CN106349294A - Aniline anthraquinone late transition metal compound and preparation method and application thereof - Google Patents
Aniline anthraquinone late transition metal compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN106349294A CN106349294A CN201610693376.4A CN201610693376A CN106349294A CN 106349294 A CN106349294 A CN 106349294A CN 201610693376 A CN201610693376 A CN 201610693376A CN 106349294 A CN106349294 A CN 106349294A
- Authority
- CN
- China
- Prior art keywords
- aniline
- anthraquinone
- metal complex
- transition metal
- late transition
- 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
- WGQDNTPYPXIPOH-UHFFFAOYSA-N aniline anthracene-9,10-dione Chemical compound NC1=CC=CC=C1.C1=CC=CC=2C(C3=CC=CC=C3C(C12)=O)=O WGQDNTPYPXIPOH-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000003623 transition metal compounds Chemical class 0.000 title abstract 4
- -1 amino hydrogen Chemical compound 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 41
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 150000001448 anilines Chemical class 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 119
- 229910052723 transition metal Inorganic materials 0.000 claims description 82
- 150000003624 transition metals Chemical class 0.000 claims description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 59
- 239000005977 Ethylene Substances 0.000 claims description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 59
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 150000001336 alkenes Chemical class 0.000 claims description 32
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 30
- 229910052763 palladium Inorganic materials 0.000 claims description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 150000002431 hydrogen Chemical class 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 22
- 239000002585 base Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 19
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 16
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004414 alkyl thio group Chemical group 0.000 claims description 12
- YLQBEKUKMJWXMC-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-ylphosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.P[c-]1cccc1 YLQBEKUKMJWXMC-UHFFFAOYSA-N 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 150000001925 cycloalkenes Chemical class 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-Methylanthraquinone Natural products C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 claims description 8
- WXVMUGXIJGKWLJ-UHFFFAOYSA-N C1=CC=CCCCC1.[Cl] Chemical compound C1=CC=CCCCC1.[Cl] WXVMUGXIJGKWLJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- QCYXGORGJYUYMT-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QCYXGORGJYUYMT-UHFFFAOYSA-N 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- MQIUMARJCOGCIM-UHFFFAOYSA-N 1,5-dichloroanthracene-9,10-dione Chemical compound O=C1C2=C(Cl)C=CC=C2C(=O)C2=C1C=CC=C2Cl MQIUMARJCOGCIM-UHFFFAOYSA-N 0.000 claims description 7
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 7
- 241001597008 Nomeidae Species 0.000 claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 230000007704 transition Effects 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 claims description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 2
- QFDKSNZVNQZXOT-UHFFFAOYSA-N 4-chloro-1-hydroxy-6-nitroanthracene-9,10-dione Chemical compound OC1=CC=C(C=2C(C3=CC(=CC=C3C(C12)=O)[N+](=O)[O-])=O)Cl QFDKSNZVNQZXOT-UHFFFAOYSA-N 0.000 claims description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- DEYYBJRTVTWNNA-UHFFFAOYSA-N [Br].C(C)(=O)OC=C Chemical compound [Br].C(C)(=O)OC=C DEYYBJRTVTWNNA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- MPLWNENKBSBMFN-UHFFFAOYSA-N hex-5-enyl acetate Chemical compound CC(=O)OCCCCC=C MPLWNENKBSBMFN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims 1
- GFBOYIQELHSHRP-UHFFFAOYSA-N [Ni].CP(C)C Chemical compound [Ni].CP(C)C GFBOYIQELHSHRP-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000539 dimer Substances 0.000 claims 1
- 150000002118 epoxides Chemical class 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 52
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 2
- 239000003426 co-catalyst Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- 150000004696 coordination complex Chemical class 0.000 description 31
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- 230000004044 response Effects 0.000 description 30
- 230000001052 transient effect Effects 0.000 description 29
- 239000000047 product Substances 0.000 description 26
- 230000037048 polymerization activity Effects 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 23
- 239000007787 solid Substances 0.000 description 23
- 238000001914 filtration Methods 0.000 description 20
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 18
- 238000001291 vacuum drying Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 206010013786 Dry skin Diseases 0.000 description 14
- 230000035484 reaction time Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
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- 239000000706 filtrate Substances 0.000 description 9
- 208000035126 Facies Diseases 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
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- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
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- DIGCBXFHKQEPMI-UHFFFAOYSA-N CC(O)=O.CCCCC=C Chemical compound CC(O)=O.CCCCC=C DIGCBXFHKQEPMI-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- HQBJSEKQNRSDAZ-UHFFFAOYSA-N 2,6-dimethoxyaniline Chemical compound COC1=CC=CC(OC)=C1N HQBJSEKQNRSDAZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 3
- 150000004056 anthraquinones Chemical class 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- XYEGKWAUWWATMS-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-2,6-dimethoxybenzamide Chemical group COC1=CC=CC(OC)=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O XYEGKWAUWWATMS-UHFFFAOYSA-N 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 2
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 2
- 0 CC(*)CCC1CC(C*)CC1 Chemical compound CC(*)CCC1CC(C*)CC1 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- DPZNOMCNRMUKPS-UHFFFAOYSA-N resorcinol dimethyl ether Natural products COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YQMUORJJDBQCOV-UHFFFAOYSA-N $l^{1}-phosphanylmethane Chemical compound [P]C YQMUORJJDBQCOV-UHFFFAOYSA-N 0.000 description 1
- PLUFITIFLBGFPN-UHFFFAOYSA-N 1,2-dichloroanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=C(Cl)C(Cl)=CC=C3C(=O)C2=C1 PLUFITIFLBGFPN-UHFFFAOYSA-N 0.000 description 1
- OPECBHGHSFBITB-UHFFFAOYSA-N 2-anilinonaphthalene-1,4-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C=C1NC1=CC=CC=C1 OPECBHGHSFBITB-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- 241001044369 Amphion Species 0.000 description 1
- VOVULSHUCMSJRB-UHFFFAOYSA-N ClC1=CC=C(C2=CC3=CC=CC(=C3C=C12)OC)OC Chemical compound ClC1=CC=C(C2=CC3=CC=CC(=C3C=C12)OC)OC VOVULSHUCMSJRB-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- CDZXWKHHGDVYEP-UHFFFAOYSA-N aniline anthracene Chemical compound NC1=CC=CC=C1.C1=CC=CC2=CC3=CC=CC=C3C=C21 CDZXWKHHGDVYEP-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides an aniline anthraquinone late transition metal compound and a preparation method and application thereof. The preparation method includes following steps: dissolving chloroanthraquinone and substituted aniline in a solvent, and reacting at certain temperature and under catalytic action to generate aniline anthraquinone ligand; dissolving the aniline anthraquinone ligand in an organic solvent, and adding a hydrogen pulling agent for reaction at proper temperature to pull off amino hydrogen to form a ligand salt compound; adding a metal precursor for reaction to obtain the aniline anthraquinone late transition metal compound. The aniline anthraquinone late transition metal compound can be used for homopolymerization or copolymerization of allyl monomer. A catalytic system is used for allyl polymerization, and both high polymer and low polymer can be obtained by selecting different co-catalysts.
Description
Technical field
The invention belongs to olefin catalytic technical field, it is related to a kind of aniline anthraquinone late transition metal complex and its preparation side
The aniline anthracene of application in method and application, more particularly to catalyzed ethylene and/or cycloolefins, polarity/function monomer homopolymerization or copolymerization
Quinone late transition metal complex and carbon monoxide-olefin polymeric and its preparation method and application method.
Background technology
Polyolefin catalyst is core and the key of olefinic polymerization industrial manufacture process, its huge number, current industrialization
Catalyst mainly have ziegler-natta catalyst system (de pat889229 (1953)；it pat545332(1956)；
it pat536899(1956)；Chem.rev., 2000,100,1169.), phillips catalyst system
(belg.pat.530617(1955)；Chem.rev., 1996,96,3327.) and metallocene catalyst system
(kaminsky.w.,berlin:springer,1999.).
In recent years, late transition metal catalyst for olefin polymerization had obtained tremendous development.Late transition metal catalyst is for alkene
High poly- the breaking through first of hydrocarbon is the alpha-diimine base nickel of nineteen ninety-five brookhart et al. report, palladium catalyst
(brookhart.m., j.am.chem.soc., 1995,117,6414.), the exploitation of this catalyst series also greatly promotes
The development of late transition metal catalyst for olefin polymerization.Grubbs etc. reports a class neutrality salicylic alidehyde imine on science and closes
Nickel (ii) catalyst (grubbs.r.h., science, 2000,287,460.), such catalyst just can in a mild condition
The polyethylene obtaining high molecular, low collateralization is it is often more important that can catalyzed ethylene be total to the alkene containing polar functional group
Gather and obtain copolymer.
Ketone-imines nickel catalyst also shows excellent catalytic performance and is widely studied.Brookhart et al. reports
Road serial ketone-imines Raney nickel (brookhart, m., organometallics., 2001,20,3217；
organometallics.,2003,22,3533；Organometallics., 2003,22,250.), even if this catalyst series
Still there is certain catalysis activity in the case of there is no promoter, obtain the polyethylene with short-chain branch, but not to pole
The polymerization of property monomer is studied.Shiono et al. reports anilino- naphthoquinone Raney nickel (macromol.rapid
Commun., 2006,27,1418.), in b (c6f5)3Show very high ethylene action under existence condition, obtain and carry long-chain branch
Polyethylene, but this catalyst polymerization activity in the presence of not having promoter is low, and also and have no research its to pole
The polymerizing power of property monomer.Kim etc. reports a class ketimide part Raney nickel under the activation of modified methylaluminoxane
(kim, i.j.organomet.chem., 2009,694,1254.), can be with the generation butylene of high selectivity, but activity is not
Too high, and article reports that it can be only generated micro high polymer.At present, in order to reach higher polymerization activity, late transition metal is urged
Agent in most cases still needs the promoters such as the boron compound of substantial amounts of alkylaluminoxane or costliness；And, utilize
Same coordination compound not only can obtain high polymer but also can obtain the catalyst system and catalyzing of the oligomer of high selectivity is also very rare
's.
Content of the invention
It is an object of the invention to provide a kind of aniline anthraquinone late transition metal complex and preparation method and application, especially
It is that the aniline anthraquinone late transition metal providing application in catalyzed ethylene and/or cycloolefins, polarity/function monomer homopolymerization or copolymerization is joined
Compound and carbon monoxide-olefin polymeric and its preparation method and application method, catalyst system and catalyzing provided by the present invention is used for olefinic polymerization,
By selecting different promoters, high polymer can be obtained and can obtain oligomer again.
The preparation method of the aniline anthraquinone late transition metal complex of the present invention, step is:
(1) chloroanthraquinone and substituted aniline are dissolved in a solvent, react under uniform temperature and catalytic action, generate aniline
Anthraquinones part；
(2) described aniline Anthraquinones part is dissolved in organic solvent, under the conditions of proper temperature:
A) add and pull out hydrogen reagent reaction, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding metal precursor, reaction；
Obtain described aniline anthraquinone late transition metal complex.
As preferred technical scheme:
The preparation method of aniline anthraquinone late transition metal complex as above, in step (1), described solvent is positive heptan
Alkane, toluene, chlorobenzene, 1,4- dioxy six alkane, octane, 4-methyl-2 pentanone or ethylenediamine；Described uniform temperature is 90～130 DEG C,
Under catalytic action, the time of reaction is 12～36h；
The system of described catalytic action includes major catalyst, promoter and alkali, and described major catalyst is double (two subunits
Acetone) palladium or three (dibenzalacetone) two palladium or acid chloride, described promoter is biaryl phosphine or big steric hindrance phosphino- two cyclopentadienyl
Ferrum, described alkali is naotbu、k3po4、cs2co3Or k2co3；
Wherein big steric hindrance phosphino- ferrocene is preferably double (diphenylphosphine) ferrocene of 1,1'-.
The preparation method of aniline anthraquinone late transition metal complex as above, in step (2), described organic solvent is
Toluene, oxolane, dichloromethane, ether, normal hexane, chlorobenzene or 1,4- dioxy six alkane；
Described proper temperature condition refers to 0～60 DEG C；
The described hydrogen reagent that pulls out is sodium hydride, hydrofining, n-BuLi, potassium tert-butoxide or two (trimethyl silicon substrate) Sodamide.；
The described hydrogen reagent and the mol ratio of described aniline Anthraquinones part of pulling out is 1～2.2:1；Addition is pulled out hydrogen reagent reaction and is referred to aniline anthracene
Quinone part and the described hydrogen reagent that pulls out react 1～10h at 0～60 DEG C, the amino hydrogen on aniline anthraquinone part are pulled out, formation is joined
Body salt compound；
Described metal precursor is trans-chloro- (phenyl) double (triphenyl phosphorus) nickel (), trans-chloro- (methyl) double (three
Methyl phosphorus) nickel (), chlorination pi-allyl nickel (ii) dimer, chlorine (cyclo-octadiene) methyl palladium or chlorination Allylpalladium (ii) dimerization
Thing；
Described metal precursor is 1:0.5～1 with the mol ratio of described aniline Anthraquinones part；After adding metal precursor
Reaction refer at 0～60 DEG C, aniline anthraquinone part salt compound and metal precursor complexation reaction 5～20h, form this
Bright provided aniline anthraquinone metal complex；
When the metal of described metal precursor is palladium, then add pyridine or dimethyl sulfoxide, react 1～6h, added
Pyridine or dimethyl sulfoxide are 1～5:1 with the mol ratio of described aniline Anthraquinones part；
After step (1) generates aniline Anthraquinones part, extract by organic solvent recrystallization or by organic solvent
Carry out purification processes；The organic solvent of recrystallization or purification by liquid extraction be toluene, dichloromethane, oxolane, ether, normal hexane,
Normal heptane, chlorobenzene, methanol or ethanol.
The preparation method of aniline anthraquinone late transition metal complex as above, described chloroanthraquinone is 1-chloroanthraquinone, 1,
The derivant of 5- dichloroanthraquinone, the derivant of 1-chloroanthraquinone or 1,5- dichloroanthraquinone；General structure is:
The structural formula of described substituted aniline is:
Wherein, r1、r2、r3、r4And r5It is independently from each other hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen
Element, nitro, aryl or aryl substituent, or further, r1And r5, r4And r5, r3And r4, r2And r3Form carbon or containing miscellaneous former
The ring structure of son；On described ring structure independent with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitre
One or more of base, aryl or aryl substituent；
Described chloroanthraquinone is 1:0.8～3 with the mol ratio of described substituted aniline；
Described major catalyst is the 2～8% of described chloroanthraquinone quality；
Described major catalyst is 1:1.2～2 with the mol ratio of promoter；
Described alkali is 1～3:1 with the mol ratio of described chloroanthraquinone；
The derivant of described 1-chloroanthraquinone is 1- chloro- 8- tectoquinone, 1- chloro- 7- tectoquinone, 1- chloro- 5,8- dimethyl
Anthraquinone or 4- chloro- 1- hydroxyl -6- nitroanthraquinone；
The derivant of described 1,5- dichloroanthraquinone is the chloro- 4- tectoquinone of 1,5- bis-, the chloro- 4,8- dimethoxy anthracene of 1,5- bis-
Quinone or the chloro- 4- tectoquinone of 1,5- bis-.
The general structure formula of described aniline Anthraquinones part is:
The aniline anthraquinone late transition metal complex that the preparation method of the present invention is obtained, has a following general structure:
Wherein, r1～r5Be independently from each other hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitro,
Aryl or aryl substituent, or further, r1And r5, r4And r5, r3And r4, r2And r3Form carbon or containing heteroatomic ring knot
Structure；
On described ring structure independent with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitro, virtue
One or more of base or aryl substituent；
r6For methyl, phenyl, benzyl or unsubstituted；
r7～r13It is independently from each other hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, nitro, hydroxyl, carboxylic
One or more of base, aryl or aryl substituent, or further, r7And r8, r8And r9, r9And r10, r11And r12, r12
And r13It is individually formed carbon or contain heteroatomic ring structure；
Described ring structure independence with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, nitro, hydroxyl, carboxylic
One or more of base, aryl or aryl substituent；
M is nickel or palladium；
L is trimethyl-phosphine, triphenylphosphine, pyridine, dimethyl sulfoxide or pi-allyl.
Present invention also offers a kind of carbon monoxide-olefin polymeric of aniline anthraquinone late transition metal complex preparation, described catalysis
Agent compositionss are made up of described aniline anthraquinone late transition metal complex and promoter；Described promoter be selected from aikyiaiurnirsoxan beta,
One of alkyl aluminum compound, alkyl aluminum chloride compound, aluminum chloride, boron compound or double-(1,5- cyclo-octadiene) nickel
More than.
A kind of carbon monoxide-olefin polymeric as above, described aikyiaiurnirsoxan beta is specially MAO (mao), tert-butyl group aluminum changes
Property MAO (mmao) or the modified MAO (dmmao) of the tert-butyl group aluminum that is dried；Described alkyl aluminum chemical combination
Thing is specially trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium；Described chlorination alkyl aluminum
Compound is specially diethylaluminum chloride or ethylaluminium dichloride；Boron compound is specially three (pentafluorophenyl group) borine；Described
Aniline anthraquinone late transition metal complex is 1:30～5000 with the mol ratio of aluminum；
Described aniline anthraquinone late transition metal complex and three (pentafluorophenyl group) borines or double-(1,5- cyclo-octadiene) nickel
Mol ratio is 1:1～10.
Present invention also offers application in the homopolymerization or copolymerization of catalyzed alkene monomer for the described carbon monoxide-olefin polymeric.
Invention still further provides above-mentioned transient metal complex is being catalyzed second with it with above-mentioned carbon monoxide-olefin polymeric
Alkene and the homopolymerization of cycloolefins, and the application in copolymerization.
As above apply, under inert gas shielding, aniline anthraquinone late transition metal complex or catalyst combination
Thing is first dissolved in solvent, is subsequently adding olefinic monomer, at -50～120 DEG C, reactive polymeric 1～1440min under 0.1～5mpa,
Prepared olefin homo or olefin copolymer；
Described solvent is toluene, chlorobenzene, normal hexane or normal heptane；
Described olefinic monomer is ethylene, cycloolefins or polarity/function monomer；
Described cycloolefins are norborene, 5- methyl -2- norborene, 5- ethyl -2- norborene, 5- butyl -2- fall
Bornylene, 5- hexyl -2- norborene, 5- decyl -2- norborene, 5- vinyl -2- norborene, 5- acrylic -2- fall
Bornylene, 5- cyclohexyl -2- norborene, 5- cyclopenta -2- norborene, dicyclopentadiene or methyldicyclopentadiene；
Described polarity/function monomer 5- norborene -2- carboxylate methyl ester, 5- norborene -2- formaldehyde, acetic acid 5- hexenyl
Ester, carbic anhydride, acrylic acid methyl ester., allyl acetate, vinyl ethyl ether, pi-allyl ether, vinyl acetate bromine third
Alkene or chloropropene；
Described polarity/function monomer is 10 with the mol ratio of aniline anthraquinone late transition metal complex or carbon monoxide-olefin polymeric
～50000:1；
Described olefin polymer includes olefin polymer and ethylene low polymer, and the molecular weight of described olefin polymer is 2000
～500000g mol-1, molecular weight distributing index (mw/mn) it is 1.4～3.0, fusing point (tm) it is 50～130 DEG C；Described ethylene is low
Polymers is mainly butylene and hexene.
Beneficial effect:
There is isolated oxygen atom in coordination compound designed by the present invention, when different promoters and oxygen atom phase separation,
Form the amphion coordination compound of different structure, the lewis acidity of effective control central metal is such that it is able to effectively to alkene
The molecular weight of polymerized hydrocarbon product and chain structure are regulated and controled.The nickel catalyst that the present invention provides can be in non-promoted dose of condition
Under show higher catalysis activity and close it is also possible to synthesize ethylene polymer or high selectivity under the conditions of different promoters
Become ethylene low polymer, and to cycloolefins, also there is very high polymerization activity, the cycloolefin homopolymers of high molecular can be obtained
With cycloolefines/ethylene copolymer ization thing, this catalyst system and catalyzing also can be used for the copolymerization of ethylene or cycloolefins and polar monomer, and has higher
Molecular weight, greater activity and higher insertion rate.
Brief description:
Fig. 1 is the aniline Anthraquinones transient metal complex crystal structure figure of embodiment 1；
Fig. 2 is the aniline Anthraquinones transient metal complex crystal structure figure of embodiment 2；
Fig. 3 is the aniline Anthraquinones transient metal complex crystal structure figure of embodiment 4；
Fig. 4 is the aniline Anthraquinones transient metal complex crystal structure figure of embodiment 6.
Wherein, c is carbon atom, and n is nitrogen-atoms, and o is oxygen atom, and p is phosphorus atoms, and ni is nickle atom, and pd is palladium atom.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate this
Bright rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content of present invention instruction, art technology
Personnel can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
The synthetic route chart of aniline anthraquinone late transition metal complex in following embodiments:
Embodiment 1
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) by mol ratio, the 1-chloroanthraquinone for 1:1.5 is dissolved in toluene with aniline, is subsequently adding catalytic action system,
Catalytic action system is double (two subunit acetone) palladiums, big steric hindrance phosphino- ferrocene and cs2co3, wherein, double (two subunits third
Ketone) palladium is the 2% of 1-chloroanthraquinone, the mol ratio of double (two subunit acetone) palladium and big steric hindrance phosphino- ferrocene is 1:1.2,
cs2co3Mol ratio with 1-chloroanthraquinone is 1:1, and under catalytic action, flow back under 90 DEG C of condition of nitrogen gas 36h, is cooled to room temperature,
Solvent toluene vacuum is drained reservation solid, remaining solid is dissolved in dichloromethane, wash with water 5 times, separatory funnel separates
Organic faciess, the excessive anhydrous magnesium sulfate of addition is dried, and filters and retains filtrate, dichloromethane solvent concentrated in vacuo, is subsequently adding just own
Alkane, separates out a large amount of red solid.Filtration under diminished pressure obtains 1- (anilino-) anthraquinone part, then washs three times with normal hexane 20ml, very
Empty drying both obtains red product, yield 95%,1h nmr(cdcl3,400mhz):11.38(s,1h,-nh),8.27-8.34(m,
2h,ar-h),7.71-7.82(m,3h,ar-h),7.51(m,2h,ar-h),7.42(m,2h,nh-ar-h),7.34(dd,2h,
nh-ar-h),7.22(m,1h,nh-ar-h).
(2) 1- (anilino-) the anthraquinone part after purification is dissolved in oxolane, at 60 DEG C:
A) add hydrogenation nak response, reaction temperature is 60 DEG C, the response time is 1h, hydrofining is joined with 1- (anilino-) anthraquinone
The mol ratio of body is 1.5:1, pulls out amino hydrogen evolution part salt compound；
B) it is subsequently adding chlorine (cyclo-octadiene) methyl palladium, chlorine (cyclo-octadiene) methyl palladium and 1- (anilino-) anthraquinone part
Mol ratio is 1:1, under nitrogen protection at 30 DEG C, reacts 5h, then adds pyridine, wherein pyridine and 1- (aniline to reaction system
Base) anthraquinone part mol ratio be 1:1, continue reaction 3h.Reaction obtains blue title complex,1h nmr(cdcl3,
400mhz):8.894(m,2h,py-h),7.96(t,1h,py-h),7.73(t,2h,py-h),-0.02(s,3h,pd-ch3),
Obtain aniline Anthraquinones transient metal complex, Fig. 1 is shown in by its corresponding crystal structure schematic diagram.
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1-r5For hydrogen, r6For methyl, r7-r13For hydrogen, m it is
Palladium, l are pyridine).
Embodiment 2
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) by mol ratio, the 1-chloroanthraquinone for 1:1.8 is dissolved in Isosorbide-5-Nitrae-dioxy six alkane with 2,6-DIPA, so
Add catalytic action system afterwards, catalytic action system is double (two subunit acetone) palladiums, big steric hindrance phosphino- ferrocene and cs2co3,
Wherein, double (two subunit acetone) palladium is the 4% of 1-chloroanthraquinone, and double (two subunit acetone) palladium is rubbed with big steric hindrance phosphine ferrocene
That ratio is 1:1.5, cs2co3Mol ratio with 1-chloroanthraquinone is 1.5:1, under catalytic action, flows back under 110 DEG C of condition of nitrogen gas
36h, is cooled to room temperature, solvent Isosorbide-5-Nitrae-dioxy six alkane vacuum is drained reservation solid, remaining solid is dissolved in dichloromethane, uses
Water washing 5 times, separatory funnel separation organic faciess, add excessive anhydrous magnesium sulfate to be dried, filter and retain filtrate, vacuum drains dichloro
Methane solvent, is subsequently adding excessive normal hexane, has yellow solid to separate out, filtration under diminished pressure falls solid, retains filtrate.Filtrate is suitably dense
Contracting, target product is recrystallized to give through multiple low-temperature, is red crystals, yield 53%.1h nmr(cdcl3,400mhz):10.95
(s,1h,-nh),8.28-8.37(dd,2h,ar-h),7.74-7.83(m,2h,ar-h),7.64(d,1h,ar-h),7.39(m,
2h,nh-ar-h),7.29(s,1h,ar-h),7.27(s,1h,ar-h),6.61(d,1h,nh-ar-h),3.09(m,2h,-
ch),1.11-1.20(dd,12h,-ch3).
(2) 1- (2,6-DIPA base) the anthraquinone part after purification is dissolved in oxolane, at 20 DEG C:
A) add hydrogenation nak response, reaction temperature is 20 DEG C, the response time is 3h, hydrofining and 1- (2,6- diisopropyls
Anilino-) anthraquinone part mol ratio be 1.1:1, pull out amino hydrogen evolution part salt compound；
(3) b) it is subsequently adding chlorine (cyclo-octadiene) methyl palladium, chlorine (cyclo-octadiene) methyl palladium and 1- (2,6- diisopropyl benzenes
Amido) anthraquinone part mol ratio be 1:1, nitrogen protection under at 0 DEG C, react 8h, then to reaction system add pyridine, wherein
Pyridine is 3:1 with the mol ratio of 1- (2,6-DIPA base) anthraquinone part, continues reaction 3h, that is, obtains the aniline of blueness
Anthraquinones transient metal complex,1h nmr(cdcl3,400mhz):7.26-8.15(m,36h,ar-h),6.13-7.09(m,
16h,ar-h),3.59(m,4h,-ch),0.95-1.07(dd,24h,-ch3), Fig. 2 is shown in by its crystal structure schematic diagram.
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1And r2For isopropyl, r3-r5For hydrogen, r6For methyl,
r7-r13For hydrogen, m be palladium, l be pyridine).
Embodiment 3
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) 1-chloroanthraquinone for 1:0.8 for the mol ratio and 2,6- dimethoxyaniline are dissolved in Isosorbide-5-Nitrae-dioxy six alkane, so
Add catalytic action system afterwards, catalytic action system is double (two subunit acetone) palladiums, big steric hindrance phosphino- ferrocene and phosphine phosphorio
The mol ratio of ferrocene is 1:2, cs2co3Mol ratio with 1-chloroanthraquinone is 2:1, under catalytic action, under 130 DEG C of condition of nitrogen gas
Backflow 12h, is cooled to room temperature, solvent Isosorbide-5-Nitrae-dioxy six alkane vacuum is drained reservation solid, remaining solid is dissolved in dichloromethane
Alkane, washes with water 5 times, separatory funnel separation organic faciess, adds excessive anhydrous magnesium sulfate to be dried, filters and retain filtrate, vacuum is dense
Contracting dichloromethane solvent, is subsequently adding normal hexane, separates out a large amount of red solid.Filtration under diminished pressure obtains solid, with positive 20ml hexane
Washed once, then washed twice with 20ml ether, vacuum drying had both obtained red product, yield 91%.1h nmr(cdcl3,
400mhz):10.83(s,1h,-nh),8.26-8.35(dd,2h,ar-h),7.67-7.79(m,3h,ar-h),7.42(t,1h,
ar-h),7.23(d,1h,ar-h),6.27(d,1h,nh-ar-h),6.69(d,2h,nh-ar-h),3.82(s,6h,-ch3).
(2) 1- (2,6- dimethoxy benzene amido) the anthraquinone part after purification is dissolved in oxolane, at 0 DEG C:
A) add hydrogenation nak response, reaction temperature is 0 DEG C, the response time is 10h, hydrofining and 1- (2,6- dimethoxys
Anilino-) anthraquinone part mol ratio be 1.3:1, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding chlorine (cyclo-octadiene) methyl palladium, chlorine (cyclo-octadiene) methyl palladium and 1- (2,6- dimethoxyanilines
Base) mol ratio of anthraquinone part is 1:1, under nitrogen protection at 30 DEG C, reacts 10h, then adds pyridine to reaction system, its
Middle pyridine is 5:1 with the mol ratio of 1- (2,6- dimethoxy benzene amido) anthraquinone part, continues reaction 3h, that is, obtains the benzene of blueness
Amine Anthraquinones transient metal complex,1h nmr(cd2cl2,400mhz):8.81(m,2h,py-h),8.17(m,1h,ar-h),
8.03(m,1h,ar-h),7.89(t,1h,py-h),7.63(m,2h,py-h),7.46(m,2h,ar-h),7.37(dd,1h,
ar-h),7.12(t,1h,ar-h),6.95-6.99(m,1h,ar-h),6.72(d,2h,ar-h),6.66(d,1h,ar-h),
3.83(s,6h,-ch3),-0.16(s,3h,pd-ch3).
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1And r2For methoxyl group, r3-r5For hydrogen, r6For methyl,
r7-r13For hydrogen, m be palladium, l be pyridine).
Embodiment 4
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) by mol ratio, the 1-chloroanthraquinone for 1:1.8 is dissolved in Isosorbide-5-Nitrae-dioxy six alkane with 2,6-DIPA, so
Add catalytic action system afterwards, catalytic action system is double (two subunit acetone) palladiums, big position phosphino- ferrocene and cs2co3, its
In, double (two subunit acetone) palladium is the 4% of 1-chloroanthraquinone, and the mol ratio of big steric hindrance phosphino- ferrocene is 1:1.5, cs2co3With
The mol ratio of 1-chloroanthraquinone is 1.5:1, and under catalytic action, flow back under 110 DEG C of condition of nitrogen gas 24h, is cooled to room temperature, by solvent
Isosorbide-5-Nitrae-dioxy six alkane vacuum drains reservation solid, and remaining solid is dissolved in dichloromethane, washes with water 5 times, separatory funnel divides
From organic faciess, add excessive anhydrous magnesium sulfate to be dried, filter and retain filtrate, vacuum is drained dichloromethane solvent, was subsequently adding
Amount normal hexane, has yellow solid to separate out, filtration under diminished pressure falls solid, retains filtrate.Filtrate suitably concentrates, and target product is through repeatedly low
Temperature is recrystallized to give, and is red crystals, yield 53%.1h nmr(cdcl3,400mhz):10.95(s,1h,-nh),8.28-
8.37(dd,2h,ar-h),7.74-7.83(m,2h,ar-h),7.64(d,1h,ar-h),7.39(m,2h,nh-ar-h),7.29
(s,1h,ar-h),7.27(s,1h,ar-h),6.61(d,1h,nh-ar-h),3.09(m,2h,-ch),1.11-1.20(dd,
12h,-ch3).
(2) 1- (2,6-DIPA base) the anthraquinone part after purification is dissolved in oxolane, at 20 DEG C:
A) add hydrogenation nak response, reaction temperature is 20 DEG C, the response time is 3h, hydrofining and 1- (2,6- diisopropyls
Anilino-) anthraquinone part mol ratio be 1:1, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding trans-chloro- (phenyl) double (triphenyl phosphorus) nickel (), trans-chloro- (phenyl) double (triphenyl phosphorus)
Nickel () is 1:1.5 with the mol ratio of 1- (2,6-DIPA base), under nitrogen protection at 30 DEG C, reacts 12h, obtains final product
To the aniline Anthraquinones transient metal complex of brown,1h nmr(cdcl3,400mhz):8.12(d,1h,ar-h),7.24-
7.48(m,17h,ar-h),6.94-7.04(m,3h,ar-h),6.88(d,2h,ar-h),6.61(d,1h,ar-h),6.48(d,
2h,ar-h),6.40(d,1h,ar-h),6.28(t,1h,ar-h),6.11(t,2h,ar-h),3.57(m,2h,-ch),0.94-
1.04(dd,12h,ch3), Fig. 3 is shown in by its corresponding crystal structure schematic diagram.
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1And r2For isopropyl, r3-r5For hydrogen, r6For phenyl,
r7-r13For hydrogen, m is nickel, and l is triphenylphosphine).
Embodiment 5
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) 1-chloroanthraquinone for 1:1 for the mol ratio and 2,6- dimethoxyaniline are dissolved in Isosorbide-5-Nitrae-dioxy six alkane, then
Add catalytic action system, catalytic action system is double (two subunit acetone) palladiums, big steric hindrance phosphino- ferrocene and cs2co3, its
In, double (two subunit acetone) palladium is the 6% of 1-chloroanthraquinone, and double (two subunit acetone) palladium is rubbed with big steric hindrance phosphino- ferrocene
That ratio is 1:2, cs2co3Mol ratio with 1-chloroanthraquinone is 2:1, and under catalytic action, flow back under 130 DEG C of condition of nitrogen gas 12h, cold
But to room temperature, solvent Isosorbide-5-Nitrae-dioxy six alkane vacuum is drained reservation solid, remaining solid is dissolved in dichloromethane, washes with water
5 times, separatory funnel separation organic faciess, add excessive anhydrous magnesium sulfate to be dried, filter and retain filtrate, dichloromethane concentrated in vacuo is molten
Agent, is subsequently adding normal hexane, separates out a large amount of red solid.Filtration under diminished pressure obtains solid, be washed once with positive 20ml hexane, then uses
20ml ether washes twice, and vacuum drying had both obtained red product, yield 91%.1h nmr(cdcl3,400mhz):10.83(s,
1h,-nh),8.26-8.35(dd,2h,ar-h),7.67-7.79(m,3h,ar-h),7.42(t,1h,ar-h),7.23(d,1h,
ar-h),6.27(d,1h,nh-ar-h),6.69(d,2h,nh-ar-h),3.82(s,6h,-ch3).
(2) 1- (2,6- dimethoxy benzene amido) the anthraquinone part after purification is dissolved in oxolane, at 0 DEG C:
A) add hydrogenation nak response, reaction temperature is 0 DEG C, the response time is 10h, hydrofining and 1- (2,6- dimethoxys
Anilino-) anthraquinone part mol ratio be 1.3:1, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding trans-chloro- (phenyl) double (triphenyl phosphorus) nickel (), trans-chloro- (phenyl) double (triphenyl phosphorus)
Nickel () is 1:0.9 with the mol ratio of 1- (2,6- dimethoxy benzene amido) anthraquinone part, under nitrogen protection at 30 DEG C, reaction
20h, that is, obtain brown 1- (2,6- dimethoxy benzene amido) anthraquinone ligand transient metal coordination compound.1h nmr(cdcl3,
400mhz):8.09(d,1h,ar-h),7.26-7.59(m,17h,ar-h),6.91-7.05(m,3h,ar-h),6.80(d,2h,
ar-h),6.59(d,1h,ar-h),6.46(d,2h,ar-h),6.38(d,1h,ar-h),6.21(t,1h,ar-h),6.09(t,
2h,ar-h),3.67(m,2h,o-ch3).
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1And r2For methoxyl group, r3-r5For hydrogen, r6For phenyl,
r7-r13For hydrogen, m is nickel, and l is triphenylphosphine).
Embodiment 6
A kind of preparation method of aniline Anthraquinones transient metal complex, comprises the following steps:
(1) by mol ratio, 1,5 dichloroanthraquinones for 1:3 are dissolved in Isosorbide-5-Nitrae-dioxy six alkane with 2,6-DIPA,
Be subsequently adding catalytic action system, catalytic action system is double (two subunit acetone) palladiums, big steric hindrance phosphino- ferrocene and
cs2co3, wherein, double (two subunit acetone) palladium is the 8% of 1,5 dichloroanthraquinones, double (two subunit acetone) palladium and big steric hindrance phosphine
The mol ratio of base ferrocene is 1:1.5, cs2co3With 1, the mol ratio of 5 dichloroanthraquinones is 3:1, under catalytic action, 110 DEG C of nitrogen
Flow back under gas bar part 30h, is cooled to room temperature, solvent Isosorbide-5-Nitrae-dioxy six alkane vacuum is drained reservation solid, will be molten for remaining solid
In dichloromethane, wash with water 5 times, separatory funnel separation organic faciess, add excessive anhydrous magnesium sulfate to be dried, filter and retain filter
Liquid, dichloromethane solvent concentrated in vacuo, it is subsequently adding normal hexane, separate out a large amount of red solid.Filtration under diminished pressure obtains solid, with just
20ml hexane washed once, then is washed twice with 20ml ether, and vacuum drying had both obtained red product, yield 91%.1h nmr
(cdcl3,400mhz):10.97(s,2h,-nh),7.66(d,2h,ar-h),7.39(m,2h,ar-h),7.28(d,4h,nh-
ar-h),6.53(d,2h,nh-ar-h),3.10(m,4h,-ch),1.11-1.19(dd,24h,-ch3).
(2) double for 1,5- after purification (2,6-DIPA base) anthraquinone parts are dissolved in oxolane, 20
At DEG C:
A) add hydrogenation nak response, reaction temperature is 50 DEG C, the response time is 5h, and hydrofining and 1,5- pair (2,6- bis- is different
Propyl group anilino-) anthraquinone part mol ratio be 2.2:1, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding trans-chloro- (phenyl) double (triphenyl phosphorus) nickel (), trans-chloro- (phenyl) double (triphenyl phosphorus)
Nickel () is 1:0.5 with the mol ratio of 1- (2,6-DIPA base) anthraquinone part, under nitrogen protection at 60 DEG C, reaction
15h, that is, obtain the aniline Anthraquinones transient metal complex of brown,1h nmr(cdcl3,400mhz):7.26-8.15(m,36h,
ar-h),6.13-7.09(m,16h,ar-h),3.59(m,4h,-ch),0.95-1.07(dd,24h,-ch3), its corresponding crystalline substance
Body structural representation is shown in Fig. 4.
Prepared aniline Anthraquinones transient metal complex, has a following structural formula:
Wherein, (r in aniline Anthraquinones transient metal complex structure1And r2For isopropyl, r3-r5For hydrogen, r6For phenyl,
r7-r13For hydrogen, m be nickel, l be triphenylphosphine).
Embodiment 7
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period with nitrogen take a breath 3 times, then sequentially add toluene and
Aniline anthraquinone late transition metal complex toluene solution (product using being obtained in embodiment 1), wherein, transition after aniline anthraquinone
The concentration of metal complex is 0.33mmol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure
(2.0mpa), after polymerization reaction time reaches the response time (60min) pre-setting, by reactor pressure release to normal pressure, will
Reaction solution is poured in 500ml beaker, adds ethanol solution hydrochloride to terminate, after washing and filtering, 60 DEG C of dryings of vacuum drying oven are to weighing apparatus
Weight, the Production rate polymerization activity according to polymer is 0.12 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn
=5.66 × 103g·mol-1, mw/mn=1.72.
Embodiment 8
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 5 times with nitrogen.Then sequentially add toluene and
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 2), wherein, aniline anthraquinone late transition metal complexes
The concentration of thing is 0.33mmol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure (1.5mpa),
After polymerization reaction time reaches the response time (60min) pre-setting, reaction solution is poured into by reactor pressure release to normal pressure
In 500ml beaker, add ethanol solution hydrochloride terminate, after washing and filtering 60 DEG C of dryings of vacuum drying oven to weight, according to polymer
Production rate polymerization activity be 0.39 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=6.65 × 103g·
mol-1, mw/mn=1.68.
Embodiment 9
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (20 DEG C), period is taken a breath 4 times with nitrogen.Then sequentially add toluene and
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4), wherein, aniline anthraquinone late transition metal complexes
The concentration of thing is 0.33mmol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure (3.0mpa),
After polymerization reaction time reaches the response time (30min) pre-setting, reaction solution is poured into by reactor pressure release to normal pressure
In 500ml beaker, add ethanol solution hydrochloride terminate, after washing and filtering 60 DEG C of dryings of vacuum drying oven to weight, according to polymer
Production rate polymerization activity be 0.2 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=4.03 × 104g·
mol-1, mw/mn=1.64, tm=124 DEG C, the degree of branching is 10c/1000c.
Embodiment 10
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 5 times with nitrogen.Then sequentially add toluene and
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4), wherein, aniline anthraquinone late transition metal complexes
The concentration of thing is 0.33mmol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure (3.0mpa),
After polymerization reaction time reaches the response time (60min) pre-setting, reaction solution is poured into by reactor pressure release to normal pressure
In 500ml beaker, add ethanol solution hydrochloride terminate, after washing and filtering 60 DEG C of dryings of vacuum drying oven to weight, according to polymer
Production rate polymerization activity be 1.01 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=3.27 × 104g·
mol-1, mw/mn=1.69, tm=114 DEG C, the degree of branching is 27c/1000c.
Embodiment 11
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (60 DEG C), period is taken a breath 5 times with nitrogen.Then sequentially add toluene and
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4), wherein, aniline anthraquinone late transition metal complexes
The concentration of thing is 0.33mmol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure (3.0mpa),
After polymerization reaction time reaches the response time (30min) pre-setting, reaction solution is poured into by reactor pressure release to normal pressure
In 500ml beaker, add ethanol solution hydrochloride terminate, after washing and filtering 60 DEG C of dryings of vacuum drying oven to weight, according to polymer
Production rate polymerization activity be 8.24 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=7.81 × 103g·
mol-1, mw/mn=1.67, tm=93 DEG C, the degree of branching is 49c/1000c.
Embodiment 12
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 3～5 times with nitrogen.Then sequentially add first
Benzene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and ni (cod)2Toluene solution, wherein,
The concentration of aniline anthraquinone late transition metal complex is 0.33mmol/l, ni (cod)2The concentration of toluene solution is 0.8mol/l,
Then autoclave is closed, be passed through ethylene, and keep constant ethylene pressure (1.5mpa), reach in polymerization reaction time and set in advance
After the response time (30min) put, reactor pressure release to normal pressure pours reaction solution in 500ml beaker into, add hydrochloric acid second
Alcoholic solution terminates, and 60 DEG C of dryings of vacuum drying oven after washing and filtering, to weight, according to the Production rate polymerization activity of polymer are
3.14×105g·mol-1·h-1, resulting polymers number-average molecular weight mn=2.80 × 104g·mol-1, mw/mn=1.77, tm=
113℃.
Embodiment 13
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (60 DEG C), period is taken a breath 4 times with nitrogen.Then sequentially add toluene,
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and ni (cod)2Toluene solution, wherein, aniline
The concentration of anthraquinone late transition metal complex is 0.33mmol/l, ni (cod)2The concentration of toluene solution is 0.8mol/l, then
Autoclave is closed, is passed through ethylene, and keep constant ethylene pressure (1.5mpa), reach in polymerization reaction time and pre-set
After response time (30min), reactor pressure release to normal pressure pours reaction solution in 500ml beaker into, add acidic alcohol molten
Liquid terminates, and after washing and filtering, 60 DEG C of dryings of vacuum drying oven are to weight.Obtain polymer 3.97g, according to the Production rate of polymer
Polymerization activity is 7.94 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=7.64 × 103g·mol-1, mw/mn
=1.60, tm=89 DEG C, the degree of branching is 58c/1000c.
Embodiment 14
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (60 DEG C), period is taken a breath 3～5 times with nitrogen.Then sequentially add first
Benzene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and ni (cod)2Toluene solution, wherein,
The concentration of aniline anthraquinone late transition metal complex is 0.33mmol/l, ni (cod)2The concentration of toluene solution is 0.8mol/l,
Then autoclave is closed, be passed through ethylene, and keep constant ethylene pressure (3.0mpa), reach in polymerization reaction time and set in advance
After the response time (10min) put, reactor pressure release to normal pressure pours reaction solution in 500ml beaker into, add hydrochloric acid second
Alcoholic solution terminates, and after washing and filtering, 60 DEG C of dryings of vacuum drying oven are to weight.Obtain polymer 4.66g, according to the yield of polymer
Calculating polymerization activity is 2.80 × 106g·mol-1·h-1, resulting polymers number-average molecular weight mn=9.51 × 103g·mol-1,
mw/mn=1.64, tm=95 DEG C.
Embodiment 15
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (60 DEG C), period is taken a breath 3～5 times with nitrogen.Then sequentially add and add
Enter toluene and aniline anthraquinone late transition metal complex (product using being obtained in embodiment 6), wherein, transition after aniline anthraquinone
The concentration of metal complex is 0.083mmol/l (product using being obtained in embodiment 10), then closes autoclave, is passed through
Ethylene, and keep constant ethylene pressure (3.0mpa), reach, in polymerization reaction time, the response time (60min) pre-setting
Afterwards, by reactor pressure release to normal pressure, reaction solution is poured in 500ml beaker, add ethanol solution hydrochloride to terminate, washing and filtering
To weight, the Production rate polymerization activity according to polymer is 5.28 × 10 to 60 DEG C of dryings of vacuum drying oven afterwards5g·mol-1·h-1,
Resulting polymers number-average molecular weight mn=8.68 × 103g·mol-1, mw/mn=1.71, tm=93 DEG C.
Embodiment 16
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 3～5 times with nitrogen.Then sequentially add first
The toluene solution of benzene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and dmmao, wherein, benzene
The concentration of amine anthraquinone late transition metal complex is 0.33mmol/l, and the concentration of dmmao toluene solution is 0.17mol/l, then
Autoclave is closed, is passed through ethylene, and keep constant ethylene pressure (1.5mpa), reach in polymerization reaction time and pre-set
After response time (10min), by reactor pressure release to normal pressure terminating reaction.According to chromatography of gases-GC-MS analysis butylene
It is 67.5% with hexene selectivity, polymerization activity is 1.37 × 106g·mol-1·h-1.
Embodiment 17
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 3～5 times with nitrogen.Then sequentially add first
Benzene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and et2Alcl (2mmol/ml just oneself
Alkane solution), wherein, the concentration of aniline anthraquinone late transition metal complex is 0.33mmol/l, et2Alcl hexane solution dense
Spend for 10mmol/l, then autoclave is closed, be passed through ethylene, and keep constant ethylene pressure (1.5mpa), in polyreaction
After time reaches the response time (10min) pre-setting, by reactor pressure release to normal pressure terminating reaction.According to chromatography of gases-
GC-MS analysis 2-butylene selectivity is 75%, and calculating polymerization activity according to proton magnetic spectrum is 6.9 × 106g·mol-1·
h-1.
Embodiment 18
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: High pressure ethylene polymerization is using with machinery
The autoclave of the 100ml of stirring and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heat time heating time continues 1h,
Then polymeric kettle is cooled to and pre-sets polymerization temperature (40 DEG C), period is taken a breath 5 times with nitrogen.Then sequentially add toluene,
Aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4) and et2(the 1.6mmol/ml normal hexane of alcl
Solution), wherein, the concentration of aniline anthraquinone late transition metal complex is 0.33mmol/l, etalcl2The concentration of hexane solution
For 10mmol/l, then autoclave is closed, be passed through ethylene, and keep constant ethylene pressure (1.5mpa), in polyreaction
Between reach the response time (10min) pre-setting after, by reactor pressure release to normal pressure terminating reaction.According to chromatography of gases-matter
Spectrum combined instrument analysis 2-butylene and 3- hexene selectivity be 85.3%, according to proton magnetic spectrum calculate polymerization activity be 1.37 ×
107g·mol-1·h-1.
Comparative example 1
Reported according to document journal of organometallic chemistry 694 (2009) 1,254 1258.,
Under conditions of mao is as promoter, polymerization activity is on a declining curve with temperature rising, reaches most highly active at 30 DEG C.Tool
Body step is under nitrogen atmosphere, adds 40ml toluene, mao (al/ni=200) promoter and 2.5 μm of ol ketone in reactor
Eneamines neutral nickel catalyst, is passed through ethylene, 30 DEG C reaction 30min obtain ethylene oligomer, polymerization activity be 2.81 ×
106g·mol-1·h-1, comparative example 1 contrasted with embodiment 18, al/ni ratio only 30 in embodiment 18, and promoter consumption is more
Few, but the activity of ethylene oligomer is up to 1.37 × 107g·mol-1·h-1, exceed an order of magnitude than comparative example.
Embodiment 19
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: normal pressure norbornene polymerization uses 50ml
Single port carries magnetic agitation and temperature controlled round-bottomed flask.Flask evacuation is continued 30min, then temperature is adjusted in advance
Setting polymerization temperature (20 DEG C), period is taken a breath 4 times with nitrogen, then sequentially adds toluene, aniline anthraquinone late transition metal complexes
The first of thing (product using being obtained in embodiment 5), norborene (7mmol/ml toluene solution) and three (pentafluorophenyl group) borine
Benzole soln, wherein, the concentration of aniline anthraquinone late transition metal complex is 0.1mmol/l, and the concentration of norborene is
1.05mol/l, the concentration of the toluene solution of three (pentafluorophenyl group) borine is 0.25mmol/l, then reaches in polymerization reaction time
After the response time (5min) pre-setting, reaction solution is poured in 500ml beaker, add ethanol solution hydrochloride to terminate, wash
After washing filtration, to weight, the Production rate polymerization yield rate according to polymer is 78% to 60 DEG C of dryings of vacuum drying oven, resulting polymers
Number-average molecular weight mn=2.43 × 104g·mol-1, mw/mn=2.50.
Embodiment 20
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: high-pressure ethylene-norborene copolymerization makes
With the autoclave of the 100ml with mechanical agitation and temperature control equipment, by autoclave evacuation and be heated to 100 DEG C, heating
Time continues 1h, is then cooled to polymeric kettle and pre-sets polymerization temperature (10 DEG C), and period is taken a breath 3 times with nitrogen, Ran Houyi
Secondary addition toluene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4), norborene (7mmol/
Ml toluene solution) and mmao (2.43mmol/ml toluene solution), wherein, the concentration of aniline anthraquinone late transition metal complex is
0.33mmol/l, the concentration of norborene is 1.167mol/l, and the concentration of mmao solution is 0.167mol/l, then by autoclave
Closing, is passed through ethylene, and keeps constant ethylene pressure (1.5mpa), reach, in polymerization reaction time, the response time pre-setting
(10min) after, reactor pressure release to normal pressure pours reaction solution in 500ml beaker into, adds ethanol solution hydrochloride to terminate,
After washing and filtering, 60 DEG C of dryings of vacuum drying oven are to weight.Obtain polymer 0.29g, according to the Production rate polymerization activity of polymer
For 1.74 × 105g·mol-1·h-1, resulting polymers number-average molecular weight mn=7.54 × 104g·mol-1, mw/mn=1.59, glass
Glass transition temperature tg=171 DEG C.
Comparative example 2
According to document polym.chem., 2015,6,2,669 2676. reports, ethylene-norbornene copolymerization, is crystallinity
Copolymer.48ml toluene, 2mlch is added in reactor2cl210 μm of ol catalyst of dissolving, 10.6mmol norborene, room temperature,
0.9mpa, reaction 2h obtain ethylene-norbornene copolymer, and most highly active is 1.75 × 105g·mol-1·h-1, but insertion rate
Less than 0.5%；Comparative example 2 is contrasted with embodiment 20, and the Copolymerization activity in embodiment 20 is 1.74 × 105g·mol-1·h-1, gather
Compound is non-crystalline copolymer, and glass transition temperature is high, insertion rate be higher than 50% although in comparative example 2 activity with implement
Example 20 polymerization activity is relatively fair, but insertion rate is less than 0.5%, more much lower than embodiment 20.
Comparative example 3
According to document polym.chem., 2015,6,2,669 2676. reports, ethylene-norbornene copolymerization, is crystallinity
Copolymer.As addition 48ml toluene, 2mlch in reactor2cl210 μm of ol catalyst of dissolving, 10.6mmol norborene, 50 DEG C,
0.9mpa, reaction 2h obtains ethylene-norbornene copolymer, and in the copolymer obtaining, norborene insertion rate is to reach highest
10.1%, but activity decrease is to 0.5 × 105g·mol-1·h-1.Comparative example 3 is contrasted with embodiment 20, being total in embodiment 20
Poly- activity is 1.74 × 105g·mol-1·h-1, polymer is non-crystalline copolymer, and glass transition temperature is high, and insertion rate is high
In 50%, when comparative example 3 insertion rate reaches 10.1%, activity reduces a lot, lower than embodiment 20 an order of magnitude it is seen that
Embodiment 20 had not only had higher polymerization activity but also had had higher insertion rate.
Embodiment 21
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: (ice drops to polarity norbornene monomer in 5-
Piece alkene -2- formaldehyde) homopolymerization use 50ml single port carry magnetic agitation and temperature controlled round-bottomed flask.Flask evacuation is continued
Then temperature is adjusted to pre-set polymerization temperature (30 DEG C) by 30min, and period is taken a breath 3～5 times with nitrogen.Then sequentially add
Toluene, mmao (2.43mmol/ml toluene solution), 5- norborene -2- formalin (product using being obtained in embodiment 3)
With the toluene solution of aniline anthraquinone late transition metal complex, wherein, the concentration of aniline anthraquinone late transition metal complex is
The concentration of 0.5mmol/l, 5- norborene -2- formaldehyde is 1.67mol/l, and the concentration of mmao solution is 1mol/l, then poly-
After the conjunction response time reaches the response time (30min) pre-setting, reaction solution is poured in 500ml beaker, add hydrochloric acid
Ethanol solution terminates, and after washing and filtering, 60 DEG C of dryings of vacuum drying oven are to weight.Obtain polymer 1.79g, according to the product of polymer
It is 87.9% that amount calculates polymerization yield rate.
Embodiment 22
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: high-pressure ethylene-acetic acid 5- hexene base ester
Copolymerization using autoclave with mechanical agitation and the 100ml of temperature control equipment, by autoclave evacuation and be heated to 100
DEG C, heat time heating time continues 1h, is then cooled to polymeric kettle and pre-sets polymerization temperature (40 DEG C), and period is taken a breath 3 times with nitrogen.
Then toluene, aniline anthraquinone late transition metal complex (product using being obtained in embodiment 4), acetic acid 5- hexene are sequentially added
The solution of base ester and dmmao (al/ni=500), wherein, the concentration of aniline anthraquinone late transition metal complex is 0.33mmol/
L, the concentration of acetic acid 5- hexene base ester is 0.62mol/l, and the concentration of dmmao solution is 0.25mol/l, then seals autoclave
Close, be passed through ethylene, and keep constant ethylene pressure (1.0mpa), reach, in polymerization reaction time, the response time pre-setting
(60min) after, reactor pressure release to normal pressure pours reaction solution in 500ml beaker into, adds ethanol solution hydrochloride to terminate,
After washing and filtering, to weight, the Production rate polymerization activity according to polymer is 1.17 × 10 to 60 DEG C of dryings of vacuum drying oven5g·
mol-1·h-1, resulting polymers number-average molecular weight mn=9.05 × 103g·mol-1, mw/mn=1.87, tm=95 DEG C, by hydrogen
It is 0.45% that nuclear-magnetism calculates acetic acid 5- hexene base ester insertion rate.
Comparative example 4
According to document j.am.chem.soc.2008,130,17,636 17637. reports, in 20 μm of ol catalyst, dmmao
Under the conditions of promoter, 25 DEG C, polymerization activity is 0.556～0.78 × 105g·mol-1·h-1, polymerization activity is with acetic acid
The mol ratio of 5- hexene base ester co-monomer inventory increases and is decreased obviously.Concretely comprise the following steps under nitrogen atmosphere, by 250ml first
Benzene adds reaction bulb, and keeping temperature is 25 DEG C, is passed through ethylene, (co-monomer feeds intake to sequentially add acetic acid 5- hexene base ester after 10min
Measure 262.5 times for coordination compound), dmmao (5mmol) promoter, 20 μm of ol catalyst, reaction 10min, ethanol solution hydrochloride
Terminating reaction obtains polymer, polymerization activity only 0.11 × 105g·mol-1·h-1, comparative example 4 is contrasted with embodiment 22, real
Apply co-monomer content in example 22 and be 1242 times of coordination compound, but the co-monomer inventory that activity is document report is coordination compound
Have a surplus for 10 times when 262.5 times.
Embodiment 23
Aniline anthraquinone late transition metal complex is in the application of catalyzed alkene monomer: high-pressure ethylene -5- norborene -2- carboxylic
Sour methyl ester copolymerization using the autoclave with mechanical agitation and the 100ml of temperature control equipment, by autoclave evacuation and heat
To 100 DEG C, heat time heating time continues 1h, is then cooled to polymeric kettle and pre-sets polymerization temperature (40 DEG C), period is changed with nitrogen
Gas 3～5 times.Then sequentially add toluene, aniline anthraquinone late transition metal complex (using in embodiment 4 be obtained product),
The solution of 5- norborene -2- carboxylate methyl ester and mmao (2.43mmol/ml toluene solution), wherein, transition gold after aniline anthraquinone
The concentration of metal complex is 0.33mmol/l, and the concentration of 5- norborene -2- carboxylate methyl ester is 1.715mol/l, mmao solution
Concentration is 0.25mol/l, then closes autoclave, is passed through ethylene, and keeps constant ethylene pressure (1.0mpa), anti-in polymerization
After reaching, between seasonable, the response time (60min) pre-setting, reactor pressure release to normal pressure pours reaction solution into 500ml
In beaker, add ethanol solution hydrochloride terminate, after washing and filtering 60 DEG C of dryings of vacuum drying oven to weight, according to the yield of polymer
Calculating polymerization activity is 0.57 × 105g mol-1 h-1, resulting polymers number-average molecular weight mn=1.09 × 104g·mol-
1, mw/mn=1.86, tm=71 DEG C, calculating 5- norborene -2- carboxylate methyl ester insertion rate by proton magnetic is 1.22%.
Claims (10)
1. the preparation method of aniline anthraquinone late transition metal complex, is characterized in that:
(1) chloroanthraquinone and substituted aniline are dissolved in a solvent, react under uniform temperature and catalytic action, generate aniline anthraquinone
Class part；
(2) described aniline Anthraquinones part is dissolved in organic solvent, under the conditions of proper temperature:
A) add and pull out hydrogen reagent reaction, pull out amino hydrogen evolution part salt compound；
B) it is subsequently adding metal precursor, reaction；
Obtain described aniline anthraquinone late transition metal complex.
2. the preparation method of aniline anthraquinone late transition metal complex according to claim 1 is it is characterised in that step
(1), in, described solvent is normal heptane, toluene, chlorobenzene, Isosorbide-5-Nitrae-dioxy six alkane, octane, 4-methyl-2 pentanone or ethylenediamine；Described
Uniform temperature is 90～130 DEG C, and under catalytic action, the time of reaction is 12～36h；
The system of described catalytic action includes major catalyst, promoter and alkali, and described major catalyst is double (two subunits third
Ketone) palladium, three (dibenzalacetone) two palladium or acid chloride, described promoter is biaryl phosphine or big steric hindrance phosphino- ferrocene,
Described alkali is naotbu、k3po4、cs2co3Or k2co3；
Wherein big steric hindrance phosphino- ferrocene is preferably double (diphenylphosphine) ferrocene of 1,1'-.
3. the preparation method of aniline anthraquinone late transition metal complex according to claim 1 is it is characterised in that step
(2), in, described organic solvent is toluene, oxolane, dichloromethane, ether, normal hexane, chlorobenzene or Isosorbide-5-Nitrae-dioxy six alkane；
Described proper temperature condition refers to 0～60 DEG C；
The described hydrogen reagent that pulls out is sodium hydride, hydrofining, n-BuLi, potassium tert-butoxide or two (trimethyl silicon substrate) Sodamide.；Described
The mol ratio pulling out hydrogen reagent with described aniline Anthraquinones part is 1～2.2:1；Addition is pulled out hydrogen reagent reaction and is referred to aniline Anthraquinones
Part and the described hydrogen reagent that pulls out react 1～10h at 0～60 DEG C, and the amino hydrogen on aniline anthraquinone part is pulled out, and form part
Salt compound；
Described metal precursor is trans-chloro- (phenyl) double (triphenyl phosphorus) nickel (), trans-chloro- (methyl) double (trimethyl
Phosphorus) nickel (), chlorination pi-allyl nickel (ii) dimer, chlorine (cyclo-octadiene) methyl palladium or chlorination Allylpalladium (ii) dimer；
Described metal precursor is 1:0.5～1 with the mol ratio of described aniline Anthraquinones part；Add anti-after metal precursor
Should refer at 0～60 DEG C, aniline anthraquinone part salt compound and metal precursor complexation reaction 5～20h, form institute of the present invention
The aniline anthraquinone metal complex providing；
When the metal of described metal precursor is palladium, then add pyridine or dimethyl sulfoxide, react 1～6h, the pyridine being added
Or dimethyl sulfoxide is 1～5:1 with the mol ratio of described aniline Anthraquinones part；
After step (1) generates aniline Anthraquinones part, carry out by organic solvent recrystallization or by organic solvent extraction
Purification processes；The organic solvent of recrystallization or purification by liquid extraction is toluene, dichloromethane, oxolane, ether, normal hexane, positive heptan
The organic solvents such as alkane, chlorobenzene, methanol or ethanol.
4. the preparation method of the aniline anthraquinone late transition metal complex according to any one of claims 1 to 3, its feature
It is, described chloroanthraquinone is the derivative of 1-chloroanthraquinone, 1,5- dichloroanthraquinone, the derivant of 1-chloroanthraquinone or 1,5- dichloroanthraquinone
Thing；
The derivant of described 1-chloroanthraquinone is 1- chloro- 8- tectoquinone, 1- chloro- 7- tectoquinone, 1- chloro- 5,8- dimethyl anthraquinone
Or 4- chloro- 1- hydroxyl -6- nitroanthraquinone；
The derivant of described 1,5- dichloroanthraquinone be the chloro- 4- tectoquinone of 1,5- bis-, the chloro- 4,8- dimethoxy anthraquinone of 1,5- bis- or
The chloro- 4- tectoquinone of 1,5- bis-；
The structural formula of described substituted aniline is:
Wherein, r1、r2、r3、r4And r5Be independently from each other hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen,
Nitro, aryl or aryl substituent, or further, r1And r5, r4And r5, r3And r4, r2And r3Form carbon or containing heteroatomic
Ring structure；
On described ring structure independent with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitro, aryl or
One or more of aryl substituent；
Described chloroanthraquinone is 1:0.8～3 with the mol ratio of described substituted aniline；
Described major catalyst is the 2～8% of described chloroanthraquinone quality；
Described major catalyst is 1:1.2～2 with the mol ratio of promoter；
Described alkali is 1～3:1 with the mol ratio of described chloroanthraquinone.
5. the aniline anthraquinone late transition metal complex that a kind of preparation method as claimed in claim 4 is obtained, is characterized in that having
Following general structure:
Wherein, r1～r5It is independently from each other hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitro, aryl
Or aryl substituent, or further, r1And r5, r4And r5, r3And r4, r2And r3Form carbon or contain heteroatomic ring structure；
On described ring structure independent with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, halogen, nitro, aryl or
One or more of aryl substituent；
r6For methyl, phenyl, benzyl or unsubstituted；r7～r13It is independently from each other hydrogen, alkyl, the substituent of alkyl, alkane
One or more of epoxide, alkylthio group, nitro, hydroxyl, carboxyl, aryl or aryl substituent, or further, r7And r8,
r8And r9, r9And r10, r11And r12, r12And r13It is individually formed carbon or contain heteroatomic ring structure；
Described ring structure independence with hydrogen, alkyl, the substituent of alkyl, alkoxyl, alkylthio group, nitro, hydroxyl, carboxyl, virtue
One or more of base or aryl substituent；
M is nickel or palladium；
L is trimethyl-phosphine, triphenylphosphine, pyridine, dimethyl sulfoxide or pi-allyl.
6. the carbon monoxide-olefin polymeric of aniline anthraquinone late transition metal complex preparation described in a kind of employing claim 5, its feature
It is: described carbon monoxide-olefin polymeric is made up of described aniline anthraquinone late transition metal complex and promoter；Described promoter
Selected from aikyiaiurnirsoxan beta, alkyl aluminum compound, alkyl aluminum chloride compound, aluminum chloride, three (pentafluorophenyl group) borines or double-(1,5-
One or more of cyclo-octadiene) nickel.
7. a kind of carbon monoxide-olefin polymeric according to claim 6 is it is characterised in that described aikyiaiurnirsoxan beta is specially methyl alumina
The modified MAO of alkane, tert-butyl group aluminum or the MAO of the tert-butyl group aluminum modification being dried；Described alkyl aluminum compound
For trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium；Described alkyl aluminum chloride compound is
Diethylaluminum chloride or ethylaluminium dichloride；
Described aniline anthraquinone late transition metal complex is 1:30～5000 with the mol ratio of aluminum；
Described aniline anthraquinone late transition metal complex and three (pentafluorophenyl group) borines or double-(1,5- cyclo-octadiene) nickel mole
Than for 1:1～10.
8. a kind of aniline anthraquinone late transition metal complex as claimed in claim 5 is in the homopolymerization or copolymerization of catalyzed alkene monomer
Application.
9. application in the homopolymerization or copolymerization of catalyzed alkene monomer for a kind of carbon monoxide-olefin polymeric as claimed in claims 6 or 7.
10. the application described according to Claim 8 with 9, is characterized in that: under inert gas shielding, transition gold after aniline anthraquinone
Metal complex or carbon monoxide-olefin polymeric are first dissolved in solvent, are subsequently adding olefinic monomer, at -50～120 DEG C, 0.1～5mpa
Lower reactive polymeric 1～1440min, prepared olefin polymer；
Described olefinic monomer is ethylene, cycloolefins or polarity/function monomer；
Described cycloolefins are norborene, 5- methyl -2- norborene, 5- ethyl -2- norborene, 5- butyl -2- norborneol
Alkene, 5- hexyl -2- norborene, 5- decyl -2- norborene, 5- vinyl -2- norborene, 5- acrylic -2- norborneol
Alkene, 5- cyclohexyl -2- norborene, 5- cyclopenta -2- norborene, dicyclopentadiene or methyldicyclopentadiene；
Described polarity/function monomer is 5- norborene -2- carboxylate methyl ester, 5- norborene -2- formaldehyde, acetic acid 5- hexenyl
Ester, carbic anhydride, acrylic acid methyl ester., allyl acetate, vinyl ethyl ether, pi-allyl ether, vinyl acetate bromine third
Alkene or chloropropene；Described solvent is toluene, chlorobenzene, normal hexane or normal heptane；
The mol ratio of described polarity/function monomer and aniline anthraquinone late transition metal complex or carbon monoxide-olefin polymeric is 10～
50000:1；
Described olefin polymer includes olefin polymer and ethylene low polymer, and the molecular weight of described olefin polymer is 2000～
500000g·mol-1, molecular weight distributing index is 1.4～3.0, and fusing point is 50～130 DEG C；Described ethylene low polymer is mainly fourth
Alkene and hexene.
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| CN107641164A (en) * | 2017-09-28 | 2018-01-30 | 东华大学 | A kind of non-homogeneous polymerization catalyst and its application in homopolymer and copolymer is prepared |
| CN107955088A (en) * | 2017-09-28 | 2018-04-24 | 东华大学 | A kind of catalyst, its preparation method, by its obtained composition and application |
| CN110935489A (en) * | 2019-05-31 | 2020-03-31 | 东华大学 | Supported transition metal catalyst system through hydrogen bond action and preparation method thereof |
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| WO2022242045A1 (en) * | 2021-05-19 | 2022-11-24 | 青岛科技大学 | Preparation of anthracene skeleton-based bimetallic catalyst, and application thereof in solution polymerization of olefin at high temperature |
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| CN107641164A (en) * | 2017-09-28 | 2018-01-30 | 东华大学 | A kind of non-homogeneous polymerization catalyst and its application in homopolymer and copolymer is prepared |
| CN107955088A (en) * | 2017-09-28 | 2018-04-24 | 东华大学 | A kind of catalyst, its preparation method, by its obtained composition and application |
| CN107955088B (en) * | 2017-09-28 | 2020-05-05 | 东华大学 | Catalyst, preparation method thereof, composition prepared from catalyst and application of composition |
| CN107602734A (en) * | 2017-10-09 | 2018-01-19 | 东华大学 | A kind of palladium-containing catalyst, its preparation method, by its obtained composition and application |
| CN107602734B (en) * | 2017-10-09 | 2019-10-18 | 东华大学 | A kind of palladium-containing catalyst, preparation method, composition as made from it and application |
| US11091567B2 (en) | 2019-04-15 | 2021-08-17 | Exxonmobil Chemical Patents Inc. | Amido-benzoquinone catalyst systems and processes thereof |
| CN110935489A (en) * | 2019-05-31 | 2020-03-31 | 东华大学 | Supported transition metal catalyst system through hydrogen bond action and preparation method thereof |
| CN110935489B (en) * | 2019-05-31 | 2021-10-26 | 东华大学 | Supported transition metal catalyst system through hydrogen bond action and preparation method thereof |
| WO2022242045A1 (en) * | 2021-05-19 | 2022-11-24 | 青岛科技大学 | Preparation of anthracene skeleton-based bimetallic catalyst, and application thereof in solution polymerization of olefin at high temperature |
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