CN108530492A - Bridged dinuclear metallocene compound and preparation method and application thereof - Google Patents
Bridged dinuclear metallocene compound and preparation method and application thereof Download PDFInfo
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- CN108530492A CN108530492A CN201810472936.2A CN201810472936A CN108530492A CN 108530492 A CN108530492 A CN 108530492A CN 201810472936 A CN201810472936 A CN 201810472936A CN 108530492 A CN108530492 A CN 108530492A
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- zrcl
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- methyl
- ethyl
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 35
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 12
- -1 Hydrogen Chemical class 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 124
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 54
- 239000003446 ligand Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 34
- 239000012074 organic phase Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 31
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 28
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 27
- 238000000926 separation method Methods 0.000 claims description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 239000006228 supernatant Substances 0.000 claims description 21
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- 239000005457 ice water Substances 0.000 claims description 18
- 229960000583 acetic acid Drugs 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000004440 column chromatography Methods 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 239000003208 petroleum Substances 0.000 claims description 12
- 229910007926 ZrCl Inorganic materials 0.000 claims description 11
- 239000002027 dichloromethane extract Substances 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002220 fluorenes Chemical class 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 239000011435 rock Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 229910000765 intermetallic Inorganic materials 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 230000006315 carbonylation Effects 0.000 claims 1
- 238000005810 carbonylation reaction Methods 0.000 claims 1
- 235000013305 food Nutrition 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 36
- 238000006116 polymerization reaction Methods 0.000 abstract description 20
- 239000004743 Polypropylene Substances 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 229920000642 polymer Polymers 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 18
- 238000003786 synthesis reaction Methods 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 239000003426 co-catalyst Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000006073 displacement reaction Methods 0.000 description 9
- 238000007172 homogeneous catalysis Methods 0.000 description 9
- 210000003097 mucus Anatomy 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000037048 polymerization activity Effects 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 4
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- DFZYPLLGAQIQTD-UHFFFAOYSA-N 2,7-ditert-butyl-9h-fluorene Chemical class CC(C)(C)C1=CC=C2C3=CC=C(C(C)(C)C)C=C3CC2=C1 DFZYPLLGAQIQTD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 0 CC1C#CC=CC1C(*)C** Chemical compound CC1C#CC=CC1C(*)C** 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/328—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an alkali metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
- C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
- C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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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)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention provides a bridged dinuclear metallocene compound and a preparation method and application thereof. The bridged dinuclear metallocene compound has a structure shown in the following general formula I:wherein: n is 2, 3 or 4; r1Is hydrogen, methyl, ethyl or phenyl; r2Is hydrogen, methyl, ethyl or phenyl; r3Hydrogen, tert-butyl, bromine or chlorine. The bridged dinuclear metallocene compound can be used for syndiotactic polymerization of propylene, and the high syndiotactic polypropylene is obtained by using toluene as a solvent and MAO as a cocatalyst.
Description
Technical field
The present invention relates to a kind of bridged binuclear metallocene compounds and preparation method thereof and the compound in propylene
Application in syndiotactic polymerization.
Background technology
Since Fina companies in 1993 since liquid phase annular-pipe reactor scale up test goes out sPP, Basell,
The offshore companies such as Huntsman, Dow, ExxonMobil company and Mitsui Dong Ya companies, light extraction petro-chemical corporation successively endeavour
In the exploitation of sPP.Fina companies and Basell, ExxonMobil, Japanese light extraction petro-chemical corporation have been achieved with the industry of sPP at present
Metaplasia is produced.
This monokaryon metallocene catalyst becomes the emphasis of scientists from all over the world's research, is catalyzed by the monokaryon of patent protection
Agent almost covers the various aspects of the research field, it is difficult to there is big original creativity.With certain abutment bridging type monokaryon
Metallocene compound connects, and it is a completely new research field to obtain doube bridge metallocene.
Alt,Helmut G(Helmut G.Alt,Rainer Ernst.Dinuclear ansa zirconocene
complexes as dual-site catalysts for the polymerization of ethylene[J]
.Journal of Molecular Catalysis A:Chemical 195. (2003) .11-27) it has synthesized bridged binuclear and has urged
Agent, structure are as follows：
The catalyst is used for propylene polymerization, activity (93000kg mol-1h-1atm-1) than corresponding monokaryon metallocene catalysis
Agent Me2Si(2-Me-I-Ind)(2-Me-4-Ph-I-Ind)ZrCl2(LZrCl2=446000kg mol-1h-1atm-1) low, still
The polyacrylic molecular weight prepared increases, and atactic degree also increases (6.1wt%versus<0.2wt%for
LZrCl2)。
Later, Alt (Deppner, M.Alkylidenverbr ü ckte, symmetrische, zweikernige
Metallocenkomplexe als Katalysatoren für die Propylenpolymerisation[J]
.Journal of organometallic chemistry.2005,690(12):2861-2871.) have also been made and grind accordingly
Study carefully, synthesized the carbon bridging asymmetry binuclear metallocene catalyst of different length, structure is as follows：
Above-mentioned catalyst, when carbon bridge length is less than 5 carbon atoms, the wider (MWD of molecular weight distribution of resulting polymers>
10).It is found in propylene polymerization, polyacrylic gained is entirely 9~11% with isotacticity.
Stephan Jungling(Jüngling,S.,R.Müllhaupt and H.Plenio.Cooperative
effects in binuclear zirconocenes:their synthesis and use as catalyst in
propene polym-erization[J].Journal of organometallic chemistry.1993,460(2):
A series of benzene bridged binuclear Zirconocenes 191-195.) are synthesized, structure is as follows：
Above-mentioned catalyst, compared with monokaryon catalyst system and catalyzing, catalysis propylene polymerization activity reduces (2.6 × 105gPP/mol Zr
H, monokaryon catalyst system and catalyzing are 3 × 105GPP/mol Zr h), molecular weight reduces (GPC：Mn=2200g/mol, monokaryon catalyst system and catalyzing
Mn=3400g/mol).Moreover, with monokaryon catalyst system and catalyzing on the contrary, with AI/Zr ratios increase, molecular weight reduce.
Sierra(Cano Sierra,J.Formation of Dinuclear Titanium and Zirconium
Complexes by Olefin Metathesis-Catalytic Preparation of Organometallic
Catalyst Systems[J].Chemistry-A European Journal.2003,9(15):The synthesis such as 3618-3622.)
Dinuclear catalyst, structure are as follows：
Above-mentioned catalyst vinyl polymerization, under room temperature (25 DEG C), activity is at a fairly low, and when temperature is 60 DEG C, activity is endured
It is high, it is catalyzed propylene polymerization, at room temperature (25 DEG C) and 60 DEG C, activity is mean level, and molecular weight is at a fairly low, at room temperature, can be with
It obtains 36% isotactic polypropylene, at 60 DEG C, obtains 12% random polypropylene.
Invention content
It is an object of the present invention to provide a kind of new bridged binuclear metallocene compounds.
Another object of the present invention is to provide the preparation methods of the bridged binuclear metallocene compound.
Another object of the present invention is to provide bridged binuclear metallocene compound the answering in propylene syndiotactic polymerization
With.
On the one hand, the present invention provides a kind of bridged binuclear metallocene compounds, with structure shown in following general formula I：
Wherein：N=2,3 or 4；
R1For hydrogen, methyl, ethyl, phenyl；
R2For hydrogen, methyl, ethyl, phenyl；
R3For hydrogen, tertiary butyl, bromine or chlorine.
Specific embodiment according to the present invention, compound shown in general formula I of the invention are selected from following compound：
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)2
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4
[(CH3)(CH2CH3)C(C5H3)(C13H8)ZrCl2]2(CH2)2
[C6H5CH(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3
[(C6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3
[(CH3)2C(C5H3)(Cl2C13H6)ZrCl2]2(CH2)4
[(CH3)(CH2CH3)C(C5H3)(Br2C13H6)ZrCl2]2(CH2)4
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)3
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4。
On the other hand, the present invention also provides a kind of ligand compounds, with structure shown in following general formula II：
Wherein：N=2,3 or 4；
R1For hydrogen, methyl, ethyl or phenyl；
R2For hydrogen, methyl, ethyl or phenyl；
R3For hydrogen, tertiary butyl, bromine or chlorine.
Specific embodiment according to the present invention, compound shown in general formula II of the invention, wherein：N=2,3 or 4；R1For
Methyl, ethyl or phenyl；R2For hydrogen, methyl, ethyl or phenyl；R3For hydrogen.
Specific embodiment according to the present invention, compound shown in general formula II of the invention, wherein：N=3；R1For hydrogen or
Phenyl；R2For hydrogen, methyl or phenyl；R3For tertiary butyl.
Specific embodiment according to the present invention, compound shown in general formula II of the invention, wherein：N=4；R1For methyl
Or ethyl；R2For methyl or ethyl；R3For bromine or chlorine.
On the other hand, the present invention also provides a kind of methods preparing bridged binuclear metallocene compound shown in general formula I, should
Method includes：
The ligand compound is reacted with butyl lithium, four lithium salts are prepared；
Four lithium salts and ZrCl4Reaction, is prepared to obtain bridged binuclear metallocene compound.
Specific embodiment according to the present invention, the method for the bridged binuclear metallocene compound described in preparation of the invention
Including：The tetrahydrofuran solution containing ligand compound shown in general formula II is taken, is added containing n-BuLi at -40 DEG C~0 DEG C
Hexane solution is warming up to 20~30 DEG C, reacts 10~20 hours, removes the solids that solvent obtains and is dissolved with tetrahydrofuran ,-
70 DEG C~-80 DEG C, ZrCl is added42THF is warmed to room temperature naturally, is reacted 24~72 hours, is drained, dichloromethane extraction 2~3
Secondary, concentration adds n-hexane tune polarity, and at -30~10 DEG C, crystallization obtains solids, as dinuclear metallocene compounds.
Specific embodiment according to the present invention, the method for the bridged binuclear metallocene compound described in preparation of the invention
It further include the process for preparing the ligand compound described in general formula II.
Preferred embodiment according to the present invention, the process packet for preparing the ligand compound described in general formula II
It includes：
Bridging dihalo hydrocarbon and luxuriant sodium reaction prepare bridging cyclopentadienyl；
Bridging cyclopentadienyl sodium is obtained by the reaction in bridging cyclopentadienyl and metallic sodium；
Bridging cyclopentadienyl sodium and reactive ketone column chromatography for separation obtain bridging fulvene；
The ligand compound described in general formula II is obtained by the reaction in bridging fulvene and fluorenes lithium.
More preferable specific embodiment according to the present invention, the process packet for preparing the ligand compound described in general formula II
It includes：
The THF solution of double halogenated alkanes is added drop-wise in the THF solution of CpNa under ice-water bath, gradually there is white precipitate production
It is raw, it adds within 10~40 minutes, is warmed to room temperature naturally, reaction is overnight；Add saturation NaCl hydrolysis, has white precipitate, take upper layer yellow
Clear liquid, vinegar acid for adjusting pH, until neutral, liquid separation takes organic phase, water phase washs 2~3 times with anhydrous ether, merges organic phase, with satisfying
And brine It, anhydrous MgSO4Dry, vacuum distillation obtains Bridged-Dicyclopentadiene；
Sodium grain is taken, adds THF, ice-water bath to drip the THF solution of Bridged-Dicyclopentadiene, color becomes yellowish when being just added dropwise, and drips off
It is warmed to room temperature naturally afterwards, yellow is gradually deepened, and reaction is overnight；Supernatant liquor is pressed onto in container, carbonyl is slowly added dropwise under ice-water bath
The THF solution of based compound drips nature and is warmed to room temperature, and 20~40 DEG C are reacted 24~36 hours；Water hydrolysis on the rocks, becomes red
Color, glacial acetic acid adjust pH to neutrality, and liquid separation takes organic phase, water phase to be extracted 2~3 times with ether, and organic phase is washed with saturated common salt
It washs, anhydrous MgSO4It is dry；Column chromatography for separation obtains substituted bridged dicyclopentadiene；
Under ice bath, substituted bridged dicyclopentadiene is added drop-wise in the diethyl ether solution of fluorene compound, has precipitation to generate, reaction 24
~36 hours, hydrolysis, vinegar acid for adjusting pH to neutrality, liquid separation took organic phase, water phase ether to extract 2~3 times, merges organic phase, full
And brine It, anhydrous magnesium sulfate drying, filtering, vacuum rotation remove solvent, using petroleum ether as mobile phase, column chromatography for separation is dense
The ligand compound is obtained after contracting.
On the other hand, the present invention also provides the bridged binuclear metallocene compounds is catalyzed as propylene syndiotactic polymerization
The application of agent.
On the other hand, the present invention also provides a kind of propylene syndiotactic polymerization catalyst comprising at least one is selected from this hair
The bright bridged binuclear metallocene compound.
The present invention introduces methyl, methylene, ethyl, phenyl on the luxuriant ring of connection and the carbon abutment of fluorenes ring, draws on fluorenyl
Enter hydrogen, tertiary butyl, bromine, chlorine, and have different bridging length, has obtained a series of bridged binuclear metallocene compound, carried
High complex compound yield, when being catalyzed propylene polymerization, activity is higher, and normality is also higher.
For example, at propylene pressure 0.1MPa, using toluene as solvent, it is added and contains 2 μm of 1 toluene solutions of ol complex compounds, MAO
(1.60M, 2.5mL), the 0.5 hour reaction time at 0 DEG C of reaction temperature are catalyzed propylene polymerization, are 1000 in aluminium/zirconium ratio, gather
It is 1.8 × 10 to close activity6Normality [rrrr]=86% between g polymer/mol Mh, sPP.
The present invention uses bridged binuclear metallocene catalyst/MAO systems, under the effect of minor proportion co-catalyst, to third
Alkene polymerization obtains greater activity.
In terms of the practical application of technical solution disclosed above, bridged binuclear metallocene olefin polymerization catalysis of the present invention
Agent advantage is apparent：Product yield is high, and it is easy to isolate and purify, and needs co-catalyst few when for being catalyzed propylene polymerization, catalytic activity
Height, normality height.
Specific implementation mode
Implementation below by way of specific embodiment the present invention will be described in detail technical solution and possessed advantageous effect, but not
Can regard as to the present invention can practical range any restriction.Unspecified method and operating condition in each embodiment,
Routine techniques according to the field or the operation according to apparatus manufacturer suggestion carry out.Ligand chemical combination obtained by each embodiment
Object and complex compound carry out structural confirmation according to the known method of fields.
Embodiment 1
1 [(CH of ligand L3)2C(C5H4)(C13H9)]2(CH2)2Synthesis
1 [(CH of ligand L3)2C(C5H4)(C13H9)]2(CH2)2Synthetic route it is as follows:
THF (40mL) solution of 1,2- dichloroethanes (24mL, 303.6mmol) is added drop-wise to the THF of CpNa under ice-water bath
In solution (4.048mol/L), gradually there are white precipitate generation, half an hour to add, be warmed to room temperature naturally, reaction is overnight；Add saturation
NaCl is hydrolyzed, and is had white precipitate in bottom of bottle, is taken upper layer yellow clear liquid, vinegar acid for adjusting pH, until neutral, liquid separation takes organic phase, water phase
It is washed (20mL × 3) three times with anhydrous ether, merges organic phase, with saturated common salt water washing, anhydrous MgSO4Dry, decompression is steamed
It evaporates, obtains ethylidene overseas Chinese federation dicyclopentadiene, colourless transparent liquid 18g, yield about 60%.
Add sodium grain (20.1g, 873.9mmol) in 500mL there-necked flasks, adds THF200mL, ice-water bath that ethylidene overseas Chinese federation is added dropwise
The THF solution of dicyclopentadiene (15g, 94.95mmol), color becomes yellowish when being just added dropwise, and is warmed to room temperature naturally after dripping off, yellow
Gradually deepen, reaction is overnight；Supernatant liquor is pressed onto in 500mL there-necked flasks, be slowly added dropwise under ice-water bath acetone (11.01g,
THF (60mL) solution 189.96mmol), drips nature and is warmed to room temperature, and 25 DEG C are reacted one day；Water hydrolysis on the rocks, becomes red
Color, glacial acetic acid adjust pH to neutrality, and liquid separation takes organic phase, water phase to be extracted three times with ether, and organic phase is washed with saturated common salt
It washs, anhydrous MgSO4It is dry；Column chromatography for separation, petroleum ether are solvent, collect first fraction, obtain ethylidene overseas Chinese federation two (6,
6- dimethyl fulvenes), the partially red grease 10.92g of yellow, yield 42%；
Under ice bath, ethylidene overseas Chinese federation two (6,6- dimethyl fulvene) (7g, 29.4mmol) be added drop-wise to FluLi (10.17g,
In ether (250mL) solution 58.8mmol), there is a little precipitation to generate, react one day, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 10.1g mucus, as ligand L 1 after concentration.
1 [(CH of complex compound3)2C(C5H3)(C13H8)ZrCl2]2(CH2)2Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.14g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.01g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.28g, 3.4mmol), is warmed to room temperature naturally, reacts 2 days, reaction
Liquid is yellow, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 406mg, yield
30%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50ml, co-catalyst MAO2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 1 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 3.6g, polymerization activity 1.8 × 106It is laggard to remove random object with dimethylbenzene by gpolymer/molMh
Row from13C NMR characterizations, calculating learn that normality is 86% between the rrrr of obtained polymer.
Embodiment 2
2 [(CH of ligand L3)2C(C5H4)(C13H9)]2(CH2)4Synthesis
With embodiment 1, Isosorbide-5-Nitrae-dichloroetane prepares bridging fulvene instead of 1,2- dichloroethanes
Under ice bath, bridging fulvene (10.172g, 29.4mmol) is added drop-wise to the ether of FluLi (10.17g, 58.8mmol)
In (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 6.97g mucus after concentration, yield 35% is as matched
Body L.
2 [(CH of complex compound3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.356g, 2mmol), there is solid
It generating, back flow reaction two days, supernatant liquor is removed in press filtration, is washed once, is drained with ether, obtained solid 1.21g, add tetrahydrofuran,
Under the conditions of -78 DEG C, ZrCl is added in liquid nitrogen ethanol bath42THF (1.3g, 3.447mmol), is warmed to room temperature naturally, reacts 2 days,
Reaction solution is yellow, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune
Polarity is put in -20 DEG C of refrigerators, and yellow substance is precipitated, and press filtration removes supernatant, and precipitation is drained, and yellow powder 1239mg, yield are obtained
72%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 2 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 3.8g, polymerization activity 1.9 × 106G polymer/mol Mh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 92% between [rrrr] of obtained polymer.
Embodiment 3
3 [(CH of ligand L3)(CH2CH3)C(C5H4)(C13H9)]2(CH2)2Synthesis
Under ice bath, ethylene bridge fulvene (7.82g, 29.4mmol) is added drop-wise to the ether of FluLi (10.17g, 58.8mmol)
In (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 6.51g mucus after concentration, yield 37% is as matched
Body L.
3 [(CH of complex compound3)(CH2CH3)C(C5H3)(C13H8)ZrCl2]2(CH2)2Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.2g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.13g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.37g, 3.63mmol), is warmed to room temperature naturally, reaction 2 days, instead
It is yellow to answer liquid, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 481mg, yield
29%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 3 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 3.64g, polymerization activity 1.82 × 106Gpolymer/molMh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 90% between [rrrr] of obtained polymer.
Embodiment 4
4 [C of ligand L6H5C(C5H4)((tBu)2C13H7)]2(CH2)3Synthesis
With 1,1,3- dichloropropane of embodiment bridging fulvene is prepared instead of 1,2- dichloroethanes
Under ice bath, bridging fulvene (11.05g, 29.4mmol) be added drop-wise to 2,7- di-tert-butyl-fluorenes lithium (16.34g,
In ether (250mL) solution 58.8mmol), there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, acetic acid tune
PH is saved to neutrality, liquid separation takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, anhydrous slufuric acid
Magnesium dries 6h, filtering, and vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 9.32g mucus after concentration, receives
Rate 34%, as ligand L 4.
4 [C of complex compound6H5C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.86g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.75g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.38g, 3.66mmol), is warmed to room temperature naturally, reaction 2 days, instead
It is yellow to answer liquid, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1478mg, yield
65%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 4 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 3.7g, polymerization activity 1.85 × 106Gpolymer/molMh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 91% between [rrrr] of obtained polymer.
Embodiment 5
5 [(C of ligand L6H5)2C(C5H4)((tBu)2C13H7)]2(CH2)3Synthesis
With 1,1,3- dichloropropane of embodiment bridging fulvene is prepared instead of 1,2- dichloroethanes
Under ice bath, bridging fulvene (14.7g, 29.4mmol) be added drop-wise to 2,7- di-tert-butyl-fluorenes lithium (16.34g,
In ether (250mL) solution 58.8mmol), there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, acetic acid tune
PH is saved to neutrality, liquid separation takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, anhydrous slufuric acid
Magnesium dries 6h, filtering, and vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 10.24g mucus after concentration,
Yield 33%, as ligand L 5.
5 [(C of complex compound6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (2.11g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.89g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.32g, 3.5mmol), is warmed to room temperature naturally, reacts 2 days, reaction
Liquid is yellow, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1795mg, yield
75%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 5 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 3.46g, polymerization activity 1.73 × 106Gpolymer/molMh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 90% between [rrrr] of obtained polymer.
Embodiment 6
6 [(CH of ligand L3)2C(C5H4)(Cl2C13H7)]2(CH2)4Synthesis
With embodiment 1, Isosorbide-5-Nitrae-dichloroetane prepares bridging fulvene instead of 1,2- dichloroethanes
Under ice bath, bridging fulvene (10.17g, 29.4mmol) is added drop-wise to the second of 2,7- dichloros fluorenes (13.64g, 58.8mmol)
In ether (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 12.36g mucus after concentration, yield 32% is as matched
Body L6.
6 [(CH of complex compound3)2C(C5H3)(Cl2C13H6)ZrCl2]2(CH2)4Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (2.63g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 2.53g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.42g, 3.78mmol), is warmed to room temperature naturally, reaction 2 days, instead
It is yellow to answer liquid, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1013mg, yield
76%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 6 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 2.1g, polymerization activity 1.05 × 106Gpolymer/molMh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 93% between [rrrr] of obtained polymer.
Embodiment 7
7 [CH of ligand L3(CH2CH3)C(C5H4)(Br2C13H7)]2(CH2)4Synthesis
With embodiment 1, Isosorbide-5-Nitrae-dichloroetane prepares bridging fulvene instead of 1,2- dichloroethanes
Under ice bath, bridging fulvene (8.64g, 29.4mmol) is added drop-wise to the ether of 2,7- dibromos fluorenes (9.7g, 58.8mmol)
In (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 10.2g mucus after concentration, yield 37% is as matched
Body L7.
7 [CH of complex compound3(CH2CH3)C(C5H3)(Br2C13H6)ZrCl2]2(CH2)4Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.88g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.65g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.29g, 3.42mmol), is warmed to room temperature naturally, reaction 2 days, instead
It is yellow to answer liquid, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1669mg, yield
78%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 7 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 2.06g, polymerization activity 1.03 × 106Gpolymer/molMh, after removing random object with dimethylbenzene
Carry out from13C NMR characterizations, calculating learn that normality is 92% between the rrrr of obtained polymer.
Embodiment 8
8 [(CH of ligand L3)2C(C5H4)(C13H9)]2(CH2)3Synthesis
With 1,1,3- dichloropropane of embodiment bridging fulvene is prepared instead of 1,2- dichloroethanes
Under ice bath, ethylene bridge fulvene (7.41g, 29.4mmol) is added drop-wise to the ether of FluLi (10.17g, 58.8mmol)
In (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 10.4g mucus, as ligand L 8 after concentration.
8 [(CH of complex compound3)2C(C5H3)(C13H8)ZrCl2]2(CH2)3Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.17g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.03g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.28g, 3.4mmol), is warmed to room temperature naturally, reacts 2 days, reaction
Liquid is yellow, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1062mg, yield
70%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50ml, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 8 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 2.2g, polymerization activity 1.1 × 106It is laggard to remove random object with dimethylbenzene by gpolymer/molMh
Row from13C NMR characterizations, calculating learn that normality is 90% between [rrrr] of obtained polymer.
Embodiment 9
9 [(CH of ligand L3)2C(C5H4)(C13H9)]2(CH2)4Synthesis
With embodiment 1, Isosorbide-5-Nitrae-dichloroetane prepares bridging fulvene instead of 1,2- dichloroethanes
Under ice bath, ethylene bridge fulvene (7.82g, 29.4mmol) is added drop-wise to the ether of FluLi (10.17g, 58.8mmol)
In (250mL) solution, there is a little precipitation to generate, react one day, be still a small amount of precipitation, hydrolysis, vinegar acid for adjusting pH to neutrality, point
Liquid takes organic phase, water phase ether to be extracted twice, and merges organic phase, saturated common salt water washing, and anhydrous magnesium sulfate dries 6h, filters,
Vacuum rotation removes solvent, and using petroleum ether as mobile phase, column chromatography for separation obtains 10.5g mucus, as ligand L 9 after concentration.
9 [(CH of complex compound3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4Synthesis
Under the conditions of ice-water bath,nBuLi (8mmol) is added drop-wise in the diethyl ether solution of ligand (1.20g, 2mmol), there is solid life
At supernatant liquor is removed in back flow reaction two days, press filtration, is washed once, is drained with ether, obtain solid 1.06g, adds tetrahydrofuran, liquid
Under the conditions of -78 DEG C, ZrCl is added in nitrogen ethanol bath42THF (1.28g, 3.4mmol), is warmed to room temperature naturally, reacts 2 days, reaction
Liquid is yellow, and solvent is removed under reduced pressure, and dichloromethane extracts twice (30mL × 2), is concentrated into 20mL, adds some n-hexane tune poles
Property, it puts in -20 DEG C of refrigerators, yellow substance is precipitated, press filtration removes supernatant, and precipitation is drained, and obtains yellow powder 1162mg, yield
75%.
Homogeneous catalysis propylene polymerization under normal pressure
By the 100mL there-necked flask ethylene gas for having magnetic stir bar, gas-guide tube displacement 3 times, under nitrogen protection, successively
It is added toluene 50mL, co-catalyst MAO 2.5mL (1.60M) [Al/M=1000], 2.0 μm of ol complex compounds 9 are passed through third under normal pressure
Alkene gas starts polymerisation at 0 DEG C, is stirred to react 30min, closes propylene gas cylinder, is terminated with 10% acidic alcohol anti-
It answers, polymer is transferred in beaker, is stood overnight, and filters and with the abundant washing copolymer of ethyl alcohol, perseverance is dried under vacuum at 80 DEG C
Weight weighs polymer quality 2.4g, polymerization activity 1.2 × 106It is laggard to remove random object with dimethylbenzene by gpolymer/molMh
Row from13C NMR characterizations, calculating learn that normality is 92% between the rrrr of obtained polymer.
Claims (10)
1. a kind of bridged binuclear metallocene compound, with structure shown in following general formula I：
Wherein：N=2,3 or 4；
R1For hydrogen, methyl, ethyl, phenyl；
R2For hydrogen, methyl, ethyl, phenyl；
R3For hydrogen, tertiary butyl, bromine or chlorine.
2. compound according to claim 1 is selected from following compound：
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)2
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4
[(CH3)(CH2CH3)C(C5H3)(C13H8)ZrCl2]2(CH2)2
[C6H5CH(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3
[(C6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3
[(CH3)2C(C5H3)(Cl2C13H6)ZrCl2]2(CH2)4
[(CH3)(CH2CH3)C(C5H3)(Br2C13H6)ZrCl2]2(CH2)4
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)3
[(CH3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4。
3. a kind of ligand compound, with structure shown in following general formula II：
Wherein：N=2,3 or 4；
R1For hydrogen, methyl, ethyl or phenyl；
R2For hydrogen, methyl, ethyl or phenyl；
R3For hydrogen, tertiary butyl, bromine or chlorine.
4. ligand compound according to claim 3, wherein：N=2,3 or 4；R1For methyl, ethyl or phenyl；R2For hydrogen,
Methyl, ethyl or phenyl；R3For hydrogen.
5. ligand compound according to claim 3, wherein：N=3；R1For hydrogen or phenyl；R2For hydrogen, methyl or phenyl；
R3For tertiary butyl.
6. ligand compound according to claim 3, wherein：N=4；R1For methyl or ethyl；R2For methyl or ethyl；R3
For bromine or chlorine.
7. a kind of method preparing bridged binuclear metallocene compound as claimed in claim 1 or 2, this method include：
It is reacted with butyl lithium according to claim 3~6 any one of them ligand compound, four lithium salts is prepared；
Four lithium salts and ZrCl4Reaction, is prepared bridged binuclear metallocene compound；
Preferably, the method for preparing bridged binuclear metallocene compound as claimed in claim 1 or 2 includes：
The tetrahydrofuran solution containing with good grounds claim 3~6 any one of them ligand compound is taken, at -40 DEG C~0 DEG C
The hexane solution containing n-BuLi is added, is warming up to 20~30 DEG C, reacts 10~20 hours, removes the solids that solvent obtains
It is dissolved with tetrahydrofuran, -70 DEG C~-80 DEG C, ZrCl is added42THF is warmed to room temperature naturally, is reacted 24~72 hours, is drained,
Dichloromethane extracts 2~3 times, and concentration adds n-hexane tune polarity, and at -30~-10 DEG C, crystallization obtains solids, as double-core cyclopentadienyl
Metallic compound.
8. according to the method described in claim 7, this method further includes preparing to be matched according to claim 3~6 any one of them
The process of body compound；
Preferably, described prepare according to the process of claim 3~6 any one of them ligand compound includes：
Bridging dihalo hydrocarbon and luxuriant sodium reaction prepare bridging cyclopentadienyl；Bridging cyclopentadienyl sodium is obtained by the reaction in bridging cyclopentadienyl and metallic sodium；Bridging cyclopentadienyl sodium
Bridging fulvene is obtained with reactive ketone column chromatography for separation；Ligand is obtained by the reaction in bridging fulvene and fluorenes lithium；
It is highly preferred that the preparation includes according to the process of claim 3~6 any one of them ligand compound：
The THF solution of double halogenated alkanes is added drop-wise in the THF solution of CpNa under ice-water bath, gradually there is a white precipitate generation, 10
It adds within~40 minutes, is warmed to room temperature naturally, reaction is overnight；Add saturation NaCl hydrolysis, have white precipitate, take upper layer yellow clear liquid,
Vinegar acid for adjusting pH, until neutral, liquid separation takes organic phase, water phase to be washed 2~3 times with anhydrous ether, merges organic phase, is eaten with saturation
Salt water washing, anhydrous MgSO4Dry, vacuum distillation obtains Bridged-Dicyclopentadiene；
Sodium grain is taken, adds THF, the THF solution of ice-water bath drop Bridged-Dicyclopentadiene, color becomes yellowish when being just added dropwise, after dripping off certainly
It is so warmed to room temperature, yellow is gradually deepened, and reaction is overnight；Supernatant liquor is pressed onto in container, carbonylation is slowly added dropwise under ice-water bath
The THF solution for closing object, drips nature and is warmed to room temperature, and 20~40 DEG C are reacted 24~36 hours；Water hydrolysis on the rocks, becomes red,
Glacial acetic acid adjusts pH to neutrality, and liquid separation takes organic phase, water phase to be extracted 2~3 times with ether, organic phase saturated common salt water washing,
Anhydrous MgSO4It is dry；Column chromatography for separation obtains substituted bridged dicyclopentadiene；
Under ice bath, substituted bridged dicyclopentadiene is added drop-wise in the diethyl ether solution of fluorene compound, has precipitation to generate, reaction 24~36
Hour, it hydrolyzes, vinegar acid for adjusting pH to neutrality, liquid separation, organic phase, water phase ether is taken to extract 2~3 times, merge organic phase, saturation food
Salt water washing, anhydrous magnesium sulfate drying, filtering, vacuum rotation remove solvent, using petroleum ether as mobile phase, column chromatography for separation, after concentration
It obtains according to claim 3~6 any one of them ligand compound.
9. application of the bridged binuclear metallocene compound as claimed in claim 1 or 2 as propylene syndiotactic polymerization catalyst.
10. a kind of propylene syndiotactic polymerization catalyst comprising at least one is selected from bridged binuclear as claimed in claim 1 or 2 cyclopentadienyl
Metallic compound.
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