CN105936659A - N,N-single ligand metal catalyst with three-dimensional structure and preparation method thereof - Google Patents
N,N-single ligand metal catalyst with three-dimensional structure and preparation method thereof Download PDFInfo
- Publication number
- CN105936659A CN105936659A CN201510882585.9A CN201510882585A CN105936659A CN 105936659 A CN105936659 A CN 105936659A CN 201510882585 A CN201510882585 A CN 201510882585A CN 105936659 A CN105936659 A CN 105936659A
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- CN
- China
- Prior art keywords
- diimine
- alpha
- aniline
- norborene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003446 ligand Substances 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title abstract description 33
- 150000004982 aromatic amines Chemical group 0.000 claims abstract description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 10
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims abstract description 10
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Chemical group 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical compound NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical compound NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- IAHOUQOWMXVMEH-UHFFFAOYSA-N 2,4,6-trinitroaniline Chemical compound NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IAHOUQOWMXVMEH-UHFFFAOYSA-N 0.000 claims abstract description 5
- DYSRXWYRUJCNFI-UHFFFAOYSA-N 2,4-dibromoaniline Chemical compound NC1=CC=C(Br)C=C1Br DYSRXWYRUJCNFI-UHFFFAOYSA-N 0.000 claims abstract description 5
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 claims abstract description 5
- XIRRDAWDNHRRLB-UHFFFAOYSA-N 2,6-dibromoaniline Chemical compound NC1=C(Br)C=CC=C1Br XIRRDAWDNHRRLB-UHFFFAOYSA-N 0.000 claims abstract description 5
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 claims abstract description 5
- QFUSCYRJMXLNRB-UHFFFAOYSA-N 2,6-dinitroaniline Chemical compound NC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O QFUSCYRJMXLNRB-UHFFFAOYSA-N 0.000 claims abstract description 5
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims abstract description 5
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 claims abstract description 5
- BVPJPRYNQHAOPQ-UHFFFAOYSA-N 4-nitronaphthalen-1-amine Chemical compound C1=CC=C2C(N)=CC=C([N+]([O-])=O)C2=C1 BVPJPRYNQHAOPQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- FSBRKZMSECKELY-UHFFFAOYSA-N 5-aminonaphthalen-2-ol Chemical compound OC1=CC=C2C(N)=CC=CC2=C1 FSBRKZMSECKELY-UHFFFAOYSA-N 0.000 claims abstract description 5
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 5
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims abstract description 5
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 199
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 86
- 238000006243 chemical reaction Methods 0.000 claims description 81
- 229910000071 diazene Inorganic materials 0.000 claims description 63
- 239000007787 solid Substances 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000003863 metallic catalyst Substances 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 17
- 150000001412 amines Chemical class 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- -1 paranitroanilinum Chemical compound 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical group FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 claims description 4
- 150000005002 naphthylamines Chemical class 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003983 crown ethers Chemical class 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- LGUKNGHOZGOFJL-UHFFFAOYSA-N 2,4,6-tris(fluoromethyl)aniline Chemical compound NC1=C(CF)C=C(CF)C=C1CF LGUKNGHOZGOFJL-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 abstract description 4
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical compound NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 abstract description 4
- BJSVKBGQDHUBHZ-UHFFFAOYSA-N 2,4,6-trifluoroaniline Chemical compound NC1=C(F)C=C(F)C=C1F BJSVKBGQDHUBHZ-UHFFFAOYSA-N 0.000 abstract description 3
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical compound NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 abstract description 3
- XJEVHMGJSYVQBQ-UHFFFAOYSA-N 2,3-dihydro-1h-inden-1-amine Chemical compound C1=CC=C2C(N)CCC2=C1 XJEVHMGJSYVQBQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 abstract 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 abstract 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 abstract 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 abstract 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 abstract 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 abstract 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 abstract 1
- 125000001246 bromo group Chemical group Br* 0.000 abstract 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 96
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 60
- 150000001875 compounds Chemical class 0.000 description 58
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 31
- 238000003756 stirring Methods 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- 238000006555 catalytic reaction Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 18
- 230000001186 cumulative effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 6
- 241000736199 Paeonia Species 0.000 description 6
- 235000006484 Paeonia officinalis Nutrition 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 125000005605 benzo group Chemical group 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 0 C[N+]1C=[*+]CC1 Chemical compound C[N+]1C=[*+]CC1 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- MCWKFFYBWFQTFL-UHFFFAOYSA-N CC[O]1(C)N=C1 Chemical compound CC[O]1(C)N=C1 MCWKFFYBWFQTFL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- MOIVWVDMFLNLOT-UHFFFAOYSA-N NC1=CC=CC=C1.[Br] Chemical compound NC1=CC=CC=C1.[Br] MOIVWVDMFLNLOT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
- C07F15/0066—Palladium compounds without a metal-carbon linkage
-
- 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
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
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Abstract
The invention provides an N,N-single ligand metal catalyst with three-dimensional structure and a preparation method thereof. The catalyst has a structural general formula as below. Mt represents nickel, palladium, cobalt, iron or copper metal atom; R1 represents bromine, chlorine, iodine, phenyl group, propyl group, butyl group, phenyl group, naphthyl group, methoxy group or ethoxy group; when R2 is aromatic amine, it represents aniline, naphthylamine, p-methylaniline, p-chloroaniline, p-fluoroaniline, p-fluoroaniline, p-bromoaniline, p-nitroaniline, o-bromoaniline, o-chloroaniline, o-nitraniline, 2,6-dichloroaniline, 2,6-difluoroaniline, 2,6-dibromoaniline, 2,6-dinitroaniline, 2,6-dimethylaniline, 2,6-diisopropyl aniline, 2,4-difluoroaniline, 2,4-dibromoaniline, 2,4-dichloroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromo aniline, 2,4,6-trifluoroaniline, 2,4,6-trinitroaniline, 6-hydroxynaphthylamine, 1-aminoindan, fluoreneamine or 4-nitro naphthylamine; and when R2 is aliphatic amine, it represents ethylamine, propylamine, butylamine, heptylamine, isopropylamine, tert-butylamine or cyclohexylamine. The preparation method is simple, less in by-products, and environmentally friendly.
Description
Technical field:
The present invention relates to the catalyst system and catalyzing for norborene and norbornene derivative addition copolymerization and preparation method；Specifically
Say and relate to a kind of stereochemical structure N, mono-ligand metallic catalyst of N-and preparation method thereof.
Background technology:
Additive poly norborene makes it have heat because of the twin nuclei (US Patent 5468819,5569730) of its uniqueness,
The advantages such as chemical stability is good, and transmittance is high and birefringence is relatively low, these character make polynorbornene become alkene
The focus of polymerization field.But, in actual application process, this polynorbornene also faces bigger difficulty, main
If a series of shortcomings such as its processing characteristics, solubility property and adhesion property are poor, limit its application.In order to improve
These are not enough, typically norborene and alpha-olefin, polar monomer are carried out copolymerization.And in this copolymerization process, efficiently,
Selection stable, resistance to polar catalyst is most important.
Since Brookhart Successful utilization alpha-diimine metal complex, catalysis alpha-olefines polymerization merging presents higher urging
After changing activity, alpha-diimine metallic catalyst, in 10 years of past, cause people pay close attention to widely.Alpha-diimine gold
The catalytic performance of metal catalyst mainly relies on electronics and the steric effect of its part, and therefore, the most is the most logical
Cross the change of substituent group on alpha-diimine part to regulate catalytic performance and the stability of its corresponding metallic catalyst.Major part work
Make mainly around changing alpha-diimine part upper skeleton structure.The framing structure of big steric hindrance can stop α-two effectively because of it
The aromatic ring structure of imine metal coordination compound rotates thus protects metal center, so, it can be greatly enhanced alpha-diimine metal
The stability of coordination compound and catalytic performance.While it is true, major part work the most both at home and abroad the most only rests on alpha-diimine metal
In the design of coordination compound Planar Bone shelf structure, the research for three-dimensional skeleton structure is the most little.
The catalyst of exploitation novel high-performance is the essential condition realizing functional poly cycloolefin, and catalyst ligand synthesizes new skill
The exploitation of art is the key determining catalytic performance.The most first design synthesis and there is the α-diketone of stereoeffect, then with arylamine
Or fatty amine carries out ketoamine condensation reaction, and change metal catalytic by the stereoeffect and electronic structure changing arylamine
Agent structure, thus reach to strengthen its heat stability and the purpose of catalysis activity.
Summary of the invention:
The present invention provides a kind of stereochemical structure N, and mono-ligand metallic catalyst of N-and preparation method thereof, it has high light transmittance, high glass
Glass transition temperature, good heat stability, oxidation stability, low hydroscopicity, low dielectric constant and good adding
Novel solid structure N of the norborene of work performance, solubility property and adhesion property and the copolymer of norbornene derivative, N-
Single ligand metallic catalyst, preparation method is simple, and by-product is few, environmentally friendly.
One stereochemical structure N of the present invention, the mono-ligand metallic catalyst of N-, its general structure is:
Mt is: nickel, palladium, cobalt, ferrum or copper central metal atom；
R1 is: bromine, chlorine, iodine, nitro, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy；
When R2 is aromatic amine, for: aniline, naphthylamines, open-chain crown ether, parachloroanilinum, para-fluoroaniline, para-fluoroaniline, to bromine
Aniline, paranitroanilinum, o-bromoaniline, o-chloraniline, adjacent fluoroaniline, ortho-nitraniline, 2,6-dichloroaniline, 2,6-
Difluoroaniline, 2,6-dibromo aniline, 2,6-dinitroaniline, 2,6-dimethylaniline, 2,6-diisopropyl aniline, 2,4-
Difluoroaniline, 2,4-dibromo aniline, 2,4 dichloro aniline, 2,4,6-trichloroaniline, 2,4,6-tribromaniline, 2,4,6-tri-
Fluoroaniline, 2,4,6-trinitroaniline, 6-hydroxyl naphthylamines, 1-aminoidan, fluorenamine or 4-nitronaphthylamine；
When R2 is fatty amine, for: ethamine, propylamine, butylamine, heptyl amice, 2-aminopropane., tert-butylamine or cyclohexylamine.
It is another object of the present invention to a kind of stereochemical structure N, the preparation method of the mono-ligand metallic catalyst of N-, including following method
Step:
(1) preparation of stereochemical structure alpha-diimine part:
6,13-dihydro-6,13-the ethylene that mol ratio is 1:2-3 is added in the reaction unit equipped with reflux condensing tube and water knockout drum
Benzo[b-15,16-diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL toluene, instead
After answering 12-24 hour, being taken away by remaining solvent under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate
(v/v=20/1) it is purified as eluant or recrystallization, obtains the alpha-diimine part that purity is more than 99%；
(2) preparation of stereochemical structure alpha-diimine metallic catalyst:
The alpha-diimine part (1) step prepared under room temperature and the slaine of weak coordination join dichloromethane with mol ratio 1:1
In alkane solution, after nitrogen protection stirring 8 hours, add enough anhydrous n-hexanes, only put a few days, from dichloromethane and just
The mixed solution of hexane separates out, peony crystal stereochemical structure alpha-diimine metal complex.The slaine of described weak coordination
Such as 1,2-dimethoxy nickelous bromide etc..
Catalyst of the present invention is a kind of novel solid structure N, the mono-ligand-metal complex of N-, its can be such as α-
Diimine nickel (II), alpha-diimine palladium (II), alpha-diimine cobalt (II), alpha-diimine ferrum (II), alpha-diimine copper (II)
Deng coordination compound.General structure is:
Mt=Ni, Pd, Co, Fe or Cu.
R1=Br, Cl, I, NO2, Me, Pr, Bu, Ph, Naph, OMe or OEt.
R2During for aromatic amine:
Or
Or
R2During for fatty amine:
Wherein:
Mt is: nickel, palladium, cobalt, ferrum or copper central metal atom；
R1 is: bromine, chlorine, iodine, nitro, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy；
When R2 is aromatic amine, for: aniline, naphthylamines, open-chain crown ether, parachloroanilinum, para-fluoroaniline, para-fluoroaniline, right
Bromaniline, paranitroanilinum, o-bromoaniline, o-chloraniline, adjacent fluoroaniline, ortho-nitraniline, 2,6-dichloroaniline, 2,6-
Difluoroaniline, 2,6-dibromo aniline, 2,6-dinitroaniline, 2,6-dimethylaniline, 2,6-diisopropyl aniline, 2,4-
Difluoroaniline, 2,4-dibromo aniline, 2,4 dichloro aniline, 2,4,6-trichloroaniline, 2,4,6-tribromaniline, 2,4,6-tri-
Fluoroaniline, 2,4,6-trinitroaniline, 6-hydroxyl naphthylamines, 1-aminoidan, fluorenamine or 4-nitronaphthylamine；
When R2 is fatty amine, for: ethamine, propylamine, butylamine, heptyl amice, 2-aminopropane., tert-butylamine or cyclohexylamine.
Novel solid structure N of the present invention, the central metal atom of the mono-ligand metallic catalyst of N-is nickel, palladium, cobalt, ferrum
Or copper.
Novel solid structure N of the present invention, the substituent group of the diketone of the mono-ligand metallic catalyst of N-is bromine, chlorine, iodine, nitre
Base, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy.
Novel solid structure N of the present invention, the aromatic amine of the mono-ligand metallic catalyst of N-be aniline, naphthylamines, to methylbenzene
Amine, parachloroanilinum, para-fluoroaniline, para-fluoroaniline, para-bromoaniline, paranitroanilinum, o-bromoaniline, o-chloraniline, neighbour
Fluoroaniline, ortho-nitraniline, 2,6-dichloroaniline, 2,6-difluoroaniline, 2,6-dibromo aniline, 2,6-dinitroaniline,
2,6-dimethylaniline, 2,6-diisopropyl aniline, 2,4 difluorobenzene amine, 2,4-dibromo aniline, 2,4 dichloro aniline, 2,4,6-
Trichloroaniline, 2,4,6-tribromaniline, 2,4,6-trifluoromethyl aniline, 2,4,6-trinitroaniline, 6-hydroxyl naphthylamines, 1-amino
Indane, fluorenamine or 4-nitronaphthylamine.
Stereochemical structure N of the present invention, the fatty amine of the mono-ligand metallic catalyst of N-be ethamine, propylamine, butylamine, heptyl amice,
2-aminopropane., tert-butylamine or cyclohexylamine.
Stereochemical structure N of the present invention, the preparation method of the mono-ligand metallic catalyst of N-is:
(1) preparation of novel solid structure alpha-diimine part:
In the reaction bulb equipped with reflux condensing tube and water knockout drum add mol ratio be the 6,13-dihydro-6,13-ethylene of 1:3 also
Pentaphene-15,16-diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL toluene, reaction
After 12-24 hour, being taken away by remaining solvent under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate
(v/v=20/1) it is purified as eluant or recrystallization, obtains the alpha-diimine part that purity is more than 99%；
(2) preparation of novel solid structure alpha-diimine metallic catalyst:
Under room temperature, alpha-diimine part and weak coordinating metal salt such as 1,2-dimethoxy nickelous bromide are added with mol ratio 1:1
In dichloromethane solution, after nitrogen protection is stirred 8 hours, add 10mL anhydrous n-hexane, place a few days, peony
Crystal novel solid structure alpha-diimine metal complex separates out from the mixed solution of dichloromethane and normal hexane.
The mono-ligand metallic catalyst of the N of stereochemical structure of the present invention, N-, it is possible to catalysis obtains having high light transmittance, high glass
Glass transition temperature, good heat stability, oxidation stability, low hydroscopicity, low dielectric constant and good adding
The norborene of work performance, solubility property and adhesion property and the copolymer of norbornene derivative.
Detailed description of the invention:
Below according to embodiment, the present invention is described in further detail.
Embodiment 1
(1)R2During for aromatic amine aniline, the preparation of stereochemical structure alpha-diimine part:
6,13-dihydro-6,13-the ethylene of 10mmol is added in equipped with the 500mL reaction bulb of reflux condensing tube and water knockout drum
Benzo[b-15,16-diketone, the aniline of 30mmol, the p-methyl benzenesulfonic acid of catalytic amount and 150mL toluene are as solvent.
Back flow reaction 24 hours at 130 DEG C.In course of reaction, the water of generation is removed with the form of water-toluene azeotropic mixture by water knockout drum
Go.Being taken away by remaining solvent under vacuo, the solid of precipitation is washed in silicagel column petrol ether/ethyl acetate (v/v=20/1) conduct
De-agent is purified, and after purification, separates out yellow crystals in the petroleum ether mixed solvent with ethyl acetate；
(2) when R2 is aromatic amine aniline, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into the alpha-diimine part of 0.2mmol, 0.2mmol
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chloride, stir after 8 hours under room temperature, add 10mL anhydrous just
Hexane, places a few days, mixed from dichloromethane and normal hexane of peony crystal novel solid structure alpha-diimine metal complex
Close in solution and separate out；
(3) catalysis of norborene is all polymerized
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.Toluene solution (the ρ of norborene it is sequentially added in bottle
=0.5g/mL), B (C6F5)3Toluene solution, the toluene solution of catalyst novel solid alpha-diimine nickel (II) coordination compound,
Toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II) coordinates
The ratio of the amount of thing/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.2 points are reacted at 60 DEG C
Zhong Hou, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, collected by suction gained
Polymer, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.Wherein the conversion ratio of polymer is
98%, catalysis activity is 5.5 × 107gpolymer/molNi·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.Toluene solution (the ρ of norborene it is sequentially added in bottle
=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-two sub-
The toluene solution of amine nickel (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/nickel (II) coordination compound/comonomer three's material is 10/1/10000, copolymerization list
In body, the ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.?
At 60 DEG C after stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands number little
Time, collected by suction resulting polymers, it is dried to constant weight in the vacuum drying oven of 40 DEG C after methanol washing for several times.Wherein gather
The conversion ratio of compound is 54-88%, and catalysis activity is 0.6-1.0 × 106gpolymer/molNi·h。
Embodiment 2
(1) when R2 is aromatic amine aniline, the preparation of the alpha-diimine part of stereochemical structure:
With embodiment 1.
(2) when R2 is aromatic amine aniline, the preparation of stereochemical structure alpha-diimine palladium (II) catalyst:
(3), under nitrogen protection, in 100mL polymerization bottle, it is separately added into 0.2mmol part, 0.2mmol ring pungent two
Alkene methyl chloride palladium and 10mL anhydrous methylene chloride, after stirring 12 hours, considered by core under room temperature while hot
Ball filters under nitrogen atmosphere, adds 10mL anhydrous n-hexane, place a few days, yellow crystals in filtrate
Novel solid structure alpha-diimine palladium (II) coordination compound separates out from the mixed solution of dichloromethane and normal hexane；
(4) catalytic polymerization of norborene
(5) with heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation simultaneously, fill
Nitrogen treatment, replaces three times, it is ensured that reaction system is in dry nitrogen environment.Fall it is sequentially added in bottle
The toluene solution (ρ=0.5g/mL) of bornylene, the toluene solution of B (C6F5) 3, catalyst novel solid α-
The toluene solution of diimine palladium (II) coordination compound, toluene.Wherein, novel solid alpha-diimine palladium (II) coordinates
The amount of thing is that the ratio of the amount of 5.0 × 10-6mol, B (C6F5) 3/ palladium (II) coordination compound/norborene three's material is
10/1/10000, cumulative volume is maintained at
(6)22mL.After reacting 20 minutes at 60 DEG C, the mixing of reaction system hydrochloric acid/methanol (v/v=1/10) is molten
Liquid carries out cancellation, stands a few hours, collected by suction resulting polymers, at 40 DEG C after washing for several times with methanol
Vacuum drying oven in be dried to constant weight.Wherein the conversion ratio of polymer is 95%, and catalysis activity is
5.4×106gpolymer/molPd·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.Toluene solution (the ρ of norborene it is sequentially added in bottle
=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-two sub-
The toluene solution of amine palladium (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/palladium (II) coordination compound/comonomer three's material is 10/1/5000, comonomer
In, the ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.
At 60 DEG C after stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands number
Hour, collected by suction resulting polymers, it is dried to constant weight in the vacuum drying oven of 40 DEG C after methanol washing for several times.Wherein
The conversion ratio of polymer is 31-80%, and catalysis activity is 1.6-4.0 × 105gpolymer/molPd·h。
Embodiment 3
(1)R2During for aromatic amine 2,6-DIPA, the preparation of stereochemical structure alpha-diimine part:
6,13-dihydro-6,13-the ethylene of 10mmol is added in equipped with the 500mL reaction bulb of reflux condensing tube and water knockout drum
Benzo[b-15,16-diketone, the 2,6-DIPA of 30mmol, the p-methyl benzenesulfonic acid of catalytic amount and 150mL toluene
As solvent.Back flow reaction 24 hours at 130 DEG C.In course of reaction, the water of generation passes through water knockout drum with water-toluene azeotropic
The form of thing removes.Being taken away by remaining solvent under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate
(v/v=20/1) it is purified as eluant, after purification, the petroleum ether mixed solvent with ethyl acetate separates out yellow brilliant
Body；
(2)R2During for aromatic amine 2,6-DIPA, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into the alpha-diimine part of 0.2mmol, 0.2mmol
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chloride, stir after 8 hours under room temperature, add 10mL anhydrous just
Hexane, places a few days, and peony crystal novel solid structure alpha-diimine nickel (II) coordination compound is from dichloromethane and normal hexane
Mixed solution separates out；
(3) catalysis of norborene is all polymerized
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After 0.5 minute, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, and sucking filtration is received
Collection resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion of polymer
Rate is 96%, and catalysis activity is 9.4 × 107gpolymer/molNi·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-
The toluene solution of diimine nickel (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is 5.0
×10-6Mol, B (C6F5)3The ratio of the amount of/nickel (II) coordination compound/comonomer three's material is 10/1/10000, in comonomer,
The ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After lower stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, takes out
Resulting polymers is collected in filter, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.Wherein polymer
Conversion ratio is 58-90%, and catalysis activity is 2.6-5.0 × 106gpolymer/molNi·h。
Embodiment 4
(1)R2During for aromatic amine 2,6-DIPA, the preparation of the alpha-diimine part of stereochemical structure:
With embodiment 3；
(2)R2During for aromatic amine 2,6-DIPA, the preparation of stereochemical structure alpha-diimine palladium (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into 0.2mmol part, 0.2mmol cyclo-octadiene methyl
Palladous chloride. and 10mL anhydrous methylene chloride, after stirring 12 hours, consider ball mistake under nitrogen atmosphere by core under room temperature while hot
Filter, adds 10mL anhydrous n-hexane in filtrate, places a few days, yellow crystals novel solid structure alpha-diimine palladium (II)
Coordination compound separates out from the mixed solution of dichloromethane and normal hexane；
(3) catalytic polymerization of norborene
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After 10 minutes, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, collected by suction
Resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion ratio of polymer
Being 92%, catalysis activity is 0.9 × 107gpolymer/molPd·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-
The toluene solution of diimine palladium (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/palladium (II) coordination compound/comonomer three's material is 10/1/5000, in comonomer,
The ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After lower stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, takes out
Resulting polymers is collected in filter, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.Wherein polymer
Conversion ratio is 35-86%, and catalysis activity is 1.7-5.1 × 105gpolymer/molPd·h。
Embodiment 5
(1)R2During for aromatic amine 4-fluoroaniline, the preparation of stereochemical structure alpha-diimine part:
6,13-dihydro-6,13-the ethylene of 10mmol is added in equipped with the 500mL reaction bulb of reflux condensing tube and water knockout drum
Benzo[b-15,16-diketone, the 2,6-DIPA of 30mmol, the concentrated sulphuric acid of catalytic amount and 150mL toluene conduct
Solvent.Back flow reaction 36 hours at 130 DEG C.In course of reaction, the water of generation passes through water knockout drum with water-toluene azeotropic mixture
Form removes.Being taken away by remaining solvent under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate
(v/v=20/1) it is purified as eluant, after purification, the petroleum ether mixed solvent with ethyl acetate separates out yellow brilliant
Body；
(2)R2During for aromatic amine 4-fluoroaniline, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into the alpha-diimine part of 0.2mmol, 0.2mmol
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chloride, stir after 8 hours under room temperature, add 10mL anhydrous just
Hexane, places a few days, and peony crystal novel solid structure alpha-diimine nickel (II) coordination compound is from dichloromethane and normal hexane
Mixed solution separates out；
(3) catalysis of norborene is all polymerized
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After 20 minutes, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, collected by suction
Resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion ratio of polymer
Being 95%, catalysis activity is 5.6 × 106gpolymer/molNi·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it being carried out evacuation, inflated with nitrogen processes simultaneously,
Replace three times, it is ensured that reaction system is in dry nitrogen environment.Be sequentially added in bottle norborene toluene solution (ρ=
0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid alpha-diimine
The toluene solution of nickel (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound be 5.0 ×
10-6Mol, B (C6F5)3The ratio of the amount of/nickel (II) coordination compound/comonomer three's material is 10/1/10000, in comonomer,
The ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After lower stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, takes out
Resulting polymers is collected in filter, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.Wherein polymer
Conversion ratio is 50-80%, and catalysis activity is 8.2-9.1 × 105gpolymer/molNi·h。
Embodiment 6
(1)R2During for aromatic amine 4-fluoroaniline, the preparation of the alpha-diimine part of stereochemical structure:
With embodiment 5.
(2)R2During for aromatic amine 4-fluoroaniline, the preparation of stereochemical structure alpha-diimine palladium (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into 0.2mmol part, 0.2mmol cyclo-octadiene methyl
Palladous chloride. and 10mL anhydrous methylene chloride, after stirring 12 hours, consider ball mistake under nitrogen atmosphere by core under room temperature while hot
Filter, adds 10mL anhydrous n-hexane in filtrate, places a few days, yellow crystals novel solid structure alpha-diimine palladium (II)
Coordination compound separates out from the mixed solution of dichloromethane and normal hexane；
(3) catalytic polymerization of norborene
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After 30 minutes, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, collected by suction
Resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion ratio of polymer
Being 90%, catalysis activity is 3.1 × 106gpolymer/molPd·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-
The toluene solution of diimine palladium (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/palladium (II) coordination compound/comonomer three's material is 10/1/5000, comonomer
In, the ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.
At 60 DEG C after stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands number
Hour, collected by suction resulting polymers, it is dried to constant weight in the vacuum drying oven of 40 DEG C after methanol washing for several times.Wherein
The conversion ratio of polymer is 30-82%, and catalysis activity is 1.4-3.8 × 105gpolymer/molPd·h。
Embodiment 7
(1)R2During for fatty amine, the preparation of the alpha-diimine part of stereochemical structure:
6,13-dihydro-6,13-the ethylene of 10mmol is added in equipped with the 500mL reaction bulb of reflux condensing tube and water knockout drum
Benzo[b-15,16-diketone, the ethamine of 30mmol, the p-methyl benzenesulfonic acid of catalytic amount and 150mL toluene are as solvent.130
Back flow reaction 12 hours at DEG C.In course of reaction, the water of generation is removed with the form of water-toluene azeotropic mixture by water knockout drum.
After reaction completely, allowing its slow cooling, only put, yellow crystals separates out from solvent；
(2)R2During for fatty amine, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into the alpha-diimine part of 0.2mmol, 0.2mmol
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chloride, stir after 8 hours under room temperature, add 10mL anhydrous just
Hexane, places a few days, and peony crystal novel solid structure alpha-diimine nickel (II) coordination compound is from dichloromethane and normal hexane
Mixed solution separates out；
(3) catalytic polymerization of norborene
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After 30 minutes, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, collected by suction
Resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion ratio of polymer
Being 90%, catalysis activity is 3.3 × 106gpolymer/molNi·h；
(5) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-
The toluene solution of diimine nickel (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/nickel (II) coordination compound/comonomer three's material is 10/1/5000, comonomer
In, the ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.
At 60 DEG C after stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands number
Hour, collected by suction resulting polymers, it is dried to constant weight in the vacuum drying oven of 40 DEG C after methanol washing for several times.Wherein
The conversion ratio of polymer is 45-79%, and catalysis activity is 4.9-8.7 × 105gpolymer/molPd·h。
Embodiment 8
(1)R2During for fatty amine, the preparation of the alpha-diimine part of stereochemical structure:
With embodiment 3；
(2)R2During for fatty amine, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst:
Under nitrogen protection, in 100mL polymerization bottle, it is separately added into 0.2mmol part, 0.2mmol cyclo-octadiene methyl
Palladous chloride. and 10mL anhydrous methylene chloride, after stirring 12 hours, consider ball mistake under nitrogen atmosphere by core under room temperature while hot
Filter, adds 10mL anhydrous n-hexane in filtrate, places a few days, yellow crystals novel solid structure alpha-diimine palladium (II)
Coordination compound separates out from the mixed solution of dichloromethane and normal hexane；
(3) catalytic polymerization of norborene
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) coordination compound
Solution, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II)
The ratio of the amount of coordination compound/norborene three's material is 10/1/10000, and cumulative volume is maintained at 22mL.React at 60 DEG C
After one hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands a few hours, and sucking filtration is received
Collection resulting polymers, is dried to constant weight after methanol washing for several times in the vacuum drying oven of 40 DEG C.The wherein conversion of polymer
Rate is 89%, and catalysis activity is 1.6 × 106gpolymer/molPd·h；
(4) norborene is closed with the catalyzed copolymerization of norbornene derivative 5-norborene-2-carboxylate methyl ester
With heat gun heating equipped with magnetic stir bar with the reaction bulb of mouth, it is carried out evacuation, at inflated with nitrogen simultaneously
Reason, replaces three times, it is ensured that reaction system is in dry nitrogen environment.The toluene solution of norborene it is sequentially added in bottle
(ρ=0.5g/mL), 5-norborene-2-carboxylate methyl ester, B (C6F5)3Toluene solution, major catalyst novel solid α-
The toluene solution of diimine palladium (II) coordination compound, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) coordination compound is
5.0×10-6Mol, B (C6F5)3The ratio of the amount of/palladium (II) coordination compound/comonomer three's material is 10/1/5000, comonomer
In, the ratio of the amount of the material of norborene/5-norborene-2-carboxylate methyl ester is 9/1-5/5, and cumulative volume is maintained at 22mL.
At 60 DEG C after stoichiometric number hour, the mixed solution of reaction system hydrochloric acid/methanol (v/v=1/10) carries out cancellation, stands number
Hour, collected by suction resulting polymers, it is dried to constant weight in the vacuum drying oven of 40 DEG C after methanol washing for several times.Wherein
The conversion ratio of polymer is 30-78%, and catalysis activity is 1.6-3.2 × 105gpolymer/molPd·h。
Claims (2)
1. a stereochemical structure N, the mono-ligand metallic catalyst of N-, its general structure is:
Mt is: nickel, palladium, cobalt, ferrum or copper central metal atom；
R1 is: bromine, chlorine, iodine, nitro, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy；
When R2 is aromatic amine, for: aniline, naphthylamines, open-chain crown ether, parachloroanilinum, para-fluoroaniline, para-fluoroaniline,
Para-bromoaniline, paranitroanilinum, o-bromoaniline, o-chloraniline, adjacent fluoroaniline, ortho-nitraniline, 2,6-dichloro-benzenes
Amine, 2,6-difluoroaniline, 2,6-dibromo aniline, 2,6-dinitroaniline, 2,6-dimethylaniline, 2,6-diisopropyl
Base aniline, 2,4 difluorobenzene amine, 2,4-dibromo aniline, 2,4 dichloro aniline, 2,4,6-trichloroaniline, 2,4,6-tri-
Bromaniline, 2,4,6-trifluoromethyl aniline, 2,4,6-trinitroaniline, 6-hydroxyl naphthylamines, 1-aminoidan, fluorenamine or 4-
Nitronaphthylamine；
When R2 is fatty amine, for: ethamine, propylamine, butylamine, heptyl amice, 2-aminopropane., tert-butylamine or cyclohexylamine.
2. a stereochemical structure N, the preparation method of the mono-ligand metallic catalyst of N-, including following method step:
(1) preparation of stereochemical structure alpha-diimine part:
6,13-dihydro-the 6,13-that mol ratio is 1:2-3 is added in the reaction unit equipped with reflux condensing tube and water knockout drum
Ethylene Benzo[b-15,16-diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL
Toluene, after reacting 12-24 hour, takes remaining solvent away under vacuo, the solid of precipitation silicagel column petroleum ether/
Ethyl acetate (v/v=20/1) is purified as eluant or recrystallization, obtains the alpha-diimine that purity is more than 99%
Part；
(2) preparation of stereochemical structure alpha-diimine metallic catalyst:
The alpha-diimine part (1) step prepared under room temperature and the slaine of weak coordination join two with mol ratio 1:1
In chloromethanes solution, after nitrogen protection is stirred 8 hours, add enough anhydrous n-hexanes, only put a few days, from dichloro
The mixed solution of methane and normal hexane separates out and obtains stereochemical structure alpha-diimine metal complex, be stereochemical structure
The mono-ligand metal of N, N-.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109456814A (en) * | 2018-12-29 | 2019-03-12 | 江苏奥克化学有限公司 | A kind of transformer oil composition and preparation method thereof |
| CN109852452A (en) * | 2018-12-29 | 2019-06-07 | 江苏奥克化学有限公司 | A kind of low-temperature resistance hybrid-engine oil and preparation method thereof |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
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Cited By (4)
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| CN109456814A (en) * | 2018-12-29 | 2019-03-12 | 江苏奥克化学有限公司 | A kind of transformer oil composition and preparation method thereof |
| CN109852452A (en) * | 2018-12-29 | 2019-06-07 | 江苏奥克化学有限公司 | A kind of low-temperature resistance hybrid-engine oil and preparation method thereof |
| CN112892595A (en) * | 2021-01-22 | 2021-06-04 | 邹育英 | Para-nitro-substituted palladium catalyst and application thereof in Heck reaction |
| CN112892594A (en) * | 2021-01-22 | 2021-06-04 | 黄志怀 | Ortho-phenyl substituted alpha-diimine iron catalyst and preparation method thereof |
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