CN108530492B - 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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- 150000001875 compounds Chemical class 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 17
- -1 Hydrogen Chemical class 0.000 claims abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 128
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 48
- 239000003446 ligand Substances 0.000 claims description 43
- 239000012074 organic phase Substances 0.000 claims description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 33
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 24
- 239000005457 ice water Substances 0.000 claims description 21
- 239000006228 supernatant Substances 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 17
- 229960000583 acetic acid Drugs 0.000 claims description 17
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 17
- 238000004440 column chromatography Methods 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 229910007926 ZrCl Inorganic materials 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 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 8
- 239000008346 aqueous phase Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 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 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- XTCAGVVVEIJFON-UHFFFAOYSA-N 9h-fluorene;lithium Chemical compound [Li].C1=CC=C2CC3=CC=CC=C3C2=C1 XTCAGVVVEIJFON-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 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
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 36
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 11
- 239000000460 chlorine Substances 0.000 abstract description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052794 bromium Inorganic materials 0.000 abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 abstract description 5
- 229920001155 polypropylene Polymers 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 229920000642 polymer Polymers 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 32
- 239000007789 gas Substances 0.000 description 27
- 238000003786 synthesis reaction Methods 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000011085 pressure filtration Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- 230000037048 polymerization activity Effects 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 9
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 9
- 239000012530 fluid Substances 0.000 description 9
- 238000007172 homogeneous catalysis Methods 0.000 description 9
- 210000003097 mucus Anatomy 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 150000002234 fulvenes Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 4
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- WTPWAEBALYUUPC-UHFFFAOYSA-N 2,7-ditert-butyl-9h-fluorene;lithium Chemical compound [Li].CC(C)(C)C1=CC=C2C3=CC=C(C(C)(C)C)C=C3CC2=C1 WTPWAEBALYUUPC-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- OYDGRFZMWQLWGV-UHFFFAOYSA-N 1-(2-cyclopenta-1,3-dien-1-ylethyl)cyclopenta-1,3-diene Chemical compound C=1C=CCC=1CCC1=CC=CC1 OYDGRFZMWQLWGV-UHFFFAOYSA-N 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- SDPURBHAHVFTGX-UHFFFAOYSA-N 2,7-dichloro-9h-fluorene Chemical compound ClC1=CC=C2C3=CC=C(Cl)C=C3CC2=C1 SDPURBHAHVFTGX-UHFFFAOYSA-N 0.000 description 1
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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 invention relates to a bridged dinuclear metallocene compound, a preparation method thereof and application of the compound in propylene syndiotactic polymerization.
Background
Since Fina corporation tried to produce sPP in liquid phase loop reactors in 1993, Basell, Huntsman, Dow, ExxonMobil corporation and foreign companies such as Mitsui east pressure corporation and British chemical corporation in Japan have been working on the development of sPP. At present, Fina company, Basell, ExxonMobil and Japan gloss petrochemical company realize the industrial production of sPP.
The mononuclear metallocene catalyst becomes the focus of research of scientists in various countries, and the mononuclear catalyst which is protected by patent almost covers all aspects of the research field, so that great original innovation is difficult to achieve. The use of a certain bridging group to connect bridged mononuclear metallocene compounds to obtain a double bridged metallocene is a new research field.
Alt, Helmut G (Helmut G. Alt, Rainer Ernst. Dinuclear and pyrocatene compounds as dual-site catalysts for the polymerization of ethylene [ J ]. Journal of Molecular Catalysis A: Chemical 195.(2003).11-27) A bridged dinuclear catalyst was synthesized, the structure of which is shown below:
the catalyst is used for propylene polymerization, and the activity (93000kg mol)-1h-1atm-1) To the corresponding mononuclear metallocene catalyst Me2Si(2-Me-I-Ind)(2-Me-4-Ph-I-Ind)ZrCl2(LZrCl2＝446000kg mol-1h-1atm-1) Low, but the molecular weight of the polypropylene produced is increased, the atactic degree is also increased (6.1 wt% versas)<0.2wt％for LZrCl2)。
Then, Alt (Deppner, M.Alkylidenferbr ükte, symmetrische, zweikernige Metallocenkomplexe als Katalysaltoren fur die dipyrromerisation [ J ]. Journal of organic chemistry.2005,690(12):2861-2871.) also made a corresponding study, synthesized carbon bridged asymmetric dinuclear metallocene catalysts of different lengths, and had the following structure:
in the above catalyst, when the carbon bridge length is less than 5 carbon atoms, the molecular weight distribution of the resulting polymer is broad (MWD > 10). In propylene polymerization, the isotactic degree of the obtained polypropylene is found to be 9-11%.
A series of benzene-bridged binuclear zirconocenes were synthesized by Stephan Jungling (J.S., R.M. Hullhaupt and H.P.O.Co. organic efficiencies in binuclear zirconocenes: the present synthesis and use as a catalyst in pro-pen poly-ionization [ J ]. Journal of organic chemistry, 1993,460(2):191-195.) and have the following structure:
the catalyst has lower catalytic activity for propylene polymerization (2.6X 10)5gPP/mol Zr h, 3X 10 for the mononuclear catalytic system5gPP/mol Zr h), molecular weight reduction (GPC: mn 2200g/mol, and a mononuclear catalytic system Mn 3400 g/mol). Furthermore, in contrast to the mononuclear catalytic system, the molecular weight decreases with increasing AI/Zr ratio.
A binuclear Catalyst has been synthesized by Sierra (Cano Sierra, J.Format of Dinuclear Titanium and Zirconium compounds by Olefin synthesis of Organometallic Catalyst Systems [ J ]. Chemistry-A European journal.2003,9(15): 3618. 3622.), etc., and has the following structure:
the catalyst is used for catalyzing ethylene polymerization, has quite low activity at room temperature (25 ℃), has very high activity at 60 ℃, catalyzes propylene polymerization, has common activity at room temperature (25 ℃) and 60 ℃, has quite low molecular weight, can obtain 36% isotactic polypropylene at room temperature, and can obtain 12% atactic polypropylene at 60 ℃.
Disclosure of Invention
It is an object of the present invention to provide a novel bridged dinuclear metallocene compound.
Another object of the present invention is to provide a method for preparing the bridged dinuclear metallocene compound.
Another object of the present invention is to provide the use of the bridged dinuclear metallocene compound in the syndiotactic polymerization of propylene.
In one aspect, the present invention provides a bridged dinuclear metallocene compound having a structure represented by the following general formula I:
wherein: n is 2, 3 or 4;
R1hydrogen, methyl, ethyl, phenyl;
R2hydrogen, methyl, ethyl, phenyl;
R3hydrogen, tert-butyl, bromine or chlorine.
According to a particular embodiment of the invention, the compounds of formula I according to the invention are selected from the following compounds:
[(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。
in another aspect, the present invention also provides a ligand compound having a structure represented by the following general formula II:
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.
According to a particular embodiment of the invention, the compounds of formula II of the invention are those wherein: n is 2, 3 or 4; r1Is methyl, ethyl or phenyl; r2Is hydrogen, methyl, ethyl or phenyl; r3Is hydrogen.
According to a particular embodiment of the invention, the compounds of formula II of the invention are those wherein: n is 3; r1Is hydrogen, or phenyl; r2Is hydrogen, methyl or phenyl; r3Is a tert-butyl group.
According to a particular embodiment of the invention, the compounds of formula II of the invention are those wherein: n is 4; r1Is methyl or ethyl; r2Is methyl or ethyl; r3Is bromine or chlorine.
In another aspect, the present invention provides a method for preparing a bridged dinuclear metallocene compound represented by the general formula I, comprising:
reacting the ligand compound with butyl lithium to prepare a tetra lithium salt;
tetralithium salt and ZrCl4Reacting to obtain the bridged dinuclear metallocene compound.
According to a specific embodiment of the present invention, the method of preparing the bridged dinuclear metallocene compound of the present invention comprises: taking tetrahydrofuran solution containing ligand compound shown in general formula II, adding n-hexane solution containing n-butyllithium at-40-0 ℃, heating to 20-30 ℃, reacting for 10-20 hours, removing solvent to obtain solid, dissolving the solid with tetrahydrofuran at-70-80 ℃, adding ZrCl4And (3) naturally heating the THF to room temperature, reacting for 24-72 hours, draining, extracting dichloromethane for 2-3 times, concentrating, adding n-hexane for polarity adjustment, and crystallizing at-30-10 ℃ to obtain a solid, namely the dinuclear metallocene compound.
According to a specific embodiment of the present invention, the method for preparing the bridged dinuclear metallocene compound of the present invention further comprises a process for preparing a ligand compound of the general formula II.
According to a preferred embodiment of the present invention, the process for preparing the ligand compound of formula II comprises:
reacting the bridged dihalogenated hydrocarbon with sodium cyclopentadiene to prepare bridged cyclopentadiene;
reacting the bridged metallocene with sodium metal to obtain bridged metallocene sodium;
performing column chromatography separation on bridged sodium cyclopentadienyl and ketone to obtain bridged fulvene;
and reacting the bridged fulvene with fluorene lithium to obtain the ligand compound shown in the general formula II.
According to a more preferred embodiment of the present invention, the process for preparing the ligand compound of formula II comprises:
dropwise adding a THF solution of the dihalogenated alkane into a THF solution of CpNa in an ice-water bath, gradually generating a white precipitate, finishing adding after 10-40 minutes, naturally heating to room temperature, and reacting overnight; adding saturated NaCl for hydrolysis, precipitating white, taking the upper layer yellow clear liquid, adjusting the pH value with acetic acid to be neutral, separating liquid, taking the organic phase, washing the water phase with anhydrous ether for 2-3 times, combining the organic phases, washing with saturated salt water, and anhydrous MgSO4Drying and distilling under reduced pressure to obtain bridged dicyclopentadiene;
taking sodium particles, adding THF, dripping a THF solution of bridged dicyclopentadiene in an ice-water bath, naturally raising the color to room temperature after dripping, gradually deepening the yellow color, and reacting overnight; pressing the supernatant into a container, slowly dripping THF solution of carbonyl compound in ice water bath, naturally heating to room temperature after dripping, and reacting for 24-36 hours at 20-40 ℃; adding ice water for hydrolysis to turn red, adjusting the pH value to be neutral by glacial acetic acid, separating liquid, taking an organic phase, extracting the aqueous phase by using diethyl ether for 2-3 times, washing the organic phase by using saturated saline solution, and carrying out anhydrous MgSO4Drying; performing column chromatography separation to obtain the substituted bridged dicyclopentadiene;
and (2) dropwise adding the substituted bridged dicyclopentadiene into an ether solution of a fluorene compound under an ice bath, generating a precipitate, reacting for 24-36 hours, hydrolyzing, adjusting the pH value of acetic acid to be neutral, separating, taking an organic phase, extracting with water-phase ether for 2-3 times, combining the organic phases, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, removing the solvent in a vacuum rotary manner, taking petroleum ether as a mobile phase, performing column chromatography separation, and concentrating to obtain the ligand compound.
On the other hand, the invention also provides the application of the bridged binuclear metallocene compound as a catalyst for syndiotactic polymerization of propylene.
In another aspect, the present invention also provides a catalyst for syndiotactic polymerization of propylene, comprising at least one bridged dinuclear metallocene compound selected from the bridged dinuclear metallocene compounds of the present invention.
According to the invention, methyl, methylene, ethyl and phenyl are introduced on a carbon bridge group connecting a cyclopentadienyl ring and a fluorene ring, hydrogen, tert-butyl, bromine and chlorine are introduced on a fluorenyl group, and different bridge-linking lengths exist, so that a series of bridged dinuclear metallocene compounds are obtained, the yield of a complex is improved, and the activity and the syndiotacticity are higher when propylene polymerization is catalyzed.
For example, propylene was polymerized by adding a toluene solution containing 2. mu. mol of complex 1 in toluene and MAO (1.60M,2.5mL) at a reaction temperature of 0 ℃ for 0.5 hour under a propylene pressure of 0.1MPa and a polymerization activity of 1.8X 10 at an aluminum/zirconium ratio of 10006g polymer/mol M.h, sPP isotacticity [ rrrr]＝86％。
The invention adopts a bridged dinuclear metallocene catalyst/MAO system, and obtains higher activity for propylene polymerization under the action of a cocatalyst with lower proportion.
From the practical application of the technical scheme disclosed above, the bridged binuclear metallocene catalyst for olefin polymerization has obvious advantages: high product yield, easy separation and purification, less cocatalyst needed when used for catalyzing propylene polymerization, high catalytic activity and high syndiotactic degree.
Detailed Description
The following examples are intended to illustrate the practice and advantageous effects of the present invention, but are not to be construed as limiting the scope of the present invention. The methods and operating conditions not specified in the examples were carried out according to the conventional techniques in the field or according to the operations recommended by the manufacturer of the apparatus. The ligand compounds and complexes obtained in the respective examples have been structurally confirmed according to a method known in the art.
Example 1
Ligand L1[ (CH)3)2C(C5H4)(C13H9)]2(CH2)2Synthesis of (2)
Ligand L1[ (CH)3)2C(C5H4)(C13H9)]2(CH2)2The synthetic route of (2) is as follows:
adding a THF (40mL) solution of 1, 2-dichloroethane (24mL, 303.6mmol) into a THF solution of CpNa (4.048mol/L) dropwise in an ice-water bath, gradually generating white precipitates, completely adding the white precipitates for half an hour, naturally raising the temperature to room temperature, and reacting overnight; adding saturated NaCl for hydrolysis, precipitating white precipitate at the bottom of the bottle, collecting the upper yellow clear solution, adjusting pH with acetic acid to neutral, separating, collecting the organic phase, washing the water phase with anhydrous diethyl ether for three times (20mL × 3), combining the organic phases, washing with saturated saline water, and anhydrous MgSO4The reaction mixture was dried and distilled under reduced pressure to obtain ethylene bisdicyclopentadiene in a yield of about 60% in the form of a colorless transparent liquid (18 g).
Adding sodium granules (20.1g, 873.9mmol) into a 500mL three-mouth bottle, adding THF200mL, dropwise adding a THF solution of ethylene-bis-cyclopentadiene (15g, 94.95mmol) in an ice water bath, wherein the color turns light yellow when dropwise adding is completed, naturally rising to room temperature after dropwise adding is completed, the yellow gradually deepens, and reacting overnight; pressing the supernatant into a 500mL three-necked bottle, slowly dropwise adding a THF (60mL) solution of acetone (11.01g, 189.96mmol) in an ice water bath, naturally heating to room temperature after dropwise adding, and reacting at 25 ℃ for one day; adding ice water for hydrolysis to obtain red color, adjusting pH to neutral with glacial acetic acid, separating, collecting organic phase, extracting water phase with diethyl ether for three times, washing organic phase with saturated saline water, and anhydrous MgSO4Drying; performing column chromatography separation, using petroleum ether as a developing agent, and collecting the first fraction to obtain ethylene-bis (6, 6-dimethyl-fulvene) and 10.92g of yellow reddish oily matter with the yield of 42%;
under ice bath, dropwise adding ethylene-bis (6, 6-dimethyl-fulvene) (7g, 29.4mmol) into a solution of FluLi (10.17g, 58.8mmol) in diethyl ether (250mL), generating a little precipitate, reacting for one day, hydrolyzing, adjusting the pH value to be neutral with acetic acid, separating liquid, taking an organic phase, extracting an aqueous phase with diethyl ether twice, combining the organic phase, washing with saturated saline, drying with anhydrous magnesium sulfate for 6h, filtering, removing the solvent in vacuum, taking petroleum ether as a mobile phase, separating by column chromatography, and concentrating to obtain 10.1g mucus, namely the ligand L1.
Complex 1[ (CH)3)2C(C5H3)(C13H8)ZrCl2]2(CH2)2Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.14g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.01g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.28g, 3.4mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 406mg of yellow powder with a yield of 30%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and a gas-guide tube was replaced with ethylene gas 3 times, and 50mL of toluene and 1.60 mL of a cocatalyst MAO2.5mL (1.60M) [ Al/M ═ 1000 ] were sequentially added under the protection of nitrogen gas]2.0. mu. mol of complex 1, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymer with the mass of 3.6g and the polymerization activity of 1.8 × 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization revealed that the rrrr syndiotacticity of the resulting polymer was calculated to be 86%.
Example 2
Ligand L2[ (CH)3)2C(C5H4)(C13H9)]2(CH2)4Synthesis of (2)
Preparation of bridged fulvenes with 1, 1, 4-dichlorobutane instead of 1, 2-dichloroethane in the same example
And (2) dropwise adding bridged fulvene (10.172g, 29.4mmol) into a solution of FluLi (10.17g, 58.8mmol) in diethyl ether (250mL) under ice bath, generating a little precipitate, reacting for one day, still obtaining a little precipitate, hydrolyzing, adjusting the pH value to be neutral by acetic acid, separating liquid, taking an organic phase, extracting the organic phase with diethyl ether twice, combining the organic phase, washing with saturated saline solution, drying with anhydrous magnesium sulfate for 6h, filtering, removing the solvent by vacuum rotation, taking petroleum ether as a mobile phase, separating by column chromatography, concentrating to obtain 6.97g of mucus, wherein the yield is 35%, and the ligand L is obtained.
Complex 2[ (CH)3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.356g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.21g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.3g, 3.447mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a freezer at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 1239mg as a yellow powder with a yield of 72%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of MAO as a cocatalyst were added in this order (Al/M1000)]2.0. mu. mol of complex 2, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymer with the mass of 3.8g and the polymerization activity of 1.9 × 106g polymer/mol Mh, removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 92%.
Example 3
Ligand L3[ (CH)3)(CH2CH3)C(C5H4)(C13H9)]2(CH2)2Synthesis of (2)
In ice bath, dropwise adding ethylene endofulvene (7.82g, 29.4mmol) into a solution of FluLi (10.17g, 58.8mmol) in diethyl ether (250mL), generating a little precipitate, reacting for one day, still obtaining a little precipitate, hydrolyzing, adjusting the pH value of acetic acid to be neutral, separating liquid, taking an organic phase, extracting the organic phase with diethyl ether twice, combining the organic phase, washing with saturated saline solution, drying with anhydrous magnesium sulfate for 6h, filtering, removing the solvent by vacuum rotation, taking petroleum ether as a mobile phase, separating by column chromatography, concentrating to obtain 6.51g of mucus, wherein the yield is 37%, and the ligand L is obtained.
Complex 3[ (CH)3)(CH2CH3)C(C5H3)(C13H8)ZrCl2]2(CH2)2Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.2g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.13g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.37g, 3.63mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 481mg of yellow powder, with a yield of 29%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of MAO as a cocatalyst were added in this order (Al/M1000)]2.0 mu mol of complex 3, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas bottle, stopping the reaction by using 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer by using ethanol, drying the polymer in vacuum at 80 ℃ to constant weight, weighing the polymer with the mass of 3.64g,polymerization Activity 1.82X 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 90%.
Example 4
Ligand L4[ C6H5C(C5H4)((tBu)2C13H7)]2(CH2)3Synthesis of (2)
Preparation of bridged fulvenes in the same example 1, 1, 3-dichloropropane instead of 1, 2-dichloroethane
Under ice bath, bridging fulvene (11.05g, 29.4mmol) is dripped into an ether (250mL) solution of 2, 7-di-tert-butylfluorene lithium (16.34g,58.8mmol), a little precipitate is generated, reaction is carried out for one day, a small amount of precipitate is still generated, hydrolysis is carried out, the pH value is adjusted to be neutral by acetic acid, liquid separation is carried out, an organic phase is taken, an aqueous phase is extracted twice by ether, the organic phase is combined, washing is carried out by saturated saline solution, anhydrous magnesium sulfate is dried for 6h, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, 9.32g of mucus is obtained after concentration, the yield.
Complex 4[ C ]6H5C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.86g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.75g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.38g, 3.66mmol), warmed up to room temperature naturally, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to yield 1478mg of yellow powder in 65% yield.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A 100mL three-port with a magnetic stirrer and an air ductThe bottle was replaced with ethylene gas 3 times, and 50mL of toluene and 2.5mL (1.60M) of co-catalyst MAO [ Al/M1000 ] were added in this order under nitrogen protection]2.0. mu. mol of complex 4, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymer with the mass of 3.7g and the polymerization activity of 1.85X 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 91%.
Example 5
Ligand L5[ (C)6H5)2C(C5H4)((tBu)2C13H7)]2(CH2)3Synthesis of (2)
Preparation of bridged fulvenes in the same example 1, 1, 3-dichloropropane instead of 1, 2-dichloroethane
Under ice bath, bridging fulvene (14.7g, 29.4mmol) is dripped into an ether (250mL) solution of 2, 7-di-tert-butylfluorene lithium (16.34g,58.8mmol), a little precipitate is generated, reaction is carried out for one day, a small amount of precipitate is still generated, hydrolysis is carried out, the pH value is adjusted to be neutral by acetic acid, liquid separation is carried out, an organic phase is taken, an aqueous phase is extracted twice by ether, the organic phase is combined, washing is carried out by saturated saline solution, anhydrous magnesium sulfate is dried for 6h, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, 10.24g of mucus is obtained after concentration, the yield.
Complex 5[ (C)6H5)2C(C5H3)((tBu)2C13H6)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (2.11g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.89g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.32g, 3.5mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, dichloromethane was extracted twice (30 mL. times.2), concentrated to 20mL, polarity was adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 1795mg of yellow powder in a yield of 75%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of MAO as a cocatalyst were added in this order (Al/M1000)]2.0. mu. mol of complex 5, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymer with the mass of 3.46g and the polymerization activity of 1.73X 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 90%.
Example 6
Ligand L6[ (CH)3)2C(C5H4)(Cl2C13H7)]2(CH2)4Synthesis of (2)
Preparation of bridged fulvenes with 1, 1, 4-dichlorobutane instead of 1, 2-dichloroethane in the same example
In ice bath, bridging fulvene (10.17g, 29.4mmol) is dripped into an ether (250mL) solution of 2, 7-dichlorofluorene (13.64g,58.8mmol), a little precipitate is generated, reaction is carried out for one day, a little precipitate is still generated, hydrolysis is carried out, the pH value is adjusted to be neutral by acetic acid, liquid separation is carried out, an organic phase is taken, an aqueous phase is extracted by ether twice, the organic phase is combined, the saturated saline solution is washed, anhydrous magnesium sulfate is dried for 6 hours, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, 12.36g of mucus is obtained after concentration, the yield is 32%, and the ligand L.
Complex 6[ (CH)3)2C(C5H3)(Cl2C13H6)ZrCl2]2(CH2)4Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (2.63g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 2.53g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.42g, 3.78mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 1013mg of yellow powder, yield 76%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of MAO as a cocatalyst were added in this order (Al/M1000)]2.0. mu. mol of complex 6, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing 2.1g of polymer mass and 1.05X 10 of polymerization activity6From the polymer/molM.h, after removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 93%.
Example 7
Ligand L7[ CH3(CH2CH3)C(C5H4)(Br2C13H7)]2(CH2)4Synthesis of (2)
Preparation of bridged fulvenes with 1, 1, 4-dichlorobutane instead of 1, 2-dichloroethane in the same example
In ice bath, bridging fulvene (8.64g, 29.4mmol) is dripped into an ether (250mL) solution of 2, 7-dibromofluorene (9.7g,58.8mmol), a little precipitate is generated, reaction is carried out for one day, a small amount of precipitate is still generated, hydrolysis is carried out, the pH value is adjusted to be neutral by acetic acid, liquid separation is carried out, an organic phase is taken, an aqueous phase is extracted by ether twice, the organic phase is combined, the saturated saline solution is washed, anhydrous magnesium sulfate is dried for 6 hours, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, 10.2g of mucus is obtained after concentration, the yield is 37%, and the ligand.
Complex 7[ CH ]3(CH2CH3)C(C5H3)(Br2C13H6)ZrCl2]2(CH2)4Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.88g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.65g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.29g, 3.42mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, dichloromethane was extracted twice (30 mL. times.2), concentrated to 20mL, polarity was adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to obtain 1669mg of yellow powder with a yield of 78%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of MAO as a cocatalyst were added in this order (Al/M1000)]2.0. mu. mol of complex 7, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymer with the mass of 2.06g and the polymerization activity of 1.03 × 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization revealed that the rrrr syndiotacticity of the resulting polymer was calculated to be 92%.
Example 8
Ligand L8[ (CH)3)2C(C5H4)(C13H9)]2(CH2)3Synthesis of (2)
Preparation of bridged fulvenes in the same example 1, 1, 3-dichloropropane instead of 1, 2-dichloroethane
In ice bath, dropwise adding ethylene endofulvene (7.41g, 29.4mmol) into a solution of FluLi (10.17g, 58.8mmol) in diethyl ether (250mL), generating a little precipitate, reacting for one day, still obtaining a little precipitate, hydrolyzing, adjusting the pH value of acetic acid to be neutral, separating liquid, taking an organic phase, extracting the organic phase with diethyl ether twice, combining the organic phase, washing with saturated saline solution, drying with anhydrous magnesium sulfate for 6h, filtering, removing the solvent by vacuum rotation, taking petroleum ether as a mobile phase, separating by column chromatography, and concentrating to obtain 10.4g of mucus, namely the ligand L8.
Complex 8[ (CH)3)2C(C5H3)(C13H8)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.17g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.03g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.28g, 3.4mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to give 1062mg of yellow powder with a yield of 70%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
A100 mL three-necked flask with a magnetic stirrer and an air duct was replaced with ethylene gas 3 times, and under nitrogen protection, 50mL of toluene and 2.5mL (1.60M) of a cocatalyst MAO (Al/M1000) were added in this order]2.0. mu. mol of complex 8, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing the polymeric substanceAmount 2.2g, polymerization Activity 1.1X 106From the polymer/molM.h, after removal of the random with xylene13C NMR characterization calculated to find the [ rrrr ] of the resulting polymer]The degree of syndiotacticity was 90%.
Example 9
Ligand L9[ (CH)3)2C(C5H4)(C13H9)]2(CH2)4Synthesis of (2)
Preparation of bridged fulvenes with 1, 1, 4-dichlorobutane instead of 1, 2-dichloroethane in the same example
In ice bath, dropwise adding ethylene endofulvene (7.82g, 29.4mmol) into a solution of FluLi (10.17g, 58.8mmol) in diethyl ether (250mL), generating a little precipitate, reacting for one day, still obtaining a little precipitate, hydrolyzing, adjusting the pH value of acetic acid to be neutral, separating liquid, taking an organic phase, extracting the organic phase with diethyl ether twice, combining the organic phase, washing with saturated saline solution, drying with anhydrous magnesium sulfate for 6h, filtering, removing the solvent by vacuum rotation, taking petroleum ether as a mobile phase, separating by column chromatography, and concentrating to obtain 10.5g of mucus, namely the ligand L9.
Complex 9[ (CH)3)2C(C5H3)(C13H8)ZrCl2]2(CH2)4Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.20g, 2mmol) to generate solid, the reflux reaction is carried out for two days, the supernatant fluid is removed by pressure filtration, washed once by ether and dried to obtain 1.06g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.28g, 3.4mmol) was allowed to spontaneously warm to room temperature, reacted for 2 days, the reaction solution was yellow, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, polarity-adjusted with some n-hexane, placed in a refrigerator at-20 ℃ to precipitate a yellow substance, the supernatant was removed by pressure filtration, and the precipitate was drained to obtain 1162mg of yellow powder in a yield of 75%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
Replacing a 100mL three-necked flask with magnetic stirrer and gas-guide tube with ethylene gas for 3 times, and sequentially adding toluene under the protection of nitrogen50mL, cocatalyst MAO2.5mL (1.60M) [ Al/M1000]2.0. mu. mol of complex 9, introducing propylene gas at normal pressure, starting polymerization reaction at 0 ℃, stirring for 30min, closing a propylene gas cylinder, stopping the reaction with 10% ethanol hydrochloride, transferring the polymer into a beaker, standing overnight, filtering, fully washing the polymer with ethanol, vacuum-drying at 80 ℃ to constant weight, weighing 2.4g of polymer mass and 1.2 × 10 of polymerization activity6From the polymer/molM.h, after removal of the random with xylene13C NMR characterization revealed that the rrrr syndiotacticity of the resulting polymer was calculated to be 92%.
Claims (9)
1. A bridged dinuclear metallocene compound selected from the following compounds:
[(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。
2. a ligand compound selected from the group consisting of:
[(CH3)2C(C5H4)(C13H9)]2(CH2)2
[(CH3)2C(C5H4)(C13H9)]2(CH2)4
[(CH3)(CH2CH3)C(C5H4)(C13H9)]2(CH2)2
[C6H5C(C5H4)((tBu)2C13H7)]2(CH2)3
[(C6H5)2C(C5H4)((tBu)2C13H7)]2(CH2)3
[(CH3)2C(C5H4)(Cl2C13H7)]2(CH2)4
[CH3(CH2CH3)C(C5H4)(Br2C13H7)]2(CH2)4
[(CH3)2C(C5H4)(C13H9)]2(CH2)3
[(CH3)2C(C5H4)(C13H9)]2(CH2)4。
3. a method for preparing the bridged dinuclear metallocene compound of claim 1, which comprises:
reacting the ligand compound according to claim 2 with butyllithium to produce a tetralithium salt;
tetralithium salt and ZrCl4Reacting to obtain the bridged dinuclear metallocene compound.
4. The method of claim 3, wherein the method of preparing the bridged dinuclear metallocene compound of claim 1 comprises:
taking tetrahydrofuran solution containing the ligand compound according to claim 2, adding n-hexane solution containing n-butyllithium at-40-0 ℃, heating to 20-30 ℃, reacting for 10-20 hours, removing the solvent to obtain solid, dissolving the solid with tetrahydrofuran, adding ZrCl at-70-80 ℃, and adding ZrCl4And (3) naturally heating the THF to room temperature, reacting for 24-72 hours, draining, extracting dichloromethane for 2-3 times, concentrating, adding n-hexane for polarity adjustment, and crystallizing at-30 to-10 ℃ to obtain a solid, namely the dinuclear metallocene compound.
5. The method according to claim 3 or 4, further comprising a process for preparing the ligand compound according to claim 2.
6. The method of claim 5, wherein the process for preparing the ligand compound of claim 2 comprises:
reacting the bridged dihalogenated hydrocarbon with sodium cyclopentadiene to prepare bridged cyclopentadiene; reacting the bridged metallocene with sodium metal to obtain bridged metallocene sodium; performing column chromatography separation on bridged sodium cyclopentadienyl and ketone to obtain bridged fulvene; and reacting the bridged fulvene with fluorene lithium to obtain the ligand.
7. The method of claim 6, wherein the process for preparing the ligand compound of claim 2 comprises:
dropwise adding a THF solution of the dihalogenated alkane into a THF solution of CpNa in an ice-water bath, gradually generating a white precipitate, finishing adding after 10-40 minutes, naturally heating to room temperature, and reacting overnight; adding saturated NaCl for hydrolysis, precipitating white, taking the upper layer yellow clear liquid, adjusting the pH value with acetic acid to be neutral, separating liquid, taking the organic phase, washing the water phase with anhydrous ether for 2-3 times, combining the organic phases, washing with saturated salt water, and anhydrous MgSO4Drying and distilling under reduced pressure to obtain bridged dicyclopentadiene;
taking sodium particles, adding THF, dripping a THF solution of bridged dicyclopentadiene in an ice-water bath, naturally raising the color to room temperature after dripping, gradually deepening the yellow color, and reacting overnight; pressing the supernatant into a container, slowly dripping THF solution of carbonyl compound in ice water bath, naturally heating to room temperature after dripping, and reacting for 24-36 hours at 20-40 ℃; adding ice water for hydrolysis to turn red, adjusting the pH value to be neutral by glacial acetic acid, separating liquid, taking an organic phase, extracting the aqueous phase by using diethyl ether for 2-3 times, washing the organic phase by using saturated saline solution, and carrying out anhydrous MgSO4Drying; performing column chromatography separation to obtain the substituted bridged dicyclopentadiene;
in ice bath, dropwise adding substituted bridged dicyclopentadiene into an ether solution of a fluorene compound, generating a precipitate, reacting for 24-36 hours, hydrolyzing, adjusting the pH value of acetic acid to be neutral, separating, taking an organic phase, extracting an aqueous phase with ether for 2-3 times, combining the organic phases, washing with saturated saline solution, drying with anhydrous magnesium sulfate, filtering, removing a solvent in a vacuum rotary manner, taking petroleum ether as a mobile phase, separating by column chromatography, and concentrating to obtain the ligand compound according to claim 2.
8. Use of the bridged dinuclear metallocene compound according to claim 1 as a catalyst for the syndiotactic polymerization of propylene.
9. A catalyst for syndiotactic polymerization of propylene, comprising at least one bridged dinuclear metallocene compound selected from the group consisting of the bridged dinuclear metallocene compounds according to claim 1.
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