CN110092744A - The bis-imine pyridine of asymmetry containing tert-butyl complex, preparation method and the application of a kind of high heat stability - Google Patents
The bis-imine pyridine of asymmetry containing tert-butyl complex, preparation method and the application of a kind of high heat stability Download PDFInfo
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- CN110092744A CN110092744A CN201810085977.6A CN201810085977A CN110092744A CN 110092744 A CN110092744 A CN 110092744A CN 201810085977 A CN201810085977 A CN 201810085977A CN 110092744 A CN110092744 A CN 110092744A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 61
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 31
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 title abstract description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 105
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 69
- -1 polyethylene Polymers 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000004698 Polyethylene Substances 0.000 claims abstract description 22
- 229920000573 polyethylene Polymers 0.000 claims abstract description 22
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- 230000001052 transient effect Effects 0.000 claims abstract description 18
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 17
- 239000002585 base Substances 0.000 claims description 72
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 41
- 239000003426 co-catalyst Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 29
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 29
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 229910052801 chlorine Inorganic materials 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052794 bromium Inorganic materials 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 229910052740 iodine Inorganic materials 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 125000004104 aryloxy group Chemical group 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- IDHCQGUWHXGMQW-UHFFFAOYSA-N 1-(2-acetylpyridin-3-yl)ethanone Chemical compound CC(=O)C1=CC=CN=C1C(C)=O IDHCQGUWHXGMQW-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910017052 cobalt Chemical group 0.000 claims description 4
- 239000010941 cobalt Chemical group 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001448 anilines Chemical class 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- 230000001681 protective effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 64
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 150000004698 iron complex Chemical class 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 102
- 230000037048 polymerization activity Effects 0.000 description 49
- 238000000034 method Methods 0.000 description 44
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 38
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- CPRZSOOKYBJCJH-UHFFFAOYSA-N 2,6-dibenzhydryl-4-tert-butylaniline Chemical compound NC=1C(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC(C(C)(C)C)=CC=1C(C=1C=CC=CC=1)C1=CC=CC=C1 CPRZSOOKYBJCJH-UHFFFAOYSA-N 0.000 description 22
- 125000006519 CCH3 Chemical group 0.000 description 22
- 238000006555 catalytic reaction Methods 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 15
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 239000013049 sediment Substances 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000012046 mixed solvent Substances 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000003480 eluent Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- MOMFXATYAINJML-UHFFFAOYSA-N 2-Acetylthiazole Chemical group CC(=O)C1=NC=CS1 MOMFXATYAINJML-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 150000004700 cobalt complex Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 description 1
- OIXUMNZGNCAOKY-UHFFFAOYSA-N 2,6-diethyl-4-methylaniline Chemical compound CCC1=CC(C)=CC(CC)=C1N OIXUMNZGNCAOKY-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 150000001398 aluminium Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- XXRGLCKZBCIEKO-DLMDZQPMSA-N azocine Chemical compound C/1=C/C=C\N=C/C=C\1 XXRGLCKZBCIEKO-DLMDZQPMSA-N 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- WCZVZNOTHYJIEI-UHFFFAOYSA-N cinnoline Chemical compound N1=NC=CC2=CC=CC=C21 WCZVZNOTHYJIEI-UHFFFAOYSA-N 0.000 description 1
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- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical class N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000002541 furyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
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- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- JDEJGVSZUIJWBM-UHFFFAOYSA-N n,n,2-trimethylaniline Chemical compound CN(C)C1=CC=CC=C1C JDEJGVSZUIJWBM-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000005054 naphthyridines Chemical class 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- 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
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides the bis-imine pyridine of asymmetry containing tert-butyl transient metal complex, preparation method and applications that one kind prepares the high heat stability of polyethylene wax.The preparation method mild condition of transient metal complex and its midbody compound of the present invention, the period is short, operating condition is simple.The complex can be applied in catalyst for ethylene polymerization, with single catalytic active center, regulation to polymer molecular weight can be realized by changing ligand structure and polymerizing condition, and have many advantages, such as that at low cost, catalytic activity is high and thermal stability outstanding.Especially provided iron complex, even if catalytic activity remains to be maintained at 2.82 × 10 under 110 DEG C of high temperature6g·mol–1(Fe)h–1, meet industrial operation temperature, thus can be used as engineering plastics compared with using under high environment temperature, there is great commercial application potentiality；Especially gained polyethylene weight average molecular weight MwIn 5.1~7.7kgmol‑1When (MMAO, 50~100 DEG C), can be used for preparing the polyethylene wax being commercially badly in need of.
Description
Technical field
The present invention relates to polyolefin catalyst technical fields, and in particular to one kind prepares containing for the high heat stability of polyethylene wax
Tert-butyl asymmetry bis-imine pyridine complex, preparation method and application.
Background technique
Pillar product of the polyolefine material as modern science and technology and social development, it is daily not only to meet people society
The demand of life, and become indispensable important materials in each big field such as hard-core technology, national defense construction.Wherein
Polyethylene (PE) is the maximum kind of yield in world's general synthetic resin, has good chemical resistance, high mechanical strength, can return
The features such as receiving, is low in cost occupies very important status in synthesis olefin material field.
And the design and exploitation of olefin polymerization catalysis, it is the key that develop polyethylene product.
Currently, the polyethylene catalysts of industrialized production and application mainly have Ziegler-Natta catalyst, metallocene catalysis
Agent and Phillips catalyst.1998, Brookhart and Gibbson reported one kind 2,6- diene amido pyridine respectively
Iron, cobalt complex (such as the A in formula 1), can with high activity polymerising ethylene, obtain highly linear polyolefin.Henceforth, more next
More research concentrates on the preparation and modification of late transition metal catalyst, such as B the and C class complex in formula 1.
Inventor seminar once introduced benzhydryl (formula 1, D, E) in pyridine diimine class iron, cobalt complex, and in virtue
The contraposition of imines phenyl ring introduces Cl, Me substituent group, and the catalytic activity and thermal stability of Lai Tigao catalyst system still have at 80 DEG C
Higher catalytic activity, and obtained the polyethylene of high molecular weight.(Polymer,2012,53,1870；Chem Comm.,2011,
47,3257)。
As novel catalyst system, however it remains the difficult point and the industrialized restraining factors of propulsion of some basic research.
Such as the thermal stability of late transition metal complex itself is poor, to easily cause the activity of catalyst with reaction temperature liter
It is high and reduce.Therefore, the improvement in addition to the raising of the catalytic performance to catalyst and to preparation condition and efficiency obtains higher
Can the catalyst of activity and high thermal stability be one of the key content of research, be also the pass that promote chemical industry as early as possible
Key.
Summary of the invention
To improve problems of the prior art, the present invention provides the imines of asymmetry containing tert-butyl shown in lower formula (I)
Yl pyridines transient metal complex:
Wherein, M is selected from iron or cobalt；
R1、R2It is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally by one or more RaIt takes
The following groups in generation: C1-6Alkyl or C1-6Alkoxy；
Each R3、R4、R5It is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally by one
Or multiple RbSubstituted following groups: C1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryl oxide
Base, C1-6Alkylidene aryl；
Each X is identical or different, is each independently selected from F, Cl, Br, I；
Each RaIt is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally one or more
RcSubstituted C1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy；
Each RbIt is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally one or more
RcSubstituted C1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy；
Each RcIt is identical or different, it is each independently selected from H, F, Cl, Br, I or following groups: C1-6Alkyl, C1-6Alkane
Oxygroup, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy.
According to an embodiment of the invention, in formula (I), R1、R2It is identical or different, it is each independently selected from H, C1-3Alkyl,
Such as selected from H, methyl, ethyl, n-propyl, isopropyl；
According to an embodiment of the invention, each R3、R4、R5It is identical or different, be each independently selected from H, F, Cl, Br,
I、C1-3Alkyl or C1-3Alkylidene aryl；
According to an embodiment of the invention, each X is identical or different, it is each independently selected from Cl, Br.
As example, it includes but is not limited to have following group definition that complex shown in formula (I) of the present invention, which is selected from,
Complex:
Complex Fe-1: wherein R1=Me, X are selected from Cl, other groups H；
Complex Fe-2: wherein R1=Et, X are selected from Cl, other groups H；
Complex Fe-3: wherein R1=i-Pr, X are selected from Cl, other groups H；
Complex Fe-4: wherein R1=Me, R2=Me, X are selected from Cl, other groups H；
Complex Fe-5: wherein R1=Et, R2=Me, X are selected from Cl, other groups H；
The present invention also provides ligand compounds shown in lower formula (II):
Wherein, R1、R2、R3、R4、R5With definitions as described above.
As example, it includes but is not limited to have following group that ligand compound shown in formula (II) of the present invention, which is selected from,
The compound of definition:
Ligand L 1:R1=Me, other groups H；
Ligand L 2:R1=Et, other groups H；
Ligand L 3:R1=i-Pr, other groups H；
Ligand L 4:R1=Me, R2=Me, other groups H；
Ligand L 5:R1=Et, R2=Me, other groups H.
The present invention also provides the preparation methods of transient metal complex shown in above-mentioned formula (I), include the following steps:
It will the ligand as shown in above formula (II) and compound MX2Complex reaction is carried out, obtains cooperating shown in the formula (I)
Object；
Wherein M, X have definition described above.
According to the present invention, the compound MX2The hydrate of halide, the halide selected from iron content or cobalt or other
One of solvate is a variety of, such as can be (DME) FeBr2、FeCl2·4H2O、FeCl2Or CoCl2·6H2In O
It is one or more.
According to the present invention, the reaction preferably carries out under anaerobic, such as in the ceiling of inert gas such as nitrogen
It is carried out under part.
According to the present invention, the compound MX2Molar ratio with formula (II) compound represented can be 1:1~1.5, excellent
It is selected as 1:1~1.3, further preferably 1:1.1.
According to the present invention, the temperature of the reaction can be 10-35 DEG C, such as 20-25 DEG C；The reaction time is that 4-8 is small
When, preferably 6-8 hours.
According to the present invention, the reaction can carry out in organic solvent, and the organic solvent can be selected from alcohols solvent
One of or it is a variety of, such as methanol, ethyl alcohol, preferred alcohol.
Preferably, the method also includes purifying complex shown in gained formula (I), the purification process includes
Following steps:
A) gained formula (I) compound represented vacuum pump is extracted into solvent, is then dissolved in organic solvent (such as anhydrous second
Ether) in, it is precipitated；
B) it is separated by solid-liquid separation after step a) precipitating, solid phase is washed and dried with anhydrous ether.
The present invention also provides the purposes of transient metal complex shown in the formula (I), and it is anti-to be used for catalysis in olefine polymerization
It answers, is preferred for catalyzed ethylene polymerization reaction.
The present invention also provides the preparation methods of ligand compound shown in above-mentioned formula (II), include the following steps:
1) by R shown in formula (III)4Replace R shown in diacetyl pyridine and formula (IV)5Substituted aniline replace anti-
It answers, obtains formula (V) compound represented；
2) formula (V) compound represented and formula (VI) compound represented obtained step 1) carries out condensation reaction, obtains
To ligand compound shown in formula (II)；
Wherein, R1、R2、R3、R4、R5With definitions as described above.
According to the present invention, in step 1), the substitution reaction can carry out under Catalyzed by p-Toluenesulfonic Acid.
According to the present invention, in step 1), the substitution reaction can carry out in aromatic hydrocarbon solvent, such as toluene, neighbour
Dimethylbenzene, meta-xylene, chlorobenzene etc. carry out preferably in toluene.
According to the present invention, in step 1), the substitution reaction can react 8-12 hours under conditions of being heated to reflux,
It is preferred that 10-12 hours.
According to the present invention, in step 1), aniline shown in diacetyl pyridine shown in the formula (III) and formula (IV)
Molar feed ratio be 1~1.5:1, preferably 1:1.
According to the present invention, after completion of the reaction, gained formula (V) compound represented can be further purified step 1), described
Purification process includes the following steps:
A1) formula (V) compound represented that step 1) obtains is dissolved in methylene chloride；
B1 it) is supported using alkali alumina and column chromatographs, with the mixed solvent (petroleum of petroleum ether and ethyl acetate
The volume ratio of ether and ethyl acetate is 100:1) it is that eluent is eluted, eluted fraction (solvent is detected by thin-layer chromatography
The mixed solvent that volume ratio for petroleum ether and ethyl acetate is 10:1 collects third flow point)；
C1 solvent, the formula purified (V) compound represented) are removed.
According to the present invention, in step 2), the condensation reaction can carry out under Catalyzed by p-Toluenesulfonic Acid.
According to the present invention, in step 2), the condensation reaction can carry out in aromatic hydrocarbon solvent, such as toluene, neighbour
Dimethylbenzene, meta-xylene, chlorobenzene etc. carry out preferably in toluene.
According to the present invention, in step 2), the condensation reaction can react 4-8 hours under conditions of being heated to reflux,
It is preferred that 6-8 hours.
According to the present invention, in step 2), formula (V) compound represented and formula (VI) compound represented mole feed intake
Than for 1:1.0~1.5, preferred molar ratio 1:1.1.
Preferably, gained formula (II) compound represented can be further purified, and the purification process may include as follows
Step:
A ') formula (II) compound represented that step 2) obtains is dissolved in methylene chloride；
B ') supported using alkali alumina and column chromatography, with the mixed solvent (petroleum of petroleum ether and ethyl acetate
The volume ratio of ether and ethyl acetate is preferably 125:1) it is that eluent is eluted, eluted fraction is detected by thin-layer chromatography, is received
Collect the second flow point；
C ') remove solvent, the formula purified (II) compound represented.
The present invention also provides the asymmetric di-imidogen pyridine ligands shown in the formula (II) containing tert-butyl, benzhydryl
The purposes of compound is used to prepare transient metal complex shown in formula (I).
The present invention also provides a kind of carbon monoxide-olefin polymerics, which is characterized in that the carbon monoxide-olefin polymeric includes major catalyst
And optional co-catalyst, wherein the major catalyst is selected from transient metal complex shown in formula (I).
According to the present invention, the co-catalyst can be selected from one of aikyiaiurnirsoxan beta, alkyl aluminum and chlorination alkyl aluminum or more
Kind.
According to the present invention, the aikyiaiurnirsoxan beta can be selected from methylaluminoxane (MAO) or triisobutyl aluminum modified aluminium methyl
One or both of oxygen alkane (MMAO).
According to the present invention, the metal Al when the carbon monoxide-olefin polymeric further includes co-catalyst, in the co-catalyst
Molar ratio with the central metal such as Fe of complex shown in formula (I) is (500~4000): 1, preferred molar ratio is (1000
~3300): 1, such as can be 1000:1,1500:1,1750:1,2000:1,2250:1,2500:1,2750:1,3250:1.
Preferably, metal Al and formula when the co-catalyst is methylaluminoxane (MAO), in methylaluminoxane (MAO)
(I) molar ratio of the central metal of complex shown in such as Fe is (1000~2500): 1, more preferable molar ratio is 2000:1.
Preferably, when the co-catalyst is triisobutyl aluminum modified methylaluminoxane (MMAO), triisobutyl aluminium changes
Metal Al and the molar ratio of the central metal such as Fe of complex shown in formula (I) in the methylaluminoxane (MMAO) of property are
(1000~3250): 1, more preferable molar ratio is 2750:1.
The present invention also provides a kind of preparation methods of polyethylene, comprising: under the action of above-mentioned carbon monoxide-olefin polymeric, makes second
Alkene carries out polymerization reaction.
Preferably, the temperature of the polymerization reaction is 30~110 DEG C, such as can be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70
℃,80℃,90℃,100℃,110℃；The time of the polymerization reaction be 5~60min, such as can be 5min, 10min,
15min,30min,45min,60min；The pressure of the polymerization reaction be 0.5~10atm, such as can be 1atm, 5atm or
10atm。
According to the present invention, the solvent of the polymerization reaction can be selected from toluene, ortho-xylene, methylene chloride, ethyl alcohol, tetrahydro
One or more of furans, hexane or hexamethylene.
According to the present invention, the polymerization reaction preferably carries out under ethylene atmosphere.
The present invention also provides above-mentioned transient metal complexes or carbon monoxide-olefin polymeric in catalysed olefin polymerization, especially
Purposes in ethylene polymerization.
The utility model has the advantages that
1. the present invention provides the bis-imine pyridines of asymmetry containing tert-butyl of a kind of high heat stability for preparing polyethylene wax to match
Body compound and its transient metal complex.Such complex contains electron donating group tert-butyl and bulky substituent two
Benzyl has single catalytic active center, can be realized by changing ligand structure and polymeric reaction condition to polymer
The regulation of molecular weight, and have many advantages, such as thermal stability outstanding, and catalytic activity is high, at low cost.
2. the present invention provides the asymmetric diimines containing tert-butyl, benzhydryl for the high heat stability for preparing polyethylene wax
The preparation method of yl pyridines ligand compound and its transient metal complex.The preparation process of two class compounds all has reaction item
The advantages that part is mild, the period is short, operating condition is simple.
3. the present invention provides the asymmetric di-imidogen pyridine ligand chemical combination containing tert-butyl, benzhydryl of high heat stability
The purposes of object and its transient metal complex.It is using the asymmetric di-imidogen metal complex prepared by intermediate as urging
Agent is applied to ethylene polymerization.Under the conditions of such as 80 DEG C, the activity of iron complex catalyzed ethylene polymerization may be up to 14.08
×106g·mol-1(Fe)·h-1, preparation-obtained polyethylene weight average molecular weight MwIn 2.1~318.2kgmol-1Between wave
It is dynamic, it shows to the extremely strong performance of control of molecular weight of polyethylene.
4. the method provided by the invention for preparing polyethylene is easy to operate, reaction condition is mild, can be used for preparing altitude line
Property polyethylene.Especially under the conditions of MMAO co-catalyst, 50~100 DEG C, gained polyethylene weight average molecular weight Mw5.1~
7.7kg·mol-1Between, it can be used for preparing the polyethylene wax being commercially badly in need of.
5. in the bis-imine pyridine complex structure for the benzhydril substituent containing large volume that the present invention designs and synthesizes,
Due to the steric hindrance effect of the benzhydryl at ortho position, so that aryl imine plane and coordinated planar are substantially at upright position,
Effective protection can be formed to metal active centres.Therefore, heretofore described complex activity is higher, and property is more stable.
6. the bis-imine pyridine transient metal complex for the tert-butyl containing electron donating group that the present invention designs and synthesizes, can
It is used to prepare the polyethylene wax being commercially badly in need of；Its high reaction activity thermal stability is stronger, and especially its iron complex catalysis is lived
Property high and thermal stability it is high, such as under the conditions of MMAO co-catalyst, 50~80 DEG C, catalytic activity 12.01~13.08 ×
106g·mol–1(Fe)h–1Between, it floats small, thermal stability is high, even if catalytic activity is still able to maintain in 110 DEG C of high temperature
2.82×106g·mol–1(Fe)h–1, meet industrial operation temperature, there is biggish application prospect.
Term definition and explanation:
Unless otherwise defined, the connotation that all scientific and technical terminologies have herein and claim theme fields technology
The normally understood connotation of personnel is identical.It should be understood that above-mentioned summary and being specified as exemplary and being only used for explaining hereafter, without right
Subject matter imposes any restrictions.In this application, unless otherwise stated, "or" used, "or" indicate "and/or".
In addition, term " includes " used and other forms, for example, it is "comprising", " containing " and " containing " and non-limiting.
Term " C1-6Alkyl " refers to the linear or branched alkyl group with 1-6 carbon atom, and the alkyl is, for example, methyl, second
Base, propyl, isopropyl, butyl, isobutyl group, tert-butyl, sec-butyl, amyl, neopentyl.
Term " C1-6Alkoxy " should be understood as preferably meaning the straight chain of formula-O- alkyl or the saturation monovalent hydrocarbon of branch
Base, wherein term " alkyl " have above-mentioned definition, for example, methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy,
Isobutoxy, sec-butoxy, tert-butoxy, amoxy, isoamoxy, hexyloxy or its isomers.Particularly, " alkoxy " is
“C1-6Alkoxy ", " C1-4Alkoxy ", " C1-3Alkoxy ", methoxyl group, ethyoxyl or propoxyl group, preferably methoxyl group, ethyoxyl
Or propoxyl group.Further preferably " C1-2Alkoxy ", especially methoxy or ethoxy.
Term " C3-10Naphthenic base " should be understood as the saturation monovalent monocyclic hydrocarbon ring for preferably meaning straight chain or branch, contain
There are such as 3,4,5,6,7 or 8 carbon atoms.C3-8Naphthenic base is, for example, monocycle hydrocarbon ring, for example, cyclopropyl, cyclobutyl, cyclopenta,
Cyclohexyl or suberyl.Particularly, the naphthenic base is C4-6Naphthenic base, C5-6Naphthenic base or cyclohexyl.For example, term " C3-6Ring
Alkyl " is interpreted as preferably meaning saturation monovalent monocyclic hydrocarbon ring, contains such as 3,4,5 or 6 carbon atoms.Specifically, C3-6
Naphthenic base is monocycle hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopenta or cyclohexyl.
Term " C3-10Cycloalkyl oxy " is interpreted as preferably meaning formula-O-ring alkyl group, wherein term " C3-10Ring
Alkyl " has definitions as described above.
Term " aryl " is interpreted as the preferred monovalence armaticity for indicating to have 6~20 carbon atoms or partial aromatic
Monocyclic, bicyclic or tricyclic hydrocarbon ring, preferably " C6-14Aryl ".Term " C6-14Aryl " be interpreted as it is preferred indicate to have 6,7,8,9,
10, monocyclic, bicyclic or tricyclic the hydrocarbon ring (" C of the monovalence armaticity of 11,12,13 or 14 carbon atoms or partial aromatic6-14Virtue
Base "), especially with the ring (" C of 6 carbon atoms6Aryl "), such as phenyl；Or xenyl, or there are 9 carbon atoms
Ring (" C9Aryl "), such as indanyl or indenyl, or the ring (" C with 10 carbon atoms10Aryl "), such as tetrahydro
Naphthalene, ihydro naphthyl or naphthalene, or the ring (" C with 13 carbon atoms13Aryl "), such as fluorenyl, or have 14
The ring (" C of a carbon atom14Aryl "), such as anthryl.
The Monocyclic examples of heteroaryl groups include, but is not limited to, thienyl, furyl, pyrrole radicals, oxazolyl, thiazole
Base, imidazole radicals, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazoles base, triazolyl, thiadiazolyl group, thiophene -4H- pyrazolyl etc. with
And their benzo derivative, such as benzofuranyl, benzothienyl, benzoxazolyl, benzo isoxazolyl, benzimidazole
Base, benzotriazole base, indazolyl, indyl, isoindolyl etc.；Or pyridyl group, pyridazinyl, pyrimidine radicals, pyrazinyl, triazine radical
Deng and their benzo derivative, such as quinolyl, quinazolyl, isoquinolyl etc.；Or azocine base, indolizine base, purine
Base etc. and their benzo derivative；Or cinnoline base, phthalazinyl, quinazolyl, quinoxalinyl, naphthyridines base, pteridyl, carbazole
Base, acridinyl, phenazinyl, phenothiazinyl, phenoxazine base etc..
Term " aryloxy " is interpreted as preferably meaning the group of formula-O- aryl or-O- heteroaryl, wherein term " virtue
Base " has above-mentioned definition.
Term " aryl C1-6Alkylidene " is interpreted as preferably meaning C1-6One substituent group of alkylidene is the group of aryl.
Wherein, C1-6Alkylidene means C1-6Further contain a substitution site in alkyl, wherein term " aryl ", " C1-6Alkyl " tool
There is above-mentioned definition.
Detailed description of the invention
Fig. 1 is that the embodiment of the present invention 1 prepares intermediate, and embodiment 2-6 prepares ligand and embodiment 7-11 prepares complex
Reacting flow chart.
Fig. 2 is complex Fe-3 crystal structure schematic diagram prepared by embodiment 9.
Fig. 3 is resulting polymers heating nucleus magnetic hydrogen spectrum figure in embodiment 12i).
Fig. 4 is resulting polymers heating nuclear-magnetism carbon spectrogram in embodiment 12i).
Fig. 5 is resulting polymers heating nucleus magnetic hydrogen spectrum figure in embodiment 17h).
Fig. 6 is resulting polymers heating nuclear-magnetism carbon spectrogram in embodiment 17h).
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can be gotten from open business unless otherwise instructed.
Methylaluminoxane (abbreviation MAO) used and modified methylaluminoxane (abbreviation MMAO) are purchased from U.S. AkzoNobel
Company.In following embodiments 12~21, the definition of Al/Fe is the metal Al and Fe in complex in co-catalyst MAO or MMAO
Molar ratio.
Embodiment 1. prepares (1- (2,6- bis- (the benzhydryl) -4- tertbutyl-aniline base) second of 2- acetyl group shown in following formula -6
Base) pyridine (IA)
It weighs 2,6-diacetylpyridine 3.26g (20mmol), 2,6- bis- (benzhydryl) -4- tertbutyl-aniline 9.63g
(20mmol) is added in reaction flask, adds toluene about 150mL in reaction flask, catalyst is then added in the reaction system again
The p-methyl benzenesulfonic acid of amount, and it is connected with water segregator.By the stirring of 12h reflux temperature, reaction mixture in a heated condition into
Row filtering, all volatile matters evaporate under pressure-lowering condition.Then, the unprocessed product obtained by alkali alumina column into
Row column chromatography, is eluted by eluent (100/1) of the mixed solvent of petroleum ether and ethyl acetate, is removed solvent, is obtained
The lurid powder of 5.01g, as IA, 2- acetyl group -6 (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl)
Pyridine, yield: 40%.Fusing point: 212-214 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3024 (w), 2957 (m), 1700 (ν (C=O), s), 1650 (ν (C=N), s), 1573
(w),1493(s),1448(s),1364(s),1413(m),1363(s),1309(w),1237(s),1192(w),1116(s),
1077(s),1029(m),997(w),949(m),892(w),867(w),814(m),765(m),739(s).
1H NMR(400MHz,CDCl3.TMS): δ 8.14 (d, J=8.0Hz, 1H, Py-Hm), 8.07 (d, J=7.6Hz,
1H,Py-Hm), 7.85 (t, J=7.6Hz, 1H, Py-Hp), 7.25-7.15 (m, 12H, aryl-H), 7.01 (t, J=8.0Hz,
8H,aryl-H),6.89(s,2H,aryl-H),5.26(s,2H,CHPh2), 2.67 (s, 3H, O=CCH3),1.11(m,9H,C
(CH3)3), 1.10 (m, 3H, N=CCH3).
13C NMR(100MHz,CDCl3.TMS):δ200.3,169.1,155.5,152.2,145.7,145.0,143.7,
142.8,137.0,131.4,129.8,129.4,128.2,127.9,126.1,126.0,125.1,124.6,122.2,52.4,
34.3,31.3,25.6,16.7.
Elemental analysis: C45H42N2O (626.84) theoretical value: C, 86.22；H,6.75；N, 4.47. experiment value: C, 86.23；
H,6.98；N,4.29.
Embodiment 2. prepares 2- shown in following formula (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(2,6- dimethyl-aniline base) ethyl) pyridine (ligand L 1)
Weigh (1- (2,6- bis- (the benzhydryl) -4- tertbutyl-aniline base) second of 2.00g (3.19mmol) 2- acetyl group -6
Base) pyridine and 0.42g (3.50mmol) 2,6- dimethylaniline be added in reaction flask, toluene solvant about 50mL, heating is added
It is stirred at reflux, adds the p-methyl benzenesulfonic acid of catalysis equivalent after half an hour in reaction flask, reaction mixture is heated to reflux
6h.It is cooled to room temperature, is evaporated in vacuo volatile matter.Then, the unprocessed residual solid obtained is carried out by alkali alumina column
Column chromatography (125:1 (v/v) is using the mixed solvent of petroleum ether and ethyl acetate as eluent) is eluted, and is removed solvent, is obtained
The lurid powder of 0.60g, as L1,2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,
6- dimethyl-aniline base) ethyl) pyridine, yield: 45%.Fusing point: 142-144 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3026 (w), 2957 (w), 1645 (ν (C=N), s), 1570 (w), 1494 (m), 1451
(m),1365(s),1326(w),1296(w),1245(s),1207(m),1124(m),1030(m),914(w),820(m),763
(s).
1H NMR(400MHz,CDCl3.TMS): δ 8.39 (d, J=7.6Hz, 1H, Py-Hm), 8.04 (d, J=7.6Hz,
1H,Py-Hm), 7.82 (t, J=8.0Hz, 1H, Py-Hp), 7.25-7.07 (m, 15H, aryl-H), 7.03 (t, J=7.2Hz,
8H,aryl-H),6.90(s,2H,aryl-H),5.30(s,2H,CHPh2), 2.12 (s, 3H, N=CCH3),2.06(s,6H,2×
CH3), 1.14 (s, 3H, N=CCH3),1.11(s,9H,C(CH3)3).
13C NMR(100MHz,CDCl3.TMS):δ169.7,167.4,155.2,154.9,148.8,145.8,144.8,
143.8,142.9,136.6,131.4,129.8,129.4,128.2,127.9,127.9,126.0,125.9,125.4,
125.0,123.0,122.3,121.8,52.3,34.3,31.3,18.0,17.0,16.4.
Elemental analysis: C53H51N3(730.01) theoretical value: C, 87.20；H,7.04；N, 5.76. experiment value: C, 87.04；H,
7.15；N,5.58.
Embodiment 3. prepares 2- shown in following formula (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(2,6- diethyl-anilino-) ethyl) pyridine (ligand L 2)
Weigh (1- (2,6- bis- (the benzhydryl) -4- tbutyl-phenyl imines of 2.00g (3.19mmol) 2- acetyl group -6
Base) ethyl) pyridine and 0.52g (3.50mmol) 2,6- diethylaniline be added in reaction flask, toluene solvant about 50mL is added,
Heating stirring reflux, the p-methyl benzenesulfonic acid of catalysis equivalent is added in reaction flask, is heated to reaction mixture after half an hour
Flow back 6h.It is cooled to room temperature, is evaporated in vacuo volatile matter.Then, the unprocessed residual solid obtained passes through alkali alumina column
It carries out column chromatography (125:1 (v/v) is using the mixed solvent of petroleum ether and ethyl acetate as eluent) to be eluted, removes solvent,
Obtain the lurid powder of 1.02g, as L2,2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6
(1- (2,6- diethyl-anilino-) ethyl) pyridine, yield: 42%.Fusing point: 138-140 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3027 (w), 2960 (w), 1638 (ν (C=N), s), 1566 (w), 1494 (w), 1447
(s),1365(s),1320(w),1294(w),1237(s),1191(m),1117(s),1029(w),865(w),823(m),761
(s).
1H NMR(400MHz,CDCl3.TMS): δ 8.38 (d, J=7.6Hz, 1H, Py-Hm), 8.04 (d, J=7.6Hz,
1H,Py-Hm), 7.82 (t, J=8.0Hz, 1H, Py-Hp),7.26–7.22(m,5H,aryl-H),7.19–7.11(m,10H,
), aryl-H 7.03 (t, J=6.8Hz, 8H, aryl-H), 6.90 (s, 2H, aryl-H), 5.30 (s, 2H, CHPh2),2.48–
2.31(s,4H,2×CH2), 2.13 (s, 3H, N=CCH3),1.18–1.14(m,9H,2×CH3, N=CCH3),1.11(s,9H,
C(CH3)3).
13C NMR(100MHz,CDCl3.TMS):δ169.58,167.05,155.13,154.86,147.77,145.84,
144.73,143.79,142.89,136.52,131.36,131.13,129.79,129.37,128.11,127.85,125.94,
125.87,125.85,124.98,123.20,122.19,121.74,53.32,52.26,34.21,31.28,24.51,
16.85,16.70,13.66.
Elemental analysis: C55H55N3.Et2O+H2O (850.20) theoretical value: C, 83.35；H,7.94；N, 4.94. experiment value:
C,83.42；H,7.14；N,5.15.
Embodiment 4. prepares 2- shown in following formula (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(2,6- diisopropyl-aniline base) ethyl) pyridine (ligand L 3)
Weigh (1- (2,6- bis- (the benzhydryl) -4- tertbutyl-aniline base) second of 2.00g (3.19mmol) 2- acetyl group -6
Base) pyridine and 0.62g (3.50mmol) 2,6-DIPA be added in reaction flask, toluene solvant about 50mL be added, adds
Thermal agitation reflux, the p-methyl benzenesulfonic acid of catalysis equivalent is added in reaction flask, is heated back to reaction mixture after half an hour
Flow 6h.It is cooled to room temperature, is evaporated in vacuo volatile matter.Then, the unprocessed residual solid obtained by alkali alumina column into
Row column chromatography (125:1 (v/v) is using the mixed solvent of petroleum ether and ethyl acetate as eluent) is eluted, and is removed solvent, is obtained
To the lurid powder of 1.00g, as L3,2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(2,6- diisopropyl-aniline base) ethyl) pyridine, yield: 40%.Fusing point: 204-206 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3061 (w), 2960 (s), 1650 (ν (C=N), s), 1570 (w), 1494 (m), 1450
(s),1363(s),1326(m),1294(m),1241(s),1190(s),1123(s),1079(m),1033(m),817(m),
764(m).
1H NMR(400MHz,CDCl3.TMS): δ 8.38 (d, J=7.6Hz, 1H, Py-Hm), 8.04 (d, J=7.2Hz,
1H,Py-Hm), 7.83 (t, J=8.0Hz, 1H, Py-Hp), 7.26-7.08 (m, 15H, aryl-H), 7.03 (t, J=7.2Hz,
8H,aryl-H),6.90(s,2H,aryl-H),5.31(s,2H,CHPh2),2.84–2.73(m,2H,CHMe2),2.15(s,3H,
N=CCH3),1.19(s,6H,2×CH3),1.17(s,9H,2×CH3, N=CCH3),1.11(s,9H,C(CH3)3).
13C NMR(100MHz,CDCl3.TMS):δ169.7,167.2,155.2,154.9,146.5,145.9,144.8,
143.8,142.9,136.6,135.8,131.4,129.8,129.4,128.2,128.0,126.0,125.9,125.0,
123.5,123.0,122.2,121.8,52.3,34.3,31.3,28.3,23.2,23.0,17.1,16.9.
Elemental analysis: C57H59N3(786.12) theoretical value: C, 87.09；H,7.57；N, 5.35. experiment value: C, 87.16；H,
7.67；N,5.32.
Embodiment 5. prepares 2- shown in following formula (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(trimethylbenzene amido) ethyl) pyridine (ligand L 4)
Weigh (1- (2,6- bis- (the benzhydryl) -4- tertbutyl-aniline base) second of 2.00g (3.19mmol) 2- acetyl group -6
Base) trimethylaniline is added in reaction flask between pyridine and 0.48g (3.50mmol) 2,4,6-, toluene solvant about 50mL is added,
Heating stirring reflux, the p-methyl benzenesulfonic acid of catalysis equivalent is added in reaction flask, is heated to reaction mixture after half an hour
Flow back 6h.It is cooled to room temperature, is evaporated in vacuo volatile matter.Then, the unprocessed residual solid obtained passes through alkali alumina column
It carries out column chromatography (125:1 (v/v) is using the mixed solvent of petroleum ether and ethyl acetate as eluent) to be eluted, removes solvent,
Obtain the lurid powder of 0.71g, as L4,2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6
(1- (trimethylbenzene amido) ethyl) pyridine, yield: 30%.Fusing point: 146-148 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3026 (w), 2960 (w), 1650 (ν (C=N), s), 1573 (w), 1494 (w), 1450
(m),1364(s),1325(w),1296(w),1245(m),1219(s),1150(w),1123(s),1079(s),1030(m),
855(m),822(m),768(m).
1H NMR(400MHz,CDCl3.TMS): δ 8.39 (d, J=7.6Hz, 1H, Py-Hm), 8.04 (d, J=7.2Hz,
1H,Py-Hm), 7.81 (t, J=7.6Hz, 1H, Py-Hp), 7.26-7.13 (m, 12H, aryl-H), 7.03 (t, J=6.8Hz,
8H,aryl-H),6.90(s,4H,aryl-H),5.31(s,2H,CHPh2),2.31(s,3H,CH3), 2.12 (s, 3H, N=
CCH3),2.03(s,6H,2×CH3), 1.16 (s, 3H, N=CCH3),1.11(s,9H,C(CH3)3).
13C NMR(100MHz,CDCl3.TMS):δ169.6,167.5,155.1,155.0,146.2,145.8,144.7,
143.8,142.9,136.5,132.1,131.4,131.3,129.8,129.4,129.3,128.5,128.1,127.9,
126.0,126.0,125.9,125.2,125.0,122.2,121.8,52.3,34.2,31.3,20.7,17.8,16.3.
Elemental analysis: C54H53N3(744.04) theoretical value: C, 87.17；H,7.18；N, 5.65. experiment value: C, 87.03；H,
7.62；N,5.30.
Embodiment 6. prepares 2- shown in following formula (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1-
(2,6- diethyl -4- metlyl-phenylamine base) ethyl) pyridine (ligand L 5)
Weigh (1- (2,6- bis- (the benzhydryl) -4- tertbutyl-aniline base) second of 2.00g (3.19mmol) 2- acetyl group -6
Base) pyridine and 0.57g (3.50mmol) 2,6- diethyl -4- methylaniline be added in reaction flask, toluene solvant is added about
50mL, heating stirring reflux, adds the p-methyl benzenesulfonic acid of catalysis equivalent in reaction flask after half an hour, carry out to reaction mixture
It is heated to reflux 6h.It is cooled to room temperature, is evaporated in vacuo volatile matter.Then, the unprocessed residual solid obtained is by alkaline oxygenated
Aluminium column carries out column chromatography (125:1 (v/v) is using the mixed solvent of petroleum ether and ethyl acetate as eluent) and is eluted, and removes molten
Agent obtains the lurid powder of 0.86g, as L5,2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -
6 (1- (2,6- diethyl -4- metlyl-phenylamine base) ethyl) pyridines, yield: 35%.Fusing point: 176-178 DEG C.
Structural identification data is as follows:
FTIR(KBr,cm-1): 3028 (w), 2961 (m), 1640 (ν (C=N), s), 1568 (m), 1494 (m), 1451
(s),1362(s),1322(w),1294(w),1242(m),1209(w),1117(s),1077(s),1030(m),862(m),
825(m),766(m),740(s).
1H NMR(400MHz,CDCl3.TMS): δ 8.39 (d, J=8.0Hz, 1H, Py-Hm), 8.04 (d, J=7.6Hz,
1H,Py-Hm), 7.81 (t, J=8.0Hz, 1H, Py-Hp), 7.26-7.13 (m, 12H, aryl-H), 7.03 (t, J=7.2Hz,
8H,aryl-H),6.94(s,2H,aryl-H),6.91(s,2H,aryl-H),5.31(s,2H,CHPh2),2.45–2.25(m,
7H,2×CH2,CH3), 2.13 (s, 3H, N=CCH3),1.17–1.13(m,9H,2×CH3, N=CCH3),1.11(s,9H,C
(CH3)3).
13C NMR(100MHz,CDCl3.TMS):δ169.6,167.2,155.1,155.0,145.8,145.2,144.7,
143.8,142.9,136.5,132.3,131.4,131.0,129.8,129.4,128.1,127.8,126.6,125.9,
125.9,125.0,122.1,121.7,52.2,34.2,31.2,24.5,20.9,16.9,16.6,13.8.
Elemental analysis: C56H57N3(772.09) theoretical value: C, 87.12；H,7.44；N, 5.44. experiment value: C, 87.13；H,
7.49；N,5.41.
Embodiment 7. prepares 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,6- bis-
Metlyl-phenylamine base) ethyl) pyridine Fe complex (Fe-1)
By 161mg (0.22mmol) 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,
6- dimethyl-aniline base) ethyl) pyridine (L1) and 39.8mg (0.20mmol) FeCl2·4H2O is dissolved under nitrogen atmosphere
In the ethyl alcohol that 10mL newly distills.The color of solution rapidly transforms into blue, forms sediment.At room temperature, to aaerosol solution into
Row stirring 8h, to ensure to react abundant.Sediment is collected by filtration, and is washed with a large amount of ether (3 × 5mL).Obtain 158mg
Blue powder, as Fe-1, yield: 92%.
Structural identification data is as follows:
FTIR(KBr；cm-1): 3027 (w), 2961 (m), 1604 (ν (C=N), w), 1582 (s), 1494 (m), 1470
(m),1446(m),1370(s),1264(s),1209(s),1030(m),810(m),773(s),742(m),700(s).
1H NMR(600MHz,CDCl3,TMS):δ78.42(s,1H,Py-Hm),78.03(s,1H,Py-Hm),67.64(s,
1H,Py-Hp),14.93(s,2H,aryl-Hm),13.71(s,2H,aryl-Hm),9.19(s.6H,2×CH3),7.05(s,4H,
aryl-H),6.77(s,2H,aryl-H),5.47(s,4H,aryl-H),4.98(s,2H,aryl-H),4.92(s,4H,aryl-
H),2.66(s,9H,C(CH3)3),-3.16(s,4H,aryl-H),-11.44(s,2H,CHPh2),-13.46(s,1H,aryl-
), H -23.49 (s, N=CCH3), -44.35 (s, N=CCH3).
Elemental analysis: C53H51N3FeCl2.Et2O (904.84) theoretical value: C, 73.01；H,6.57；N, 4.64. experiment value:
C,73.36；H,6.05；N,4.72.
Embodiment 8. prepares 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,6- bis-
Ethyl-anilino-) ethyl) pyridine Fe complex (Fe-2)
By 167mg (0.22mmol) 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,
6- diethyl-anilino-) ethyl) pyridine (L2) and 39.8mg (0.20mmol) FeCl2·4H2O is dissolved under nitrogen atmosphere
In the ethyl alcohol that 10mL newly distills.The color of solution rapidly transforms into blue, forms sediment.At room temperature, to aaerosol solution into
Row stirring 8h, to ensure to react abundant.Sediment is collected by filtration, and is washed with a large amount of ether (3 × 5mL).Obtain 170mg
Blue powder, as Fe-2, yield: 96%.
Structural identification data is as follows:
FTIR(KBr；cm-1): 3026 (w), 2966 (m), 1602 (ν (C=N), w), 1577 (m), 1495 (w), 1447
(s),1373(s),1314(w),1266(s),1205(s),1112(m),1079(w),1029(s),807(s),769(m),741
(s),700(s).
1H NMR(600MHz,CDCl3,TMS):δ78.13(s,1H,Py-Hm),77.46(s,1H,Py-Hm),72.03(s,
1H,Py-Hp),14.74(s,2H,aryl-Hm),14.07(s,2H,aryl-Hm),7.15(s,4H,aryl-H),6.75(s,2H,
aryl-H),5.95(s,4H,aryl-H),4.90(s,2H,aryl-H),4.78(s,4H,aryl-H),3.85(s,4H,2×
CH2),2.81(s,9H,C(CH3)3),-4.02(s,4H,aryl-H),-4.49(s,6H,2×CH3),-12.55(s,1H,
aryl-Hp),-14.60(s,2H,CHPh2), -29.35 (s, N=CCH3), -41.59 (s, N=CCH3).
Elemental analysis: C55H55N3FeCl2.Et2O (932.89) theoretical value: C, 73.39；H,6.81；N, 4.50. experiment value:
C,73.97；H,6.30；N,4.59.
Embodiment 9. prepares 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,6- bis-
Isopropyl-anilino-) ethyl) pyridine Fe complex (Fe-3)
By 173mg (0.22mmol) 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,
6- diisopropyl-aniline base) ethyl) pyridine (L3) and 39.8mg (0.20mmol) FeCl2·4H2O is dissolved under nitrogen atmosphere
In the ethyl alcohol that 10mL newly distills.The color of solution rapidly transforms into blue, forms sediment.At room temperature, to aaerosol solution into
Row stirring 8h, to ensure to react abundant.Sediment is collected by filtration, and is washed with a large amount of ether (3 × 5mL).Obtain 122mg
Blue powder, as Fe-3, yield: 67%.
Fe-3 crystal structure schematic diagram is as shown in Figure 2.
As seen from the figure, the central metal Fe of complex Fe-3 use pentacoordinate mode, respectively with three nitrogen-atoms N1, N2,
N3 and two chlorine atom Cl1, Cl2 is connected, in the cubic wimble structure of distortion.Wherein three nitrogen-atoms and Cl1 atom form four
Side cone bottom, Cl2 occupy the cubic vertex of a cone.Due to three-dimensional effect, Fe atom and vertex of a cone Cl2 atomic distance are aboutSubstrate
Spacing N (1)-Fe (1), N (3)-Fe (1), N (2)-Fe (1) and Cl (the 1)-Fe (1) of each atom and Fe atom are followed successively by WithIn addition, imine group is almost and pyrrole
In the same plane, plane where (the benzhydryl) -4- of 2,6- bis- tbutyl-phenyl on one side and cone baseplane skeleton are several for phenazine ring
Vertical, torsional angle is 83.8 °, and torsional angle is smaller between plane where the aryl rings of another side and cone baseplane skeleton, is 73.5 °.
Structural identification data is as follows:
FTIR(KBr；cm-1): 3024 (w), 2960 (m), 1605 (ν (C=N), w), 1576 (m), 1494 (m), 1447
(s),1368(s),1321(w),1270(s),1201(m),1103(m),1030(s),937(m),807(m),767(s),743
(s),700(s).
1H NMR(600MHz,CDCl3,TMS):δ81.83(s,1H,Py-Hm),79.39(s,1H,Py-Hm),76.53(s,
1H,Py-Hp),14.03(s,4H,aryl-Hm),7.32(s,4H,aryl-H),6.89(s,2H,aryl-H),6.18(s,4H,
aryl-H),4.66(s,2H,aryl-H),4.52(s,4H,aryl-H),2.85(s,9H,C(CH3)3),-4.21(s,6H,2×
CH3),-5.12(s,4H,aryl-H),-6.40(s,6H,2×CH3),-12.22(s,1H,aryl-Hp),-15.28(s,2H,
CHPh2), -17.61 (s, 2H, 2 × CH), -35.04 (s, N=CCH3), -42.42 (s, N=CCH3).
Elemental analysis: C57H59N3FeCl2(912.87) theoretical value: C, 75.00；H,6.51；N, 4.60. experiment value: C,
74.06；H,6.52；N,4.37.
Embodiment 10. prepares 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (front threes
Base anilino-) ethyl) pyridine Fe complex (Fe-4)
By 164mg (0.22mmol) 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (
Trimethylbenzene amido) ethyl) pyridine (L4) and 39.8mg (0.20mmol) FeCl2·4H2O is dissolved in 10mL under nitrogen atmosphere
In the ethyl alcohol newly distilled.The color of solution rapidly transforms into blue, forms sediment.At room temperature, aaerosol solution is stirred
8h is mixed, to ensure to react abundant.Sediment is collected by filtration, and is washed with a large amount of ether (3 × 5mL).Obtain 155mg blue
Powder, as Fe-4, yield: 89%.
Structural identification data is as follows:
FTIR(KBr；cm-1): 3024 (w), 2960 (m), 1607 (ν (C=N), w), 1579 (m), 1475 (w), 1449
(s),1370(s),1264(s),1218(w),1195(s),1078(m),1031(s),861(s),812(m),769(m),744
(s),704(s).
1H NMR(600MHz,CDCl3,TMS):δ77.31(s,2H,Py-Hm),70.06(s,1H,Py-Hp),23.08(s,
3H,CH3),14.06(s,2H,aryl-Hm),13.91(s,2H,aryl-Hm),9.51(s,6H,2×CH3),7.12(s,4H,
aryl-H),6.83(s,2H,aryl-H),5.73(s,4H,aryl-H),4.87(s,2H,aryl-H),4.81(s,4H,aryl-
H),2.69(s,9H,C(CH3)3),-3.24(s,4H,aryl-H),-10.80(s,2H,CHPh2), -25.77 (s, N=
CCH3), -43.31 (s, N=CCH3).
Elemental analysis: C54H53N3FeCl2(870.78) theoretical value: C, 74.48；H,6.14；N, 4.83. experiment value: C,
73.18；H,6.06；N,4.63.
Embodiment 11. prepares 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,6- bis-
Ethyl -4- metlyl-phenylamine base) ethyl) pyridine Fe complex (Fe-5)
By 170mg (0.22mmol) 2- (1- (2,6- bis- (benzhydryl) -4- tertbutyl-aniline base) ethyl) -6 (1- (2,
6- diethyl -4- metlyl-phenylamine base) ethyl) pyridine (L5) and 39.8mg (0.20mmol) FeCl2·4H2O, in nitrogen atmosphere
Under, it is dissolved in the ethyl alcohol that 10mL newly distills.The color of solution rapidly transforms into blue, forms sediment.At room temperature, to suspension
Solution is stirred 8h, to ensure to react abundant.Sediment is collected by filtration, and is washed with a large amount of ether (3 × 5mL).?
To 160mg blue powder, as Fe-5, yield: 89%.
Structural identification data is as follows:
FTIR(KBr；cm-1): 3029 (w), 2963 (s), 1605 (ν (C=N), w), 1582 (m), 1495 (m), 1449
(s),1425(w),1369(s),1264(s),1214(m),1075(m),1033(s),860(s),808(m),770(m),745
(s),704(s).
1H NMR(600MHz,CDCl3,TMS):δ78.26(s,1H,Py-Hm),76.79(s,1H,Py-Hm),76.32(s,
1H,Py-Hp),23.07(s,3H,CH3),14.26(s,2H,aryl-Hm),13.75(s,2H,aryl-Hm),7.26(s,4H,
aryl-H),6.85(s,2H,aryl-H),6.19(s,4H,aryl-H),4.74(s,2H,aryl-H),4.65(s,4H,aryl-
H),4.32(s,2H,CH2),3.82(s,2H,CH2),2.92(s,9H,C(CH3)3),-4.20(s,4H,aryl-H),-4.94
(s,6H,2×CH3),-14.23(s,2H,CHPh2), -31.98 (s, N=CCH3), -41.22 (s, N=CCH3).
Elemental analysis: C56H57N3FeCl2(898.84) theoretical value: C, 74.83；H,6.39；N, 4.68. experiment value: C,
74.06；H,6.36；N,4.53.
Embodiment 12. is using combining catalyzed ethylene polymerization under complex Fe-1 and co-catalyst MAO high pressure:
A) under ethylene atmosphere, the toluene solution of the catalyst Fe -1 (2 μm of ol) of 30ml is injected into 250ml equipped with machinery
In the stainless steel autoclave of stirring, it is subsequently added into 30ml toluene, the co-catalyst MAO (1.46mol/ of the desired amount of 2.1mL is added
L is in toluene), continuously adding toluene makes reaction solution total volume 100mL.Al/Fe=2000:1 at this time.Mechanical stirring starts,
It is kept for 400 revs/min, when polymerization temperature reaches 30 DEG C, ethylene is filled with into reaction kettle, polymerization reaction starts.It is protected at 30 DEG C
The ethylene pressure of 10atm is held, stirring carries out polymerization reaction 30min.The ethanol solution neutralization reaction liquid being acidified with 10% hydrochloric acid, obtains
It precipitates, is washed for several times with ethyl alcohol, drying to constant weight for 50 DEG C of vacuum, 2.12g polymer of weighing to obtain, polymerization activity: 2.12 to polymer
×106g/mol(Fe)h-1, polymerizable molecular amount Mw=318.2kg mol-1(MwFor the matter average molecular weight of polymer, surveyed by GPC
Examination gained), polymer Tm=134.2 DEG C of (TmFor the melting temperature of polymer, as obtained by DSC test).
B) be substantially with method a), difference in the present embodiment: polymerization temperature is 40 DEG C.Polymerization activity: 5.07 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=179.4kg mol-1, polymer Tm=132.3 DEG C.
C) be substantially with method a), difference in the present embodiment: polymerization temperature is 50 DEG C.Polymerization activity: 5.70 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=114.1kg mol-1, polymer Tm=132.0 DEG C.
D) be substantially with method a), difference in the present embodiment: polymerization temperature is 60 DEG C.Polymerization activity: 7.39 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=111.6kg mol-1, polymer Tm=133.1 DEG C.
E) be substantially with method a), difference in the present embodiment: polymerization temperature is 70 DEG C.Polymerization activity: 8.01 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=63.9kg mol-1, polymer Tm=131.3 DEG C.
F) be substantially with method a), difference in the present embodiment: polymerization temperature is 80 DEG C.Polymerization activity: 12.88 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=23.2kg mol-1, polymer Tm=131.3 DEG C.
G) be substantially with method a), difference in the present embodiment: polymerization temperature is 90 DEG C.Polymerization activity: 12.39 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=15.8kg mol-1, polymer Tm=131.2 DEG C.
H) be substantially with method a), difference in the present embodiment: polymerization temperature is 100 DEG C.Polymerization activity: 7.79 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=14.9kg mol-1, polymer Tm=130.5 DEG C.
I) be substantially with method a), difference in the present embodiment: polymerization temperature is 110 DEG C.Polymerization activity: 2.82 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=8.5kg mol-1, polymer Tm=128.7 DEG C.
Resulting polymers 100mg is taken, 3ml deuterated 1 is dissolved in, it is poly- to test this under the conditions of 135 DEG C for 1,2,2- tetrachloroethanes
Close object1H data, as shown in Figure 3.Signal accumulation 100 times, displacement 5.90 (ppm) and 5.00 (ppm) at obtain two groups it is multiple
Signal peak, it was demonstrated that be vinyl group (- CH=CH2)。
Resulting polymers 100mg is taken, 3ml deuterated 1 is dissolved in, it is poly- to test this under the conditions of 135 DEG C for 1,2,2- tetrachloroethanes
Close object13C data, as shown in Figure 4.Signal accumulation 6000 times, two groups are obtained at displacement 114.4 (ppm) and 139.6 (ppm)
Signal peak is shown to be the vinylic end group of polyethylene long-chain, it was demonstrated that resulting polymers are highly linear polyethylene.
J) be substantially with method f), difference in the present embodiment: (1.46mol/L is in toluene by the co-catalyst MAO of 1.1mL
In) make Al/Fe=1000:1.Polymerization activity: 2.11 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=135.5kg mol-1,
Polymer Tm=133.5 DEG C.
K) be substantially with method f), difference in the present embodiment: (1.46mol/L is in toluene by the co-catalyst MAO of 1.5mL
In) make Al/Fe=1500:1.Polymerization activity: 7.50 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=52.0kg mol-1, gather
Close object Tm=132.2 DEG C.
L) be substantially with method f), difference in the present embodiment: (1.46mol/L is in toluene by the co-catalyst MAO of 1.8mL
In) make Al/Fe=1750:1.Polymerization activity: 8.27 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=29.0kg mol-1, gather
Close object Tm=131.4 DEG C.
M) be substantially with method f), difference in the present embodiment: (1.46mol/L is in toluene by the co-catalyst MAO of 2.4mL
In) make Al/Fe=2250:1.Polymerization activity: 11.12 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=13.3kg mol-1,
Polymer Tm=129.6 DEG C.
N) be substantially with method f), difference in the present embodiment: (1.46mol/L is in toluene by the co-catalyst MAO of 2.6mL
In) make Al/Fe=2500:1.Polymerization activity: 10.85 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=11.2kg mol-1,
Polymer Tm=130.3 DEG C.
O) it is substantially with method f), difference in the present embodiment: polymerization time 5min.Polymerization activity: 26.51 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=5.0kg mol-1, polymer Tm=127.8 DEG C.
P) it is substantially with method f), difference in the present embodiment: polymerization time 10min.Polymerization activity: 26.10 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=9.8kg mol-1, polymer Tm=129.3 DEG C.
Q) it is substantially with method f), difference in the present embodiment: polymerization time 15min.Polymerization activity: 20.36 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=12.9kg mol-1, polymer Tm=130.1 DEG C.
R) it is substantially with method f), difference in the present embodiment: polymerization time 45min.Polymerization activity: 9.08 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=38.8kg mol-1, polymer Tm=130.5 DEG C.
S) it is substantially with method f), difference in the present embodiment: polymerization time 60min.Polymerization activity: 7.63 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=46.6kg mol-1, polymer Tm=131.2 DEG C.
T) it is substantially with method f), difference in the present embodiment: polymerization pressure 1atm.Polymerization activity: 0.60 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=1.7kg mol-1, polymer Tm=118.6 DEG C.
U) it is substantially with method f), difference in the present embodiment: polymerization pressure 5atm.Polymerization activity: 8.02 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=12.0kg mol-1, polymer Tm=129.6 DEG C.
Embodiment 13. utilizes the vinyl polymerization under complex Fe-2 and MAO joint catalysis pressurization:
Substantially with embodiment 12f), difference is: major catalyst Fe-2.Polymerization activity: 13.87 × 106g/mol(Fe)
h-1, polymerizable molecular amount Mw=13.9kg mol-1, polymer Tm=130.3 DEG C.
Embodiment 14. utilizes the vinyl polymerization under complex Fe-3 and MAO joint catalysis pressurization:
Substantially with embodiment 12f), difference is: major catalyst Fe-3.Polymerization activity: 2.55 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=33.4kg mol-1, polymer Tm=131.6 DEG C.
Embodiment 15. utilizes the vinyl polymerization under complex Fe-4 and MAO joint catalysis pressurization:
Substantially with embodiment 12f), difference is: major catalyst Fe-4.Polymerization activity: 11.61 × 106g/mol(Fe)
h-1, polymerizable molecular amount Mw=18.8kg mol-1, polymer Tm=132.1 DEG C.
Embodiment 16. utilizes the vinyl polymerization under complex Fe-5 and MAO joint catalysis pressurization:
Substantially with embodiment 12f), difference is: major catalyst Fe-5.Polymerization activity: 10.26 × 106g/mol(Fe)
h-1, polymerizable molecular amount Mw=17.3kg mol-1, polymer Tm=130.6 DEG C.
Embodiment 17. utilizes the vinyl polymerization under complex Fe-1 and MMAO joint catalysis pressurization:
A) under ethylene atmosphere, the toluene solution of the catalyst Fe -1 (2.0 μm of ol) of 30ml is injected into 250ml equipped with machine
In the stainless steel autoclave of tool stirring, it is subsequently added into 30ml toluene, the co-catalyst MMAO of the desired amount of 1.5mL is added
(2.0mol/L is in toluene), continuously adding toluene makes reaction solution total volume 100mL.Al/Fe=2000:1 at this time.Machinery stirs
Beginning is mixed, is kept for 400 revs/min, when polymerization temperature reaches 30 DEG C, ethylene is filled with into reaction kettle, polymerization reaction starts.30
The ethylene pressure of 10atm is kept at DEG C, stirring carries out polymerization reaction 30min.With in the ethanol solution of 10% hydrochloric acid acidification and instead
Liquid is answered, polymer precipitating is obtained, is washed for several times with ethyl alcohol, drying to constant weight for 50 DEG C of vacuum, 1.50g polymer of weighing to obtain, and polymerization is lived
Property: 1.50 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=12.6kg mol-1(MwFor the matter average molecular weight of polymer, pass through
GPC test gained), polymer Tm=126.7 DEG C of (TmFor the melting temperature of polymer, as obtained by DSC test).
B) be substantially with method a), difference in the present embodiment: polymerization temperature is 40 DEG C.Polymerization activity: 8.90 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=9.0kg mol-1, polymer Tm=123.7 DEG C.
C) be substantially with method a), difference in the present embodiment: polymerization temperature is 50 DEG C.Polymerization activity: 12.01 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=7.7kg mol-1, polymer Tm=128.9 DEG C.
D) be substantially with method a), difference in the present embodiment: polymerization temperature is 60 DEG C.Polymerization activity: 12.39 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=7.7kg mol-1, polymer Tm=128.4 DEG C.
E) be substantially with method a), difference in the present embodiment: polymerization temperature is 70 DEG C.Polymerization activity: 12.84 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=7.3kg mol-1, polymer Tm=129.1 DEG C.
F) be substantially with method a), difference in the present embodiment: polymerization temperature is 80 DEG C.Polymerization activity: 13.08 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=7.2kg mol-1, polymer Tm=130.4 DEG C.
G) be substantially with method a), difference in the present embodiment: polymerization temperature is 90 DEG C.Polymerization activity: 5.28 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=3.4kg mol-1, polymer Tm=124.8 DEG C.
H) be substantially with method a), difference in the present embodiment: polymerization temperature is 100 DEG C.Polymerization activity: 2.97 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=2.1kg mol-1, polymer Tm=119.8 DEG C.
Resulting polymers 100mg is taken, 3ml deuterated 1 is dissolved in, it is poly- to test this under the conditions of 135 DEG C for 1,2,2- tetrachloroethanes
Close object1H data, as shown in Figure 5.Signal accumulation 100 times.
Resulting polymers 100mg is taken, 3ml deuterated 1 is dissolved in, it is poly- to test this under the conditions of 135 DEG C for 1,2,2- tetrachloroethanes
Close object13C data, as shown in Figure 6.Signal accumulation 6000 times.
I) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 0.8mL
In) make Al/Fe=1000:1.Polymerization activity: 2.11 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=41.6kg mol-1, gather
Close object Tm=129.4 DEG C.
J) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 1.1mL
In) make Al/Fe=1500:1.Polymerization activity: 10.36 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=22.3kg mol-1,
Polymer Tm=131.2 DEG C.
K) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 1.9mL
In) make Al/Fe=2500:1.Polymerization activity: 13.68 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=7.1kg mol-1, gather
Close object Tm=129.2 DEG C.
L) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 2.1mL
In) make Al/Fe=2750:1.Polymerization activity: 14.08 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=6.7kg mol-1, gather
Close object Tm=129.0 DEG C.
M) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 2.2mL
In) make Al/Fe=3000:1.Polymerization activity: 11.21 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=5.2kg mol-1, gather
Close object Tm=127.8 DEG C.
M) be substantially with method f), difference in the present embodiment: (2.0mol/L is in toluene by the co-catalyst MMAO of 2.4mL
In) make Al/Fe=3250:1.Polymerization activity: 9.47 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=4.3kg mol-1, gather
Close object Tm=126.7 DEG C.
N) it is substantially with method l), difference in the present embodiment: polymerization time 5min.Polymerization activity: 35.06 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=3.2kg mol-1, polymer Tm=125.8 DEG C.
O) it is substantially with method l), difference in the present embodiment: polymerization time 10min.Polymerization activity: 21.12 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=3.6kg mol-1, polymer Tm=124.9 DEG C.
P) it is substantially with method l), difference in the present embodiment: polymerization time 15min.Polymerization activity: 15.32 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=4.2kg mol-1, polymer Tm=126.5 DEG C.
Q) it is substantially with method l), difference in the present embodiment: polymerization time 45min.Polymerization activity: 9.86 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=6.8kg mol-1, polymer Tm=128.1 DEG C.
R) it is substantially with method l), difference in the present embodiment: polymerization time 60min.Polymerization activity: 7.54 ×
106g/mol(Fe)h-1, polymerizable molecular amount Mw=9.3kg mol-1, polymer Tm=129.0 DEG C.
S) it is substantially with method l), difference in the present embodiment: polymerization pressure 1atm.Polymerization activity: 0.7 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=0.6kg mol-1, polymer Tm=125.1 DEG C.
T) it is substantially with method l), difference in the present embodiment: polymerization pressure 5atm.Polymerization activity: 8.10 × 106g/
mol(Fe)h-1, polymerizable molecular amount Mw=4.2kg mol-1, polymer Tm=125.2 DEG C.
Embodiment 18. utilizes the vinyl polymerization under complex Fe-2 and MMAO joint catalysis pressurization:
Substantially with embodiment 17l), difference is: the co-catalyst MMAO (2.0mol/L of major catalyst Fe-2,2.1mL
In toluene) make Al/Fe=2750:1.Polymerization activity: 10.74 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=6.6kg
mol-1, polymer Tm=127.6 DEG C.
Embodiment 19. utilizes the vinyl polymerization under complex Fe-3 and MMAO joint catalysis pressurization:
Substantially with embodiment 17l), difference is: the co-catalyst MMAO (2.0mol/L of major catalyst Fe-3,2.1mL
In toluene) make Al/Fe=2750:1.Polymerization activity: 6.12 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=6.0kg
mol-1, polymer Tm=127.5 DEG C.
Embodiment 20. utilizes the vinyl polymerization under complex Fe-4 and MMAO joint catalysis pressurization:
Substantially with embodiment 17l), difference is: the co-catalyst MMAO (2.0mol/L of major catalyst Fe-4,2.1mL
In toluene) make Al/Fe=2750:1.Polymerization activity: 11.50 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=5.6kg
mol-1, polymer Tm=127.8 DEG C.
Embodiment 21. utilizes the vinyl polymerization under complex Fe-5 and MMAO joint catalysis pressurization:
Substantially with embodiment 17l), difference is: the co-catalyst MMAO (2.0mol/L of major catalyst Fe-5,2.1mL
In toluene) make Al/Fe=2750:1.Polymerization activity: 9.52 × 106g/mol(Fe)h-1, polymerizable molecular amount Mw=5.1kg
mol-1, polymer Tm=127.8 DEG C.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. transient metal complex shown in lower formula (I):
Wherein, M is selected from iron or cobalt；
Each R1、R2It is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally by one or more Ra
Substituted following groups: C1-6Alkyl or C1-6Alkoxy；
Each R3、R4、R5It is identical or different, it is each independently selected from H, F, Cl, Br, I or optionally by one or more RbReplace
Following groups: C1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy, C1-6Alkylidene
Aryl；
Each X is identical or different, is each independently selected from F, Cl, Br, I；
Each RaIt is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally by one or more RcIt takes
The C in generation1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy；
Each RbIt is identical or different, it is each independently selected from H, F, Cl, Br, I, it is unsubstituted or optionally by one or more RcIt takes
The C in generation1-6Alkyl, C1-6Alkoxy, C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy；
Each RcIt is identical or different, it is each independently selected from H, F, Cl, Br, I or following groups: C1-6Alkyl, C1-6Alkoxy,
C3-10Naphthenic base, C3-10Cycloalkyl oxy, aryl, aryloxy.
2. transient metal complex as described in claim 1, which is characterized in that in formula (I), R1、R2It is identical or different, respectively
Independently selected from H, C1-3Alkyl, such as selected from H, methyl, ethyl, n-propyl, isopropyl；
Each R3、R4、R5It is identical or different, it is each independently selected from H, F, Cl, Br, I, C1-3Alkyl or C1-3Alkylidene aryl；
Each X is identical or different, is each independently selected from Cl, Br；
Preferably, it includes but is not limited to the complex with following group definition that complex shown in the formula (I), which is selected from:
Complex Fe-1: wherein R1=Me, X are selected from Cl, other groups H；
Complex Fe-2: wherein R1=Et, X are selected from Cl, other groups H；
Complex Fe-3: wherein R1=i-Pr, X are selected from Cl, other groups H；
Complex Fe-4: wherein R1=Me, R2=Me, X are selected from Cl, other groups H；
Complex Fe-5: wherein R1=Et, R2=Me, X are selected from Cl, other groups H.
3. ligand compound shown in lower formula (II):
Wherein, R1、R2、R3、R4、R5With definition described in claims 1 or 2；
Preferably, it includes but is not limited to the compound with following group definition that the ligand compound, which is selected from:
Ligand L 1:R1=Me, other groups H；
Ligand L 2:R1=Et, other groups H；
Ligand L 3:R1=i-Pr, other groups H；
Ligand L 4:R1=Me, R2=Me, other groups H；
Ligand L 5:R1=Et, R2=Me, other groups H.
4. the preparation method of ligand compound as claimed in claim 3, includes the following steps:
1) by R shown in formula (III)4Replace R shown in diacetyl pyridine and formula (IV)5Substituted aniline carries out substitution reaction, obtains
To formula (V) compound represented；
2) benzene compound shown in the formula (V) obtained step 1) and formula (VI) compound represented carry out condensation reaction, obtain
Ligand compound shown in formula (II)；
Wherein, R1、R2、R3、R4、R5With definition described in claims 1 or 2；
Preferably, in step 1), the substitution reaction carries out under Catalyzed by p-Toluenesulfonic Acid；
Preferably, in step 1), R shown in the formula (III)4Replace R shown in diacetyl pyridine and formula (IV)5Replace
The molar feed ratio of aniline is 1~1.5:1, also preferably 1:1；
Preferably, in step 2), the condensation reaction carries out under Catalyzed by p-Toluenesulfonic Acid；
Preferably, in step 2), the molar feed ratio of formula (V) compound represented and formula (VI) compound represented is 1:1
~1.5, further preferably molar ratio is 1:1.1.
5. the purposes of ligand compound as claimed in claim 3, which is characterized in that be used to prepare transition metal shown in formula (I)
Complex.
6. the preparation method of transient metal complex as claimed in claim 1 or 2, which comprises the steps of:
By ligand compound as claimed in claim 3 and compound MX2Complex reaction is carried out, obtains cooperating shown in the formula (I)
Object；
Wherein M, X have and define described in claims 1 or 2；
Preferably, the compound MX2The hydrate or other solvates of halide, the halide selected from iron content or cobalt
One of or it is a variety of, such as can be (DME) FeBr2、FeCl2·4H2O、FeCl2Or CoCl2·6H2One of O or more
Kind；
Preferably, the reaction carries out under anaerobic, such as carries out under the protective condition of inert gas such as nitrogen；
Preferably, the compound MX2It is 1:1~2, also preferably 1:1~1.5 with the molar ratio of formula (II) compound represented,
Further preferably 1:1.1.
7. the purposes of transient metal complex as claimed in claim 1 or 2, which is characterized in that it is used for catalysed olefin polymerization,
It is preferred for catalyzed ethylene polymerization reaction.
8. a kind of carbon monoxide-olefin polymeric, which is characterized in that the carbon monoxide-olefin polymeric includes that major catalyst and optional helping are urged
Agent, wherein the major catalyst is selected from transient metal complex of any of claims 1 or 2；
Preferably, the co-catalyst is selected from one of aikyiaiurnirsoxan beta, alkyl aluminum and chlorination alkyl aluminum or a variety of；
Preferably, the aikyiaiurnirsoxan beta is selected from methylaluminoxane (MAO) or triisobutyl aluminum modified methylaluminoxane (MMAO)
One or two；
Preferably, metal Al and formula (I) institute when the carbon monoxide-olefin polymeric further includes co-catalyst, in the co-catalyst
The molar ratio of the central metal of the complex shown such as Fe is (500~4000): 1, preferred molar ratio is (1000~3300): and 1,
It such as can be 1000:1,1500:1,1750:1,2000:1,2250:1,2500:1,2750:1,3000:1,3250:1；
Preferably, metal Al and formula (I) when the co-catalyst is methylaluminoxane (MAO), in methylaluminoxane (MAO)
Shown in complex central metal such as Fe molar ratio be (1000~2500): 1, more preferable molar ratio be 2000:1；
Preferably, triisobutyl aluminum modified when the co-catalyst is triisobutyl aluminum modified methylaluminoxane (MMAO)
Methylaluminoxane (MMAO) in metal Al and the molar ratio of the central metal such as Fe of complex shown in formula (I) be
(1000~3250): 1, more preferable molar ratio is 2750:1.
9. transient metal complex as described in any one of claims 1-3 or carbon monoxide-olefin polymeric according to any one of claims 8 exist
Purposes in catalysed olefin polymerization, especially ethylene polymerization.
10. a kind of preparation method of polyethylene, comprising: under the action of carbon monoxide-olefin polymeric according to any one of claims 8, make ethylene
Carry out polymerization reaction；
Preferably, the temperature of the polymerization reaction be 30~140 DEG C, such as can be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C,
80℃,90℃,100℃,110℃；The time of the polymerization reaction be 5~60min, such as can be 5min, 10min,
15min,45min,60min；The pressure of the polymerization reaction is 0.5~10atm, such as can be 1atm, 5atm or 10atm；
Preferably, the polymerization reaction carries out under ethylene atmosphere.
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