中国科学院长春应用化学研究所 | A kind of preparation method of oligomeric Metalloporphyrins and polycarbonate |
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