CN105936659B - Mono- ligand metallic catalysts of stereochemical structure N, N and preparation method thereof - Google Patents
Mono- ligand metallic catalysts of stereochemical structure N, N and preparation method thereof Download PDFInfo
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- CN105936659B CN105936659B CN201510882585.9A CN201510882585A CN105936659B CN 105936659 B CN105936659 B CN 105936659B CN 201510882585 A CN201510882585 A CN 201510882585A CN 105936659 B CN105936659 B CN 105936659B
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- Prior art keywords
- alpha
- diimine
- stereochemical structure
- enb
- preparation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000003863 metallic catalyst Substances 0.000 title claims abstract description 21
- 239000003446 ligand Substances 0.000 title claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 53
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000001412 amines Chemical class 0.000 claims abstract description 21
- -1 paranitroanilinum Chemical compound 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000004982 aromatic amines Chemical group 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000000460 chlorine Substances 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
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 6
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [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
- 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
- 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 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 195
- 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 76
- 229910000071 diazene Inorganic materials 0.000 claims description 57
- 239000007787 solid Substances 0.000 claims description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 50
- 230000003197 catalytic effect Effects 0.000 claims description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 10
- 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
- 239000003480 eluent Substances 0.000 claims description 6
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-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 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 claims 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical class BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims 1
- UEMGWPRHOOEKTA-UHFFFAOYSA-N 1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1 UEMGWPRHOOEKTA-UHFFFAOYSA-N 0.000 claims 1
- 125000001894 2,4,6-trinitrophenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O 0.000 claims 1
- 125000003456 2,6-dinitrophenyl group Chemical group [H]C1=C([H])C(=C(*)C(=C1[H])[N+]([O-])=O)[N+]([O-])=O 0.000 claims 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 125000004129 indan-1-yl group Chemical group [H]C1=C([H])C([H])=C2C(=C1[H])C([H])([H])C([H])([H])C2([H])* 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 20
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 abstract description 8
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 abstract description 8
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 abstract description 8
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 abstract description 8
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 abstract description 5
- GVPODVKBTHCGFU-UHFFFAOYSA-N 2,4,6-tribromoaniline Chemical class NC1=C(Br)C=C(Br)C=C1Br GVPODVKBTHCGFU-UHFFFAOYSA-N 0.000 abstract description 4
- IAHOUQOWMXVMEH-UHFFFAOYSA-N 2,4,6-trinitroaniline Chemical class NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IAHOUQOWMXVMEH-UHFFFAOYSA-N 0.000 abstract description 4
- LGUKNGHOZGOFJL-UHFFFAOYSA-N 2,4,6-tris(fluoromethyl)aniline Chemical class NC1=C(CF)C=C(CF)C=C1CF LGUKNGHOZGOFJL-UHFFFAOYSA-N 0.000 abstract description 4
- DYSRXWYRUJCNFI-UHFFFAOYSA-N 2,4-dibromoaniline Chemical class NC1=CC=C(Br)C=C1Br DYSRXWYRUJCNFI-UHFFFAOYSA-N 0.000 abstract description 4
- KQCMTOWTPBNWDB-UHFFFAOYSA-N 2,4-dichloroaniline Chemical class NC1=CC=C(Cl)C=C1Cl KQCMTOWTPBNWDB-UHFFFAOYSA-N 0.000 abstract description 4
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical class CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 abstract description 4
- XIRRDAWDNHRRLB-UHFFFAOYSA-N 2,6-dibromoaniline Chemical class NC1=C(Br)C=CC=C1Br XIRRDAWDNHRRLB-UHFFFAOYSA-N 0.000 abstract description 4
- JDMFXJULNGEPOI-UHFFFAOYSA-N 2,6-dichloroaniline Chemical class NC1=C(Cl)C=CC=C1Cl JDMFXJULNGEPOI-UHFFFAOYSA-N 0.000 abstract description 4
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 abstract description 4
- QFUSCYRJMXLNRB-UHFFFAOYSA-N 2,6-dinitroaniline Chemical class NC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O QFUSCYRJMXLNRB-UHFFFAOYSA-N 0.000 abstract description 4
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 abstract description 4
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 abstract description 4
- CYSPWCARDHRYJX-UHFFFAOYSA-N 9h-fluoren-1-amine Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2N CYSPWCARDHRYJX-UHFFFAOYSA-N 0.000 abstract description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000005002 naphthylamines Chemical class 0.000 abstract description 4
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 abstract description 4
- NATVSFWWYVJTAZ-UHFFFAOYSA-N 2,4,6-trichloroaniline Chemical class NC1=C(Cl)C=C(Cl)C=C1Cl NATVSFWWYVJTAZ-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003983 crown ethers Chemical class 0.000 abstract description 3
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical group FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical class NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 abstract description 2
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 abstract description 2
- CEPCPXLLFXPZGW-UHFFFAOYSA-N 2,4-difluoroaniline Chemical class NC1=CC=C(F)C=C1F CEPCPXLLFXPZGW-UHFFFAOYSA-N 0.000 abstract 1
- HOSGXJWQVBHGLT-UHFFFAOYSA-N 6-hydroxy-3,4-dihydro-1h-quinolin-2-one Chemical group N1C(=O)CCC2=CC(O)=CC=C21 HOSGXJWQVBHGLT-UHFFFAOYSA-N 0.000 abstract 1
- XSCFKJGIAYKLRV-UHFFFAOYSA-N n-naphthalen-1-ylnitramide Chemical class C1=CC=C2C(N[N+](=O)[O-])=CC=CC2=C1 XSCFKJGIAYKLRV-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 96
- 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
- 239000003054 catalyst Substances 0.000 description 31
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 31
- 229920000642 polymer Polymers 0.000 description 25
- 239000000463 material Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 22
- 230000001186 cumulative effect Effects 0.000 description 16
- 238000006073 displacement reaction Methods 0.000 description 16
- 238000001291 vacuum drying Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 241000736199 Paeonia Species 0.000 description 6
- 235000006484 Paeonia officinalis Nutrition 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 4
- 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 3
- BVPJPRYNQHAOPQ-UHFFFAOYSA-N 4-nitronaphthalen-1-amine Chemical class C1=CC=C2C(N)=CC=C([N+]([O-])=O)C2=C1 BVPJPRYNQHAOPQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- MOIVWVDMFLNLOT-UHFFFAOYSA-N NC1=CC=CC=C1.[Br] Chemical compound NC1=CC=CC=C1.[Br] MOIVWVDMFLNLOT-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 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
- 238000002834 transmittance Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- HWFFFQWCACGJBD-UHFFFAOYSA-N NC1=CC=CC=C1.[F] Chemical group NC1=CC=CC=C1.[F] HWFFFQWCACGJBD-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
- 239000003795 chemical substances by application Substances 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
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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
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Abstract
The present invention provides a kind of stereochemical structure N, the mono- ligand metallic catalysts of N and preparation method thereof, and its general structure is：
Description
Technical field：
The present invention relates to the catalyst system and catalyzing and preparation method for ENB and norbornene derivative addition copolymerization；
Relate in particular to a kind of stereochemical structure N, the mono- ligand metallic catalysts of N- and preparation method thereof.
Background technology：
Additive poly ENB causes its tool because of its unique twin nuclei (US Patent 5468819,5569730)
There is heat, the advantages that chemical stability is good, and light transmittance is high and birefringence is relatively low, these properties cause polynorbornene to become
The focus of field of olefin polymerisation.However, in the application process of reality, this polynorbornene also faces bigger difficulty,
A series of mainly its processing characteristics, shortcomings such as solubility property and adhesion property are poor, limits its application.In order to improve
ENB and alpha-olefin, polar monomer, are typically copolymerized by these deficiencies.And in this copolymerization process, efficiently, surely
The selection of fixed, resistance to polar catalyst is then most important.
Since Brookhart Successful utilization alpha-diimine metal complexs, catalysis alpha-olefines polymerization merging shows higher
After catalytic activity, alpha-diimine metallic catalyst, in past ten years causing people widely pays close attention to.Alpha-diimine metal
The catalytic performance of catalyst is mainly the electronics and steric effect by its part, and therefore, relatively more at present mainly passes through
The change of substituent corresponds to the catalytic performance and stability of metallic catalyst to adjust it on alpha-diimine part.Most of work
Mainly around change alpha-diimine part upper skeleton structure.The skeleton structure of big steric hindrance can effectively prevent alpha-diimine because of it
The aromatic ring structure of metal complex is rotated so as to protect metal center, so, it can greatly enhance alpha-diimine metal combination
The stability and catalytic performance of thing.Nevertheless, most of work also only rests on alpha-diimine metal combination both at home and abroad at present
In the design of object plane skeleton structure, the research for three-dimensional skeleton structure is also seldom.
The catalyst for developing novel high-performance is the necessary condition for realizing functional poly cycloolefin, and catalyst ligand synthesizes
The exploitation of new technology is to determine the key of catalytic performance.How first to design and synthesize α-diketone with stereoeffect, then with
Arylamine or fatty amine carry out ketoamine condensation reaction, and change metal by changing stereoeffect and the electronic structure of arylamine
Catalyst structure, so as to reach the purpose for strengthening its heat endurance and catalytic activity.
The content of the invention：
The present invention provides a kind of stereochemical structure N, the mono- ligand metallic catalysts of N- and preparation method thereof, and it has high printing opacity
Property, high glass-transition temperature, good heat endurance, oxidation stability, low hydroscopicity, low dielectric constant and good
Processing characteristics, the novel solid structure of the copolymer of the ENB and norbornene derivative of solubility property and adhesion property
The mono- ligand metallic catalyst of N, N-, preparation method is simple, and accessory substance is few, environmentally friendly.
A kind of stereochemical structure N of the present invention, the mono- ligand metallic catalysts of N-, its general structure are：
Mt is：Nickel, palladium, cobalt, iron 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, it is：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- dichloroanilines, 2,6- difluorobenzenes
Amine, 2,6- dibromo anilines, 2,6- dinitroanilines, 2,6- dimethylanilines, 2,6- diisopropyl anilines, 2,4 difluorobenzene amine,
2,4- dibromo anilines, 2,4 dichloro aniline, 2,4,6- trichloroanilines, 2,4,6- tribromanilines, 2,4,6- trifluoromethyl anilines, 2,4,6-
Trinitroaniline, 6- hydroxyls naphthylamines, 1- aminoidans, fluorenamine or 4- nitronaphthylamines；
When R2 is fatty amine, it is：Ethamine, propylamine, butylamine, heptyl amice, isopropylamine, 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 catalysts of N-, including it is as follows
Method and step：
(1) preparation of stereochemical structure alpha-diimine part：
It is 1 that mol ratio is added in the reaction unit equipped with reflux condensing tube and water knockout drum:2-3 6,13- dihydro -6,
13- ethylene pentacene -15,16- diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL first
Benzene, after reacting 12-24 hours, remaining solvent is taken away under vacuo, the solid of precipitation is in silicagel column petroleum ether/acetic acid second
Ester (v/v=20/1) is purified as eluant, eluent 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 and the metal salt of weak coordination at room temperature prepared by (1) step is with mol ratio 1:1 is added to dichloro
In dichloromethane, after nitrogen protection stirring 8 hours, add enough anhydrous n-hexanes, put a few days only, from dichloromethane and just oneself
Separated out in the mixed solution of alkane, peony crystal stereochemical structure alpha-diimine metal complex.The metal salt of the weak coordination is such as
1,2- dimethoxy nickelous bromides etc..
Catalyst of the present invention is a kind of mono- ligand-metal complex of novel solid structure N, N-, and it for example can be
Alpha-diimine nickel (II), alpha-diimine palladium (II), alpha-diimine cobalt (II), alpha-diimine iron (II), alpha-diimine copper (II) etc.
Complex.General structure is：
Mt=Ni, Pd, Co, Fe or Cu.
R1=Br, Cl, I, NO2, Me, Pr, Bu, Ph, Naph, OMe or OEt.
R2For aromatic amine when：
Or
Or
R2For fatty amine when：
Wherein：
Mt is：Nickel, palladium, cobalt, iron 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, it is：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- dichloroanilines, 2,6- difluorobenzenes
Amine, 2,6- dibromo anilines, 2,6- dinitroanilines, 2,6- dimethylanilines, 2,6- diisopropyl anilines, 2,4 difluorobenzene amine,
2,4- dibromo anilines, 2,4 dichloro aniline, 2,4,6- trichloroanilines, 2,4,6- tribromanilines, 2,4,6- trifluoromethyl anilines, 2,4,6-
Trinitroaniline, 6- hydroxyls naphthylamines, 1- aminoidans, fluorenamine or 4- nitronaphthylamines；
When R2 is fatty amine, it is：Ethamine, propylamine, butylamine, heptyl amice, isopropylamine, tert-butylamine or cyclohexylamine.
The central metal atom of the mono- ligand metallic catalysts of novel solid structure N, N- of the present invention be nickel, palladium, cobalt,
Iron or copper.
The substituent of the diketone of the mono- ligand metallic catalysts of novel solid structure N, N- of the present invention be bromine, chlorine, iodine,
Nitro, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy.
The aromatic amine of the mono- ligand metallic catalysts of novel solid structure N, N- of the present invention is aniline, naphthylamines, to first
Base aniline, parachloroanilinum, para-fluoroaniline, para-fluoroaniline, para-bromoaniline, paranitroanilinum, o-bromoaniline, o-chloraniline, adjacent fluorine
Aniline, ortho-nitraniline, 2,6- dichloroanilines, 2,6- difluoroanilines, 2,6- dibromo anilines, 2,6- dinitroanilines, 2,6- bis-
Methylaniline, 2,6- diisopropyl anilines, 2,4 difluorobenzene amine, 2,4- dibromo anilines, 2,4 dichloro aniline, 2,4,6- trichloro-benzenes
Amine, 2,4,6- tribromanilines, 2,4,6- trifluoromethyl anilines, 2,4,6- trinitroanilines, 6- hydroxyls naphthylamines, 1- aminoidans, fluorenamine
Or 4- nitronaphthylamines.
The fatty amine of the mono- ligand metallic catalyst of stereochemical structure N of the present invention, N- is ethamine, propylamine, butylamine, heptan
Amine, isopropylamine, tert-butylamine or cyclohexylamine.
The preparation method of the mono- ligand metallic catalyst of stereochemical structure N of the present invention, N- is：
(1) preparation of novel solid structure alpha-diimine part：
It is 1 that mol ratio is added in the reaction bulb equipped with reflux condensing tube and water knockout drum:3 6,13- dihydro -6,13- second
Pentacene -15,16- diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL toluene are supportted, instead
After answering 12-24 hours, remaining solvent is taken away under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate (v/
V=20/1) purified as eluant, eluent or recrystallization, obtain the alpha-diimine part that purity is more than 99%；
(2) preparation of novel solid structure alpha-diimine metallic catalyst：
At room temperature by alpha-diimine part and weak coordinating metal salt such as 1,2- dimethoxies nickelous bromide with mol ratio 1:1 adds
Enter into dichloromethane solution, after nitrogen protection is stirred 8 hours, add 10mL anhydrous n-hexanes, place a few days, peony crystal
Novel solid structure alpha-diimine metal complex separates out from the mixed solution of dichloromethane and n-hexane.
The mono- ligand metallic catalyst of the N of stereochemical structure of the present invention, N-, it can be catalyzed to obtain with high light transmittance,
High glass-transition temperature, good heat endurance, oxidation stability, low hydroscopicity, low dielectric constant and good
The ENB of processing characteristics, solubility property and adhesion property and the copolymer of norbornene derivative.
Embodiment：
Below according to embodiment, the present invention is described in further detail.
Embodiment 1
(1)R2For aromatic amine aniline when, the preparation of stereochemical structure alpha-diimine part：
10mmol 6,13- dihydro -6,13- second is added in the 500mL reaction bulbs equipped with reflux condensing tube and water knockout drum
Support
Pentacene -15,16- diketone, 30mmol aniline, the p-methyl benzenesulfonic acid and 150mL toluene of catalytic amount are as molten
Agent.Back flow reaction 24 hours at 130 DEG C.In course of reaction, the water of generation is removed by water knockout drum in the form of water-toluene azeotropic mixture
Go.Remaining solvent is taken away under vacuo, the solid of precipitation is made in silicagel column with petrol ether/ethyl acetate (v/v=20/1)
Purified for eluant, eluent, after purification, yellow crystals are separated out in the in the mixed solvent of petroleum ether and 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 bottles, 0.2mmol alpha-diimine part, 0.2mmol second are separately added into
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chlorides, after stirring 8 hours at room temperature, 10mL anhydrous n-hexanes are added, are placed
A few days, peony crystal novel solid structure alpha-diimine metal complex are analysed from the mixed solution of dichloromethane and n-hexane
Go out；
(3) the catalysis homopolymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.After being reacted 2 minutes at 60 DEG C,
Reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is polymerize obtained by collected by suction
Thing, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 98%, is urged
It is 5.5 × 10 to change activity7gpolymer/molNi·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine nickel (II) complex.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/nickel (II) complex/comonomer three's material is 10/1/10000, in comonomer, drop
The ratio between amount of material of bornylene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After reacting a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered
Resulting polymers are collected, are dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein turn of polymer
Rate is 54-88%, and catalytic 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 bottles, 0.2mmol parts, 0.2mmol cyclo-octadiene methyl are separately added into
Palladium bichloride and 10mL anhydrous methylene chlorides, after stirring 12 hours at room temperature, ball is considered by core while hot and filtered under nitrogen atmosphere,
10mL anhydrous n-hexanes are added in filtrate, place a few days, yellow crystals novel solid structure alpha-diimine palladium (II) complex
Separated out from the mixed solution of dichloromethane and n-hexane；
(4) catalytic polymerization of ENB
(5) reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, filled
Nitrogen treatment, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene of ENB is sequentially added into bottle
Solution (ρ=0.5g/mL), B (C6F5) 3 toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) complex
Solution, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10-6mol, the palladiums (II) of B (C6F5) 3/
The ratio between amount of complex/ENB three's material is 10/1/10000, and cumulative volume is maintained at
(6)22mL.After being reacted 20 minutes at 60 DEG C, reaction system hydrochloric acid/methanol (v/v=1/10) mixed solution
It is quenched, stands a few hours, collected by suction resulting polymers, is done after being washed for several times with methanol in 40 DEG C of vacuum drying chamber
It is dry to constant weight.Wherein the conversion ratio of polymer is 95%, and catalytic activity is 5.4 × 106gpolymer/molPdh；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine palladium (II) complex.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/palladium (II) complex/comonomer three's material is 10/1/5000, in comonomer, drops ice
The ratio between amount of material of piece alkene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.It is anti-at 60 DEG C
Should be after a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered and is received
Collect resulting polymers, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.The wherein conversion of polymer
Rate is 31-80%, and catalytic activity is 1.6-4.0 × 105gpolymer/molPd·h。
Embodiment 3
(1)R2For aromatic amine 2,6-DIPA when, the preparation of stereochemical structure alpha-diimine part：
10mmol 6,13- dihydro -6,13- second is added in the 500mL reaction bulbs equipped with reflux condensing tube and water knockout drum
Support pentacene -15,16- diketone, 30mmol 2,6-DIPA, the p-methyl benzenesulfonic acid and 150mL toluene of catalytic amount
As solvent.Back flow reaction 24 hours at 130 DEG C.In course of reaction, the water of generation is by water knockout drum with water-toluene azeotropic mixture
Form removes.Remaining solvent is taken away under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate (v/v=
20/1) purified as eluant, eluent, after purification, yellow crystals are separated out in the in the mixed solvent of petroleum ether and ethyl acetate；
(2)R2For aromatic amine 2,6-DIPA when, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol alpha-diimine part, 0.2mmol second are separately added into
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chlorides, after stirring 8 hours at room temperature, 10mL anhydrous n-hexanes are added, are placed
A few days, peony crystal novel solid structure alpha-diimine nickel (II) complex is from the mixed solution of dichloromethane and n-hexane
Separate out；
(3) the catalysis homopolymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.Reacted 0.5 minute at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 96%,
Catalytic activity is 9.4 × 107gpolymer/molNi·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine nickel (II) complex.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/nickel (II) complex/comonomer three's material is 10/1/10000, in comonomer, drop
The ratio between amount of material of bornylene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After reacting a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered
Resulting polymers are collected, are dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein turn of polymer
Rate is 58-90%, and catalytic activity is 2.6-5.0 × 106gpolymer/molNi·h。
Embodiment 4
(1)R2For aromatic amine 2,6-DIPA when, the preparation of the alpha-diimine part of stereochemical structure：
With embodiment 3；
(2)R2For aromatic amine 2,6-DIPA when, the preparation of stereochemical structure alpha-diimine palladium (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol parts, 0.2mmol cyclo-octadiene methyl chlorides are separately added into
Change palladium and 10mL anhydrous methylene chlorides, after stirring 12 hours at room temperature, ball is considered by core while hot and filtered under nitrogen atmosphere,
In filtrate add 10mL anhydrous n-hexanes, place a few days, yellow crystals novel solid structure alpha-diimine palladium (II) complex from
Separated out in the mixed solution of dichloromethane and n-hexane；
(3) catalytic polymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.Reacted 10 minutes at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 92%,
Catalytic activity is 0.9 × 107gpolymer/molPd·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine palladium (II) complex.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/palladium (II) complex/comonomer three's material is 10/1/5000, in comonomer, drops ice
The ratio between amount of material of piece alkene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.It is anti-at 60 DEG C
Should be after a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered and is received
Collect resulting polymers, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.The wherein conversion of polymer
Rate is 35-86%, and catalytic activity is 1.7-5.1 × 105gpolymer/molPd·h。
Embodiment 5
(1)R2For aromatic amine 4- fluoroanilines when, the preparation of stereochemical structure alpha-diimine part：
10mmol 6,13- dihydro -6,13- second is added in the 500mL reaction bulbs equipped with reflux condensing tube and water knockout drum
Support pentacene -15,16- diketone, 30mmol 2,6-DIPA, the concentrated sulfuric acid of catalytic amount and 150mL toluene conducts
Solvent.Back flow reaction 36 hours at 130 DEG C.In course of reaction, the water of generation is by water knockout drum with water-toluene azeotropic mixture
Form removes.Remaining solvent is taken away under vacuo, the solid of precipitation is in silicagel column petrol ether/ethyl acetate
(v/v=20/1) purified as eluant, eluent, after purification, it is brilliant to separate out yellow in the in the mixed solvent of petroleum ether and ethyl acetate
Body；
(2)R2For aromatic amine 4- fluoroanilines when, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol alpha-diimine part, 0.2mmol second are separately added into
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chlorides, after stirring 8 hours at room temperature, 10mL anhydrous n-hexanes are added, are placed
A few days, peony crystal novel solid structure alpha-diimine nickel (II) complex is from the mixed solution of dichloromethane and n-hexane
Separate out；
(3) the catalysis homopolymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.Reacted 20 minutes at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 95%,
Catalytic activity is 5.6 × 106gpolymer/molNi·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine nickel (II) complex.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/nickel (II) complex/comonomer three's material is 10/1/10000, in comonomer, drop
The ratio between amount of material of bornylene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.At 60 DEG C
After reacting a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered
Resulting polymers are collected, are dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein turn of polymer
Rate is 50-80%, and catalytic activity is 8.2-9.1 × 105gpolymer/molNi·h。
Embodiment 6
(1)R2For aromatic amine 4- fluoroanilines when, the preparation of the alpha-diimine part of stereochemical structure：
With embodiment 5.
(2)R2For aromatic amine 4- fluoroanilines when, the preparation of stereochemical structure alpha-diimine palladium (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol parts, 0.2mmol cyclo-octadiene methyl chlorides are separately added into
Change palladium and 10mL anhydrous methylene chlorides, after stirring 12 hours at room temperature, ball is considered by core while hot and filtered under nitrogen atmosphere,
In filtrate add 10mL anhydrous n-hexanes, place a few days, yellow crystals novel solid structure alpha-diimine palladium (II) complex from
Separated out in the mixed solution of dichloromethane and n-hexane；
(3) catalytic polymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.Reacted 30 minutes at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 90%,
Catalytic activity is 3.1 × 106gpolymer/molPd·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine palladium (II) complex.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/palladium (II) complex/comonomer three's material is 10/1/5000, in comonomer, drops ice
The ratio between amount of material of piece alkene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.It is anti-at 60 DEG C
Should be after a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered and is received
Collect resulting polymers, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.The wherein conversion of polymer
Rate is 30-82%, and catalytic activity is 1.4-3.8 × 105gpolymer/molPd·h。
Embodiment 7
(1)R2For fatty amine when, the preparation of the alpha-diimine part of stereochemical structure：
10mmol 6,13- dihydro -6,13- second is added in the 500mL reaction bulbs equipped with reflux condensing tube and water knockout drum
Pentacene -15,16- diketone is supportted, 30mmol ethamine, the p-methyl benzenesulfonic acid and 150mL toluene of catalytic amount are as solvent.130
Back flow reaction 12 hours at DEG C.In course of reaction, the water of generation is removed by water knockout drum in the form of water-toluene azeotropic mixture.Instead
Should completely after, allow its slow cooling, put only, yellow crystals separate out from solvent；
(2)R2For fatty amine when, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol alpha-diimine part, 0.2mmol second are separately added into
Glycol dimethyl ether nickelous bromide and 10mL anhydrous methylene chlorides, after stirring 8 hours at room temperature, 10mL anhydrous n-hexanes are added, are placed
A few days, peony crystal novel solid structure alpha-diimine nickel (II) complex is from the mixed solution of dichloromethane and n-hexane
Separate out；
(3) catalytic polymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine nickel (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ nickel (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.Reacted 30 minutes at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 90%,
Catalytic activity is 3.3 × 106gpolymer/molNi·h；
(5) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine nickel (II) complex.Wherein, the amount of novel solid alpha-diimine nickel (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/nickel (II) complex/comonomer three's material is 10/1/5000, in comonomer, drops ice
The ratio between amount of material of piece alkene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.It is anti-at 60 DEG C
Should be after a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered and is received
Collect resulting polymers, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.The wherein conversion of polymer
Rate is 45-79%, and catalytic activity is 4.9-8.7 × 105gpolymer/molPd·h。
Embodiment 8
(1)R2For fatty amine when, the preparation of the alpha-diimine part of stereochemical structure：
With embodiment 3；
(2)R2For fatty amine when, the preparation of stereochemical structure alpha-diimine nickel (II) catalyst：
Under nitrogen protection, in 100mL polymerization bottles, 0.2mmol parts, 0.2mmol cyclo-octadiene methyl chlorides are separately added into
Change palladium and 10mL anhydrous methylene chlorides, after stirring 12 hours at room temperature, ball is considered by core while hot and filtered under nitrogen atmosphere,
In filtrate add 10mL anhydrous n-hexanes, place a few days, yellow crystals novel solid structure alpha-diimine palladium (II) complex from
Separated out in the mixed solution of dichloromethane and n-hexane；
(3) catalytic polymerization of ENB
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), B (C6F5)3Toluene solution, the toluene of catalyst novel solid alpha-diimine palladium (II) complex it is molten
Liquid, toluene.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10-6Mol, B (C6F5)3/ palladium (II) coordinates
The ratio between amount of thing/ENB three's material is 10/1/10000, and cumulative volume is maintained at 22mL.A hour is reacted at 60 DEG C
Afterwards, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, poly- obtained by collected by suction
Compound, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.Wherein the conversion ratio of polymer is 89%,
Catalytic activity is 1.6 × 106gpolymer/molPd·h；
(4) catalyzed copolymerization of ENB and norbornene derivative 5- ENB -2- carboxylate methyl esters is closed
The reaction bulb equipped with magnetic stir bar and with branch mouth is heated with heat gun, while it is vacuumized, nitrogen charging
Gas disposal, displacement is three times, it is ensured that reaction system is in dry nitrogen environment.The toluene that ENB is sequentially added into bottle is molten
Liquid (ρ=0.5g/mL), 5- ENB -2- carboxylate methyl esters, B (C6F5)3Toluene solution, major catalyst novel solid α-two it is sub-
The toluene solution, toluene of amine palladium (II) complex.Wherein, the amount of novel solid alpha-diimine palladium (II) complex is 5.0 × 10- 6Mol, B (C6F5)3The ratio between amount of/palladium (II) complex/comonomer three's material is 10/1/5000, in comonomer, drops ice
The ratio between amount of material of piece alkene/5- ENB -2- carboxylate methyl esters is 9/1-5/5, and cumulative volume is maintained at 22mL.It is anti-at 60 DEG C
Should be after a few hours, reaction system is quenched with the mixed solution of hydrochloric acid/methanol (v/v=1/10), stands a few hours, is filtered and is received
Collect resulting polymers, dried after being washed for several times with methanol in 40 DEG C of vacuum drying chamber to constant weight.The wherein conversion of polymer
Rate is 30-78%, and catalytic activity is 1.6-3.2 × 105gpolymer/molPd·h。
Claims (2)
1. the mono- ligand metallic catalyst of a kind of stereochemical structure N, N-, its general structure are：
Mt is：Nickel, palladium, cobalt, iron or copper central metal atom；
R1 is：Bromine, chlorine, iodine, nitro, methyl, propyl group, butyl, phenyl, naphthyl, methoxy or ethoxy；
R2When being aromatic group, it is：Phenyl, naphthyl, p-methylphenyl, rubigan, p-fluorophenyl, p-bromophenyl, p-nitrophenyl
Base, o-bromophenyl, Chloro-O-Phenyl, o-fluorophenyl, O-Nitrophenylfluorone, 2,6- dichlorophenyls, 2,6- difluorophenyls, 2,6- dibromobenzenes
Base, 2,6- dinitrophenyls, 2,6- 3,5-dimethylphenyls, 2,6- diisopropyl phenyls, 2,4 difluorobenzene base, 2,4- dibromo phenyls,
2,4 dichloro benzene base, 2,4,6- trichlorophenyls, 2,4,6- tribromos phenyl, 2,4,6- trifluorophenyls, 2,4,6- trinitrophenyls,
6- hydroxynaphenyls, 1- indanyls, fluorenyl or 4- nitro naphthyls；
R2When being fat group, it is：Ethyl, propyl group, butyl, heptyl, isopropyl, the tert-butyl group or cyclohexyl.
2. a kind of preparation method of the mono- ligand metallic catalyst of stereochemical structure N, N-, including following method and step：
(1) preparation of stereochemical structure alpha-diimine part：
It is 1 that mol ratio is added in the reaction unit equipped with reflux condensing tube and water knockout drum:2-3 6,13- dihydro -6,13- second
Pentacene -15,16- diketone and aromatic amine or fatty amine, and the p-methyl benzenesulfonic acid of catalytic amount and 50-300mL toluene are supportted, instead
After answering 12-24 hours, take remaining solvent away under vacuo, the solid of precipitation silicagel column with petrol ether/ethyl acetate v/v=
20/1 is purified as eluant, eluent or recrystallization, obtains the alpha-diimine part that purity is more than 99%；
(2) preparation of stereochemical structure alpha-diimine metallic catalyst：
At room temperature will（1）The metal salt of the alpha-diimine part prepared and weak coordination is walked with mol ratio 1:1 is added to dichloromethane
In solution, after nitrogen protection stirring 8 hours, enough anhydrous n-hexanes are added, put a few days only, from dichloromethane and n-hexane
Separated out in mixed solution and obtain stereochemical structure alpha-diimine metal complex, as stereochemical structure N, the mono- ligand metals of N-.
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| CN1181089A (en) * | 1995-01-24 | 1998-05-06 | 纳幕尔杜邦公司 | 'Alpha'-olefines and olefin polymers and processes therefor |
| CN1226256A (en) * | 1996-07-23 | 1999-08-18 | 纳幕尔杜邦公司 | Polymerization process for olefins |
| CN102399323A (en) * | 2011-10-09 | 2012-04-04 | 南昌大学 | N,O-single ligand metal catalyst with stereochemical structure and preparation method thereof |
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| CN1181089A (en) * | 1995-01-24 | 1998-05-06 | 纳幕尔杜邦公司 | 'Alpha'-olefines and olefin polymers and processes therefor |
| CN1226256A (en) * | 1996-07-23 | 1999-08-18 | 纳幕尔杜邦公司 | Polymerization process for olefins |
| CN102399323A (en) * | 2011-10-09 | 2012-04-04 | 南昌大学 | N,O-single ligand metal catalyst with stereochemical structure and preparation method thereof |
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