CN108840887B - Bridged dinuclear metallocene compound for sPP (sPP), and preparation method and application thereof - Google Patents
Bridged dinuclear metallocene compound for sPP (sPP), and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000460 chlorine Chemical group 0.000 claims abstract description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Chemical group 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 94
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- 239000003446 ligand Substances 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- 239000012074 organic phase Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 238000004440 column chromatography Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 230000007935 neutral effect Effects 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000005457 ice water Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 3
- 239000007864 aqueous solution Substances 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 31
- -1 polypropylene Polymers 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 37
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000007789 gas Substances 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000011085 pressure filtration Methods 0.000 description 14
- 239000006228 supernatant Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 229910007926 ZrCl Inorganic materials 0.000 description 7
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 7
- 238000007172 homogeneous catalysis Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 5
- XTCAGVVVEIJFON-UHFFFAOYSA-N 9h-fluorene;lithium Chemical compound [Li].C1=CC=C2CC3=CC=CC=C3C2=C1 XTCAGVVVEIJFON-UHFFFAOYSA-N 0.000 description 4
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 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
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000002234 fulvenes Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- 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
- 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
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
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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 for sPP (sPP), and a preparation method and application thereof. The bridged dinuclear metallocene compound has a structure shown in the following general formula I:
Description
Technical Field
The invention relates to a bridged dinuclear metallocene compound for sPP (sPP), a preparation method thereof and application of the compound in the syndiotactic polymerization of propylene.
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%.
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].
A series of benzene-bridged binuclear zirconocenes are synthesized in Journal of organometallic chemistry, 1993,460(2): 191-195), and have the following structures:
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
An object of the present invention is to provide a novel bridged dinuclear metallocene compound for sPP.
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;
r is hydrogen, tertiary 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:
[(C5H4)CH((tBu)2C13H6)ZrCl2]2(CH2)4；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)2；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)3；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)4；
[(C5H4)CH((tBu)2C13H6)ZrCl2]2(CH2)3；
[(C5H4)CH(Cl2C13H6)ZrCl2]2(CH2)3；
[(C5H4)CH(Br2C13H6)ZrCl2]2(CH2)3。
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;
r is hydrogen, tertiary 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; r is hydrogen.
According to a particular embodiment of the invention, the compounds of formula II of the invention are those wherein: n is 3 or 4; r is tertiary butyl.
According to a particular embodiment of the invention, the compounds of formula II of the invention are those wherein: n is 3; r is 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 according to any one of claims 3 to 6 with butyllithium to prepare a tetralithium 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 12-72 hours, usually for 24-36 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.
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.
Preferably, the process for preparing the ligand compound of formula II comprises:
reacting the dicarbonyl compound with cyclopentadiene, and separating by column chromatography to obtain the difructene;
and (3) reacting the bis-fulvene with fluorene lithium, and performing column chromatography separation to obtain the ligand compound shown in the general formula II.
More preferably, the process for preparing the ligand compound of formula II comprises:
under ice bath, adding cyclopentadiene dropwise into dialdehyde water solution, adding methanol, adding pyrrolidine dropwise in ice water bath to gradually turn yellow and slowly deepen yellow, reacting for 2-5h, adding water and acetic acid to adjust pH to neutral, separating, collecting organic phase, and collecting water phaseExtracting with water and diethyl ether, mixing organic phases, washing with saturated NaCl, anhydrous MgSO4Drying; filtering, removing solvent under reduced pressure, separating by column chromatography with petroleum ether as mobile phase, and concentrating to obtain bridged difenofulvene; and (2) dropwise adding the bridged bis-fulvene into an ether solution of the fluorene compound in an ice bath, generating a precipitate, refluxing for 24-72 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 under reduced pressure, 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, hydrogen, tert-butyl, bromine and chlorine are introduced into fluorenyl, and different carbon bridge lengths are provided, so that a series of bridged dinuclear metallocene compounds are obtained, the complex yield is improved, and the activity and the syndiotacticity are higher when the catalyst is used for catalyzing propylene polymerization.
For example, propylene was polymerized by adding a toluene solution containing 2. mu. mol of complex 3 in toluene (MAO (1.60M,2.5mL) at a reaction temperature of 0 ℃ for 0.5 hour under a propylene pressure of 0.1MPa and a toluene solvent, and the polymerization activity was 2.4X 10 at an aluminum/zirconium ratio of 10006gPolymer/molM.h, sPP isotacticity [ rrrr]＝95％。
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: the method has the advantages of simple steps, easy separation and purification, less cocatalyst requirement when the catalyst is 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[ (C)5H4)CH((tBu)2C13H9)]2(CH2)4Synthesis of (2)
Ligand L1[ (C)5H4)CH((tBu)2C13H9)]2(CH2)4The synthetic route of (2) is as follows:
under ice bath, adding cyclopentadiene (75mL, 911.5mmol) dropwise into a methanol solution of hexanedial (51.95g, 455.7mmol), slowly adding pyrrolidine 45mL dropwise under ice water bath, gradually turning yellow and slowly deepening yellow, reacting for 5h, adding water, adjusting pH to neutral with acetic acid, separating, collecting organic phase, extracting aqueous phase with anhydrous ether for 3 times, combining organic phases, washing with saturated NaCl, and anhydrous MgSO4Drying; filtering, removing solvent, separating by column chromatography with petroleum ether as mobile phase, collecting the second fraction, and concentrating to obtain 33.49g of diffulvene with yield of 35%.
Under ice bath, bridging diffulvene (6.3g, 30mmol) is dripped into an ether (150mL) solution of 2, 7-di-tert-butylfluorene lithium (16.67g,60mmol), precipitation is generated, the solution is refluxed for two days, hydrolyzed, acetic acid is used for adjusting pH to be neutral, liquid is separated, an organic phase is taken, an aqueous phase is extracted twice by ether, the organic phase is combined, washed by saturated saline solution, dried for 6 hours by anhydrous magnesium sulfate, filtered, decompressed to remove a solvent, and column chromatography separation is carried out by taking petroleum ether as a mobile phase, so that 6.8g of L1 is obtained after concentration, and the yield is 30%.
Complex 1[ (C)5H4)CH(C13H8)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.52g, 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 1.41g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.36g, 3.6mmol) 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 928mg of yellow powder in 48% yield.
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 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 5.2g of polymer mass and 2.6X 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 92%.
Example 2
Ligand L2[ (C)5H4)CH(C13H9)]2(CH2)2Synthesis of (2)
In the same way as in example 1, succinaldehyde was used instead of adipic dialdehyde to prepare bridged fulvene;
under ice bath, bridging diffulvene (6.3g, 30mmol) is dripped into an ether (150mL) solution of lithium fluorene (9.96g,60mmol), precipitation is generated, the solution is refluxed for two days, 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, the solution is washed by saturated saline solution, anhydrous magnesium sulfate is dried for 6 hours, filtration is carried out, the solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, and 4.59g L2 is obtained after concentration, and the yield is 30.
Complex 2[ (C)5H4)CH(C13H8)ZrCl2]2(CH2)2Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.02g, 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 0.98g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.36g, 3.67mmol) 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 679mg of yellow powder in a yield of 45%.
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 4.4g of polymer mass and 2.2 × 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 92%.
Example 3
Ligand L3[ (C)5H4)CH(C13H9)]2(CH2)3Synthesis of
In the same way as in example 1, glutaraldehyde was used instead of adipic dialdehyde to prepare bridged fulvene;
in ice bath, bridging diffulvene (5.88g, 30mmol) is dripped into an ether (250mL) solution of lithium fluorene (9.96g,60mmol), a little precipitate is generated, reaction is carried out for one day, a little precipitate is still generated, hydrolysis is carried out, acetic acid is used for adjusting pH to be neutral, 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, drying is carried out for 6h by anhydrous magnesium sulfate, filtration is carried out, a solvent is removed by vacuum rotation, column chromatography separation is carried out by taking petroleum ether as a mobile phase, and the yield is 37%, wherein 5.82 35.
Complex 3[ (C)5H4)CH(C13H8)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.05g, 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 0.95g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.29g, 3.47mmol) 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 725mg of yellow powder with a yield of 50%.
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 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 4.8g of polymer mass and 2.4 × 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 syndiotactic degree is 95%。
Example 4
Ligand L4[ (C)5H4)CH(C13H9)]2(CH2)4Synthesis of (2)
Bridged fulvenes were prepared as in example 1;
in ice bath, bridging fulvene (6.3g, 30mmol) is dripped into an ether (250mL) solution of lithium fluorene (9.96g,60mmol), a little precipitate is generated, reaction is carried out for one day, a little precipitate is still generated, hydrolysis is carried out, acetic acid is used for adjusting pH to be neutral, liquid separation is carried out, an organic phase is taken, water phase ether is extracted twice, the organic phase is combined, saturated saline solution is used for washing, anhydrous magnesium sulfate is used for drying for 6h, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is used as a mobile phase, column chromatography separation is carried out, and mucus with the yield of 34% is obtained, namely the ligand L4.
Complex 4[ (C)5H4)CH(C13H8)ZrCl2]2(CH2)4Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.076g, 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 1.02g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.35g, 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, 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 790mg of yellow powder, yield 51%.
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 4, introducing propylene gas at normal pressure, starting polymerization reaction at 0 deg.C, stirring for 30min, closing propylene gas cylinder, stopping reaction with 10% ethanol hydrochloride, transferring the polymer to a beaker, standing overnight, filtering, and filling with ethanolThe polymer was washed separately, dried at 80 ℃ under vacuum to constant weight, 5g of polymer was weighed, and the polymerization activity was 2.5X 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)5H4)CH((tBu)2C13H7)]2(CH2)3Synthesis of (2)
In the same way as in example 1, glutaraldehyde was used instead of adipic dialdehyde to prepare bridged fulvene;
in ice bath, bridged fulvene (5.88g, 30mmol) is dropwise added into an ether (250mL) solution of 2, 7-di-tert-butylfluorene lithium (16.67g,60mmol), a little precipitate is generated, the 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 used as a mobile phase, column chromatography separation is carried out, and 7.41g L5 is obtained after concentration.
Complex 5[ (C)5H4)CH((tBu)2C13H6)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.5g, 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 1.42g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.37g, 3.68mmol) 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 898mg of yellow powder with a yield of 46%.
Homogeneous catalysis of propylene polymerization at atmospheric pressure
Ethylene is used for a 100mL three-mouth bottle with a magnetic stirrer and an air guide tubeThe gas was replaced 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 5, 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 5.1g of polymer mass and 2.55 multiplied by 10 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 6
Ligand L6[ (C)5H4)CH(Cl2C13H7)]2(CH2)3Synthesis of (2)
In the same way as in example 1, glutaraldehyde was used instead of adipic dialdehyde to prepare bridged fulvene;
in ice bath, bridged fulvene (5.88g, 30mmol) is dropwise added into an ether (250mL) solution of 2, 7-dichlorofluorene (13.92g,58.8mmol), a little precipitate is generated, the reaction is carried out for one day, hydrolysis is carried out, acetic acid is used for adjusting the pH value to be neutral, liquid separation is carried out, an organic phase is taken, an aqueous phase is extracted twice by using ether, the organic phase is combined, the washing is carried out by using saturated saline solution, anhydrous magnesium sulfate is dried for 6h, filtration is carried out, a solvent is removed by vacuum rotation, petroleum ether is used as a mobile phase, column chromatography separation is carried out, and 6.95g L6 is obtained after concentration.
Complex 6[ (C)5H4)CH(Cl2C13H6)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is dripped into ether solution of ligand (1.32g, 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 1.24g of solid, tetrahydrofuran and liquid nitrogen ethanol bath are added, ZrCl is added under the condition of minus 78 DEG C42THF (1.34g, 3.61mmol) was naturally warmed to room temperature, reacted for 2 days to give a yellow reaction solution, the solvent was removed under reduced pressure, extracted twice with dichloromethane (30 mL. times.2), concentrated to 20mL, and added with n-hexane to adjust the polarityAnd putting the mixture in a refrigerator at the temperature of 20 ℃ below zero to separate out yellow substances, performing pressure filtration to remove supernate, and draining precipitates to obtain yellow powder 849mg with the yield of 48 percent.
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 4.2g of polymer mass and 2.1 × 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[ (C)5H4)CH(Br2C13H7)]2(CH2)3Synthesis of (2)
In the same way as in example 1, glutaraldehyde was used instead of adipic dialdehyde to prepare bridged fulvene;
under ice bath, bridged fulvene (5.88g, 30mmol) is dropwise added into an ether (250mL) solution of 2, 7-dibromofluorene (19.38g,60mmol), 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, washing is carried out by saturated saline solution, drying is carried out for 6h by anhydrous magnesium sulfate, filtration is carried out, the solvent is removed by vacuum rotation, petroleum ether is taken as a mobile phase, column chromatography separation is carried out, and 8.27g L7 is obtained after concentration.
Complex 7[ (C)5H4)CH(Br2C13H6)ZrCl2]2(CH2)3Synthesis of (2)
Under the condition of ice-water bath,nBuLi (8mmol) is added into ether solution of ligand (1.67g, 2mmol) dropwise to generate solid, reflux reaction is carried out for two days, supernatant is removed by pressure filtration, andwashing with diethyl ether once, draining to obtain solid 1.55g, adding tetrahydrofuran, liquid nitrogen ethanol bath, adding ZrCl at-78 deg.C42THF (1.34g, 3.61mmol) 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 973mg of yellow powder with a yield of 47%.
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 4.1g of polymer mass and 2.05X 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 95%.
Claims (12)
1. A bridged dinuclear metallocene compound having the structure represented by the following general formula I:
wherein: n is 2, 3 or 4;
r is hydrogen, tertiary butyl, bromine or chlorine.
2. The compound according to claim 1, selected from the following compounds:
[(C5H4)CH((tBu)2C13H6)ZrCl2]2(CH2)4；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)2；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)3；
[(C5H4)CH(C13H8)ZrCl2]2(CH2)4；
[(C5H4)CH((tBu)2C13H6)ZrCl2]2(CH2)3；
[(C5H4)CH(Cl2C13H6)ZrCl2]2(CH2)3；
[(C5H4)CH(Br2C13H6)ZrCl2]2(CH2)3。
3. a ligand compound having the structure shown in formula II:
wherein: n is 2, 3 or 4;
r is hydrogen, tertiary butyl, bromine or chlorine.
4. The ligand compound according to claim 3, wherein: n is 2, 3 or 4; r is hydrogen.
5. The ligand compound according to claim 3, wherein: n is 3 or 4; r is tertiary butyl.
6. The ligand compound according to claim 3, wherein: n is 3; r is bromine or chlorine.
7. A method for preparing the bridged dinuclear metallocene compound of claim 1 or 2, which comprises:
reacting the ligand compound according to any one of claims 3 to 6 with butyllithium to prepare a tetralithium salt;
tetralithium salt and ZrCl4Reacting to obtain the bridged dinuclear metallocene compound.
8. The production method according to claim 7, wherein the method for producing the bridged dinuclear metallocene compound according to claim 1 or 2 comprises:
taking a tetrahydrofuran solution containing the ligand compound according to any one of claims 3 to 6, adding an n-hexane solution containing n-butyllithium at-40 ℃ to 0 ℃, heating to 20 to 30 ℃, reacting for 10 to 20 hours, removing the solvent to obtain a solid, dissolving the solid with tetrahydrofuran at-70 ℃ to-80 ℃, and adding ZrCl4And (3) naturally raising the temperature to room temperature, reacting for 12-72 hours, draining, extracting with dichloromethane for two or three times, concentrating, adding n-hexane for polarity adjustment, and crystallizing at-30 to-10 ℃ to obtain a solid, namely the dinuclear metallocene compound.
9. The method according to claim 7 or 8, which further comprises a process for producing the ligand compound according to any one of claims 3 to 6.
10. The method according to claim 9, wherein the process for preparing the ligand compound according to any one of claims 3 to 6 comprises:
under ice bath, adding cyclopentadiene dropwise into a dialdehyde aqueous solution, adding methanol, adding pyrrolidine dropwise in an ice water bath, gradually turning yellow and slowly deepening the yellow color, reacting for 2-5h, adding water, adjusting the pH value to be neutral with acetic acid, separating liquid, taking an organic phase, extracting an aqueous phase with anhydrous ether, combining the organic phases, washing with saturated NaCl, and carrying out anhydrous MgSO (MgSO) extraction4Drying; filtering, removing solvent under reduced pressure, separating by column chromatography with petroleum ether as mobile phase, and concentrating to obtain bridged difenofulvene; in ice bath, bridged bifluorene is added dropwise to fluoreneAnd (2) generating a precipitate in an ether solution of the compound, refluxing for 24-72 hours, hydrolyzing, adjusting the pH value to be neutral by using acetic acid, separating liquid, taking an organic phase, extracting the organic phase by using water phase ether for 2-3 times, combining the organic phase, washing by using saturated saline solution, drying by using anhydrous magnesium sulfate, filtering, removing the solvent by reducing pressure, taking petroleum ether as a mobile phase, performing column chromatography separation, and concentrating to obtain the ligand compound.
11. Use of the bridged dinuclear metallocene compound according to claim 1 or 2 as a catalyst for the syndiotactic polymerization of propylene.
12. 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 or 2.
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| Helmut G. Alt et al..Dinuclear ansa zirconocene complexes as dual-site catalysts for the polymerization of ethylene.《Journal of Molecular Catalysis A: Chemical》.2002,第195卷 * |
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