CN112940158A - Supported metallocene catalyst and preparation method and application thereof - Google Patents
Supported metallocene catalyst and preparation method and application thereof Download PDFInfo
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- 239000012968 metallocene catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 112
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- -1 mercapto, carboxyl Chemical group 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000005977 Ethylene Substances 0.000 claims abstract description 34
- 239000004698 Polyethylene Substances 0.000 claims abstract description 34
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 30
- 229920000573 polyethylene Polymers 0.000 claims abstract description 28
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 27
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 23
- 150000002367 halogens Chemical class 0.000 claims abstract description 23
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 230000002902 bimodal effect Effects 0.000 claims abstract description 12
- 230000000737 periodic effect Effects 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 150000001336 alkenes Chemical class 0.000 claims abstract description 7
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000013067 intermediate product Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims description 14
- 238000003379 elimination reaction Methods 0.000 claims description 14
- 238000006138 lithiation reaction Methods 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Chemical group 0.000 claims description 6
- 239000010936 titanium Chemical group 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Chemical group 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 84
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 35
- 229910052757 nitrogen Inorganic materials 0.000 description 34
- 238000003756 stirring Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 23
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000008859 change Effects 0.000 description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- ASGNRCDZSRNHOP-UHFFFAOYSA-N 2-methyl-4-phenyl-1h-indene Chemical compound C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 ASGNRCDZSRNHOP-UHFFFAOYSA-N 0.000 description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 10
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 10
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- 229920000642 polymer Polymers 0.000 description 8
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- 230000003197 catalytic effect Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910007932 ZrCl4 Inorganic materials 0.000 description 4
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- NJHHIOOKFSESTG-UHFFFAOYSA-N 2-methyl-1h-cyclopenta[a]naphthalene Chemical compound C1=CC=CC2=C(CC(C)=C3)C3=CC=C21 NJHHIOOKFSESTG-UHFFFAOYSA-N 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- 229910003865 HfCl4 Inorganic materials 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical class Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- INGBASMTNLKRJM-UHFFFAOYSA-N [Li].CC=1CC2=C3C(=CC=C2C=1)C=CC=C3 Chemical compound [Li].CC=1CC2=C3C(=CC=C2C=1)C=CC=C3 INGBASMTNLKRJM-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 125000001979 organolithium group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a supported metallocene catalyst and a preparation method and application thereof, which are used for olefin polymerization, the supported metallocene catalyst comprises a carrier and a metallocene compound, the metallocene compound is supported on the carrier, and the metallocene compound has a cis structure and a trans structure in a spatial structure, as shown in the following formula I:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is group VAAn element; r1，R2，R3，R4The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl. The polyethylene product obtained by using the catalyst of the invention in ethylene polymerization has a broad molecular weight distribution or a bimodal distribution through GPC analysis.
Description
Technical Field
The invention relates to a supported metallocene catalyst and a preparation method thereof, and relates to a method for preparing bimodal polyethylene by using a single reactor and a single metallocene catalyst system, and the obtained polyethylene.
Background
Polyolefin resin, as one of important synthetic materials, directly affects the development of national economy. At present, the polyolefin industry in China develops rapidly, but the yield and the performance can not meet the market demand, and particularly the demand of high-performance polyolefin materials increases rapidly, so that how to improve the performance of general high polymer materials such as polyethylene and the like is a hot spot of research of people. The bimodal polyethylene consists of high molecular weight polyethylene and low molecular weight polyethylene, the high molecular weight part can ensure the physical mechanical strength of the polymer, and the low molecular weight part can improve the processability of the polymer, so that compared with common polyethylene products, the bimodal molecular weight distribution polymer, particularly polyethylene, can give consideration to good mechanical properties and processability, and is widely applied in recent years.
To achieve these characteristics, there are three methods for industrially producing bimodal polyethylene currently, in which polymers having different molecular weights are produced through two reactors by a parallel reaction tank process and then blended in a molten state, but this method is expensive and it is difficult to control the uniformity of product quality.
The method has the advantages of flexible operation, convenient product switching and higher equipment investment cost. The currently used tandem production processes in industrial production mainly include Borstar process by Borealis corporation in finland, CX process by Mitsui corporation in japan, Unipol ii process by UCC corporation in usa, and spherinene process by Basell corporation in england.
The method adopts a single reaction kettle process, uses a catalyst with multiple active points, or a single catalyst and multiple carriers, or a mixed catalyst, and common catalyst systems comprise a composite bimetallic catalyst system, a Ziegler-Natta/metallocene composite catalyst, a Ziegler-Natta/Ziegler-Natta composite catalyst, a double metallocene composite catalyst, a chromium-based/metallocene composite catalyst, a metallocene/late transition metal composite catalyst and the like. This process is considered a revolutionary advance due to the substantial reduction in equipment costs. At present, the method is realized in some chemical companies, for example, UCC of the United states adopts a gas phase method and a suitable mixed catalyst in a Unipol process unit to synthesize a bimodal polyethylene product. The Prodigy catalyst developed by Univation corporation produces bimodal HDPE in a single reactor. Both british BP and Phillips companies have performed corresponding research and development work.
For example, WO99/03899 by Mobil corporation, this type of catalyst has been reported to have better copolymerization performance than Ziegler-Natta catalysts because metallocene catalysts have better copolymerization performance, and the molecular weight of polymers obtained by Ziegler-Natta catalysts is relatively large, so that the high molecular weight portion of the obtained resin has low branching degree, even no branching, while the low molecular weight portion is highly branched, and the material cannot achieve balance between processability and strength, and does not achieve ideal compounding effect.
In the prior art, chinese patent CN 109705242a discloses a supported metallocene catalyst and a preparation method and application thereof, wherein a single metallocene catalyst composite carrier has a double-activity center, and the composite carrier comprises a first carrier and a second carrier; the first carrier is an inorganic carrier modified by antimony chloride and alkyl aluminum, and the second carrier is carboxylated polystyrene, wherein the inorganic carrier is silicon dioxide or silica gel. Chinese patent CN 106589178A discloses a method for preparing a vanadium and metallocene bimetallic catalyst, which requires high temperature calcination to obtain vanadium oxide in oxidation state, then the vanadium oxide is reacted under reduction condition to obtain pre-reduced vanadium oxide in low oxidation state, and then the vanadium/metallocene bimetallic catalyst is loaded with a metallocene composition on an inorganic carrier to obtain the vanadium/metallocene composite catalyst, and the vanadium/metallocene composite catalyst is applied to olefin preparation.
Both single metallocene catalyst composite supports and bimetallic catalysts require special design in the preparation of the catalyst, so that the prepared catalyst contains two active centers, one for producing low molecular weight polyethylene and the other for producing high molecular weight polyethylene. The synergistic effect of a bimetallic catalyst or a dual-carrier system needs to be considered when a catalytic system is designed, so that the limitation of catalyst selection is increased, and the important significance is provided for developing a single-carrier supported single metallocene catalyst to prepare a bimodal polyethylene product.
Disclosure of Invention
The invention mainly aims to provide a supported metallocene catalyst and a preparation method thereof, an ethylene polymerization method and prepared polyethylene, so as to overcome the defects that a composite carrier or a bimetallic catalyst in the prior art is low in catalyst activity, limited in selection and undesirable in the prepared polymer when the polyethylene with wide molecular weight distribution is prepared.
In order to achieve the above object, the present invention provides a supported metallocene catalyst for olefin polymerization, the supported metallocene catalyst comprising a support and a metallocene compound, the metallocene compound being supported on the support, the metallocene compound having both cis and trans structures in a steric structure, as shown in formula i or formula ii below:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl.
The supported metallocene catalyst is characterized in that M is an IIIB or IVB element in a periodic table of elements; x, equal to or different from each other, are independently selected from halogen; q is the same or different and is independently selected from alkyl; the R is1，R2，R3，R4Is hydrogen, alkyl of C1-C10, alkenyl of C3-C10, alkoxy of C3-C6 or aryl.
The supported metallocene catalyst of the invention, wherein M is zirconium, hafnium or titanium; x is chlorine or bromine; the R is1，R2，R3，R4Independently hydrogen, alkyl of C1-C4, alkenyl of C3-C4, alkoxy of C3-C5 or aryl.
The supported metallocene catalyst of the present invention, wherein R is1，R2，R3，R4Independently hydrogen, methyl, isopropyl, butyl, a benzene ring or substituted benzene.
In order to achieve the above object, the present invention also provides a method for preparing a supported metallocene catalyst for olefin polymerization, the supported metallocene catalyst comprising a support and a metallocene compound, the method for preparing the metallocene compound comprising:
step 1, ligands A1 and Q2TA2Preparing an intermediate product 1 through reaction, carrying out lithiation reaction on a ligand A2 and an alkyl lithium reagent to prepare an intermediate product 2, and carrying out salt elimination reaction on the intermediate product 1 and the intermediate product 2 to obtain an intermediate product 3, wherein the formula is shown as the following formula III;
step 2, intermediate 3 with MX4The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4Are the same or different from each other and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl; a is halogen.
The preparation method of the supported metallocene catalyst comprises the steps that T is C or Si, Q is alkyl, and the ligand A1 is subjected to lithiation reaction with an alkyl lithium reagent and then subjected to lithiation reaction with Q2TA2The salt elimination reaction takes place to give intermediate 1.
The preparation method of the supported metallocene catalyst comprises the steps of enabling X to be halogen, enabling M to be zirconium, hafnium or titanium, enabling an intermediate product 3 to be subjected to lithiation reaction with an alkyl lithium reagent, and enabling the intermediate product to be subjected to lithiation reaction with MX4The salt elimination reaction occurs to obtain the metallocene compound.
The preparation method of the supported metallocene catalyst provided by the invention has the advantages that the metallocene compounds with cis-structure and trans-structure are directly supported on the carrier without separation to obtain the supported metallocene catalyst.
In order to achieve the above object, the present invention provides an ethylene polymerization process using the above supported metallocene catalyst.
The ethylene polymerization process of the present invention, wherein the process is carried out in a single reactor.
The polyethylene prepared by the ethylene polymerization method has a bimodal distribution and/or a molecular weight distribution width of 5-7.
The invention has the beneficial effects that:
the invention provides a supported single metallocene catalyst, wherein an active component metallocene compound has a quasi-C2 symmetrical structure, although the metallocene compound is a single compound, a cis (syn) structure and a trans (anti) structure exist in a space structure, and the two compounds with different space structures are freely transformed in an ethylene polymerization process to respectively obtain different molecular weight polymers, so that finally obtained polyethylene has wide molecular weight distribution and even bimodal distribution.
The invention also provides a preparation method of the metallocene compound, the prepared cis-structure and trans-structure metallocene compound can be directly loaded on a carrier to obtain the metallocene catalyst without separation operation, and the process is simple and is suitable for industrial production.
When the supported single metallocene catalyst is used for ethylene polymerization, the cis-structure metallocene compound and the trans-structure metallocene compound have the same requirements on reaction conditions, the reaction conditions are easy to select, the molecular weight distribution of the obtained polyethylene is wide, and the balance between the processability and the strength can be realized.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the product obtained in example 2.
FIG. 2 shows the nuclear magnetic spectrum of the product obtained in example 3.
FIG. 3 is the nuclear magnetic spectrum of the product obtained in example 5.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention provides a supported metallocene catalyst for olefin polymerization, which comprises a carrier and a metallocene compound, wherein the metallocene compound is supported on the carrier, and the metallocene compound has a cis structure and a trans structure in a spatial structure, and is shown as the following formula I or formula II:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl.
The active component metallocene compound of the supported single metallocene catalyst has a quasi-C2 symmetrical structure, although the metallocene compound is a single compound, cis (syn) and trans (anti) structures exist on the space structure, the two compounds with different space structures are freely transformed in the ethylene polymerization process to respectively obtain polymers with different molecular weights, so that the finally obtained polyethylene has wide molecular weight distribution and even bimodal distribution.
In one embodiment, M is an iiib or ivb element of the periodic table of elements, including the lanthanides and the series elements; x, equal to or different from each other, are independently selected from halogen; the above-mentionedQ, equal to or different from each other, is independently selected from alkyl; the R is1，R2，R3，R4Independently hydrogen, alkyl of C1-C10, alkenyl of C3-C10, alkoxy of C3-C6 or aryl.
In another embodiment, M is zirconium, hafnium or titanium; x is chlorine or bromine; the R is1，R2，R3，R4Independently hydrogen, alkyl of C1-C4, alkenyl of C3-C4, alkoxy of C3-C5 or aryl.
In yet another embodiment, the R is1，R2，R3，R4Independently hydrogen, methyl, isopropyl, butyl, a benzene ring or substituted benzene.
The supported metallocene catalyst of the present invention is not particularly limited in the proportional relationship between the cis-structured and trans-structured metallocene compounds, and the cis-structured and trans-structured metallocene compounds are converted with each other during the ethylene polymerization process.
The carrier in the present invention is not particularly limited, and may be a carrier that is conventional in the art, such as silica gel. The relationship between the amounts of the active ingredient and the carrier can be reasonably adjusted by one skilled in the art according to the needs.
The invention also provides a preparation method of the supported metallocene catalyst, which can obtain a product shown in formula I or formula II according to the structure of the ligand A1, wherein the preparation method of the metallocene compound as an active component comprises the following steps:
step 1, ligands A1 and Q2TA2Preparing an intermediate product 1 through reaction, carrying out lithiation reaction on a ligand A2 and an alkyl lithium reagent to prepare an intermediate product 2, and carrying out salt elimination reaction on the intermediate product 1 and the intermediate product 2 to obtain an intermediate product 3, wherein the formula is shown as the following formula III;
step 2, intermediate 3 with MX4The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4Are the same or different from each other and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl; a is halogen.
According to the preparation method of the metallocene compound, the prepared cis-structure and trans-structure metallocene compounds can be directly loaded on a carrier to obtain the metallocene catalyst without separation operation, the process is simple, the synthesis yield is high, the product purification is easy, and the preparation method is suitable for industrial production.
In one embodiment, the preparation of the metallocene compounds of the invention is carried out under protection of an inert gas, such as nitrogen or the like.
In one embodiment, T is C or Si, Q is alkyl, and the ligand A1 is lithiated with an alkyllithium reagent prior to lithiation with Q2TA2The salt elimination reaction takes place to give intermediate 1. X is halogen, M is zirconium, hafnium or titanium, the intermediate product 3 is firstly subjected to lithiation reaction with an alkyl lithium reagent and then is subjected to lithiation reaction with MX4The salt elimination reaction occurs to obtain the metallocene compound.
In another embodiment, the alkyllithium reagent is, for example, n-butyllithium, and ligand A1 is reacted with the alkyllithium reagent in an organic solvent, for example, anhydrous diethyl ether, at a temperature of, for example, 0 deg.C to room temperature. The reaction product is further reacted with Q2TA2Hair generating saltElimination reaction to give intermediate 1, the salt elimination reaction temperature being, for example, -78 ℃ to room temperature.
In another embodiment, ligand A2 is reacted with an alkyllithium reagent, such as n-butyllithium, in an organic solvent, such as anhydrous diethyl ether, at a temperature of, for example, 0 deg.C to room temperature, to provide intermediate 2.
The reaction of intermediate 1 and intermediate 2 is: intermediate 1 and intermediate 2 are each dissolved in an organic solvent, such as anhydrous ether, and intermediate 2 is then slowly added dropwise to intermediate 1, for example at a temperature below 0 ℃, and after completion of the addition, the reaction is carried out at room temperature to give intermediate 3.
In another embodiment, intermediate 3 is reacted with an alkyllithium reagent, such as n-butyllithium, in an organic solvent, such as anhydrous methyl t-butyl ether, at a temperature of, for example, 0 ℃ to room temperature. Reaction product with MX4The salt elimination reaction takes place to give the metallocene compound, the reaction temperature being, for example, -78 ℃ to room temperature.
The invention also provides an ethylene polymerization method, the catalyst is the supported metallocene catalyst, and the method is carried out in a single reactor to obtain a polyethylene product with wide molecular weight distribution.
In one embodiment, the ethylene polymerization process of the present invention is as follows:
pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding the obtained supported metallocene catalyst into a polymerization kettle, and washing with 0.2kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring pressure control ethylene feeding, heating to the polymerization temperature, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging polyethylene, and cleaning the polymerization kettle.
The amount of the solvent used in the present invention is not strictly limited, and can be controlled by those skilled in the art according to the actual reaction and the need for convenient post-treatment.
The process of the present invention is illustrated below by means of specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1:
synthesis of intermediate 1 in the reaction scheme:
weighing ligand A in a glove box1(Fw-281.35, 28.14 g, 100mmol) was placed in a 1000mL two-neck round-bottom flask, which was removed from the glove box and transferred to a Sclenk system. Dissolved in 500mL of anhydrous ether under a high-purity nitrogen atmosphere. The round-bottomed flask was placed in an ice-water bath at a temperature below 0 ℃ and a solution of n-butyllithium in hexane (2.40M/L solution, 44ml, 105mmol) was slowly added dropwise with constant stirring under a highly pure nitrogen atmosphere. After the dropwise addition, the reaction system naturally rises to room temperature, and the solution is dark red. The reaction was incubated at 25 ℃ for 4 h. The organolithium solution prepared above was slowly added dropwise to a solution containing dimethyldichlorosilane (Me) using a Teflon capillary under nitrogen blanket2SiCl2Fw 129.06, d 1.07g/mL, 60.0mL,500mmol) in anhydrous ether (30mL,<0 ℃) in solution. The reaction is stirred overnight under the protection of nitrogen, LiCl is filtered out by a siphon filtration method under the protection of nitrogen, and the residual solid LiCl is extracted and washed by a small amount of anhydrous ether and siphoned and filtered. The combined filtrates were vacuumed to remove the solvent and unreacted Me2SiCl2Intermediate 1 was obtained in 98% yield.
Synthesis of intermediate 2 in the reaction scheme:
the 2-methylbenzindene organic molecule (Fw ═ 180.25,18.02g, 100mmol) was weighed into a 1000mL two-necked round-bottomed flask in an inert gas glove box, and the round-bottomed flask was transferred from the glove box to a Schlenk system. The 2-methylbenzindene is dissolved in 500mL of anhydrous ether under the protection of high-purity nitrogen, and the round-bottom flask is placed in an ice-water bath below 0 ℃. To the above 2-methylbenzindene ethyl ether solution was slowly dropped an n-butyllithium hexane solution (2.40M/L, 41.6mL,100mmol), and after completion of the dropping, the reaction system was allowed to react while keeping warm at 25 ℃ for 5 hours to obtain an ethyl ether solution of 2-methylbenzindene lithium salt (intermediate 2).
Synthesis of intermediate 3 in the reaction scheme:
dissolving intermediate product 1 in anhydrous ether (500mL) under nitrogen protection, cooling to less than 0 deg.C, slowly adding ether solution of intermediate product 2 dropwise into ether solution of intermediate product 1 by capillary siphon method, naturally heating to room temperature after dropwise addition, and stirring at 28 deg.C under high purity nitrogen atmosphere overnight. The above dark red solution was siphoned to remove LiCl, and the remaining solid was washed once with a small amount of anhydrous ether and siphoned. The combined filtrates were vacuum decompressed to remove the solvent and vacuum dried to a constant weight to give intermediate 3 with a purity of greater than 95%.
Example 2:
to an ampoule containing 35.177 g of intermediate (517.74g/mol,10mmol) was added 150mL of anhydrous methyl t-butyl ether to give a suspension of ligand. At room temperature, add 8.33mL with a syringenBuLi/hexane (2.4mol/L) gave a red-brown solution. Stirring was continued at room temperature for 4 h. 3.773g ZrCl were removed from the glovebox4(thf)2(377.25g/mol,10mmol) in a 350mL Schlenk reaction flask in N2150mL of anhydrous methyl tert-butyl ether was added under protection to give a suspension. Slowly adding lithium salt solution of ligand into ZrCl at room temperature4(thf)2After completion of the dropwise addition, the suspension of (1.5) was stirred at room temperature for 8 hours. The reaction suspension was cherry red. Pumping out the volatile matter to constant weightTo obtain the complex. The product was a red solid with finer particles (dark red on suction from dichloro). The nuclear magnetization is shown in FIG. 1, and the dichloro and hexane in nuclear magnetization are contained in the deuterated solvent, and the product contains 0.5eq of tetrahydrofuran and 0.8eq of methyl tert-butyl ether. The nuclear magnetic purity is more than 90%. The product contained 2eq LiCl.
Example 3:
synthesis of (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] zirconium dichloride complex
0.64g of the starting material a (Fw-219.28, 2.9mmol) was weighed into an ampoule, and dissolved in 30mL of anhydrous ether. In high purity N2The ampoule was cooled in an ice-water bath at 0 ℃ with stirring under protection, and 1.75mL of nBuLi/hexane (2.01mol/L,3.5mmol) was slowly added dropwise thereto using a syringe. After the dropwise addition, the reaction system naturally rises to room temperature, and the solution turns into black red. The reaction was stirred at rt for 4 h. N is a radical of2The above lithium salt solution was slowly added dropwise (20min) to 1.75mL dimethyldichlorosilane (Me) in an ice-water bath at 0 ℃ under protection2SiCl2Fw 129.04, d 1.07g/mL,14.5mmol) in anhydrous ether (20 mL). The solution appeared dark red, producing a large amount of LiCl, the reaction was stirred overnight at room temperature and was suction dried to give an off-white solid.
0.60g of the starting material b (Fw-206.28, 2.9mmol) was weighed into an ampoule and dissolved in 20mL of anhydrous ether to give a colorless solution. In high purity N2The ampoule was cooled and stirred in an ice-water bath at 0 ℃ under protection, and 1.45mL of nBuLi/hexane (2.01mol/L,2.9mmol) was slowly added dropwise thereto using a syringe. And (3) naturally heating the reaction system, changing the solution from colorless to yellow and finally to orange, and stirring at room temperature for 5 hours to obtain a product 2.
The product 1 which had been drained off was dissolved in 30mL of anhydrous ether, and the solution was dark red. And (3) placing the ether solution of the product 1 in a low-temperature cooling bath at the temperature of-30 ℃ for cooling and stirring, slowly dripping the ether solution of the product 2 into the product 1 (15min), naturally heating the reaction system after dripping is finished, enabling the solution to be black red, and stirring at room temperature overnight. LiCl was removed, the solvent was spin dried, and recrystallized from petroleum ether to give 300mg of an off-white solid as product 3.
The above product 3 (Fw-481.70, 1.12mmol,540mg) was dissolved in anhydrous ether as an off-white suspension. Placing the ampoule in ice-water bath at 0 deg.C, cooling and stirring, adding water, stirring, and adding water21.42mL of nBuLi/hexane (1.6mol/L,2.24mmol) was added slowly with protection, the insolubles were gradually dissolved and the solution turned yellow. Naturally heating to room temperature, and stirring for 5 hours at room temperature to obtain the ligand lithium salt solution. 0.262g ZrCl was taken out of the glove box4(Fw-233.04, 1.12mmol) in an ampoule under N2Under protection, 30mL of anhydrous ether was added. Reacting ZrCl4The ether solution is placed in a low-temperature cooling bath at the temperature of minus 40 ℃ for cooling and stirring, and the lithium salt solution of the ligand is slowly added into ZrCl4After completion of the dropwise addition, the temperature was naturally raised to room temperature, and the mixture was stirred at room temperature overnight. A yellow solid precipitated and was filtered off and dried to give 482mg of product as an orange solid in 66.7% yield. The nuclear magnetic results are shown in FIG. 2.
Example 4:
(2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ]]Indole) dimethylsilyl group]Synthesis of hafnium dichloride Complex by the same procedure as in example 3, HfCl4Substitution of ZrCl4。
Example 5:
synthesis of [ (2-methyl-4-phenyl-indene) (N-methyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (procedure same as example 3), product nuclear magnetization is shown in FIG. 3.
Example 6:
[ (2-methyl-4-phenyl-indene) (N-methyl- [1, 2-b)]Indole) dimethylsilyl group]Synthesis of hafnium dichloride Complex by the same procedure as in example 3, HfCl4Substitution of ZrCl4。
A catalyst loading step: under the protection of nitrogen, 1g of carrier was mixed with 20ml of toluene solution at 40 ℃ to form suspension A, and 2ml of MAO (methylaluminoxane) solution/toluene solution with a concentration of 1.1mol/L was added dropwise to suspension A, and reacted for 2 hours to form suspension B. Meanwhile, 25. mu.mol of the complex obtained in example 2-6 was weighed and dissolved in 10ml of a toluene solution to obtain a solution C, 2.3ml of a 1.1mol/L MAO/toluene solution was added dropwise to the solution C, and the reaction was stirred at 40 ℃ for 1 hour to obtain an activated catalyst solution D. The solution D was added dropwise to the suspension B and the reaction was stirred at 40 ℃ for 2 h. And (3) standing for layering, removing a supernatant, washing for 3 times by using 20ml of toluene, and vacuumizing and drying for 4 hours at the temperature of 40 ℃ to finally obtain the catalyst with good fluidity.
Example 7:
polymerization experiment: the catalyst is [ (2-methyl-4-phenyl-indene) (N-phenyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex.
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 310mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 60 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 850g of polyethylene, and cleaning the polymerization kettle. The catalytic activity of the catalyst is 2740g PE/gcat, the molecular weight distribution is 5.9, and the molecular weight Mw is 360100.
Example 8:
polymerization experiment: the catalyst was (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 3 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; 305mg of the catalyst is added into a polymerization kettle, and 0.2Kg of hexane is used for washing to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 80 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 1200g of polyethylene, and cleaning the polymerization kettle. The catalyst has catalytic activity of 3934g PE/gcat, molecular weight distribution of 5.3 and molecular weight Mw 252520.
Example 9:
polymerization experiment: (2-methyl-4-phenyl-indene) (N-methyl-indene [2,1-b ] indole) dimethylsilyl ] hafnium dichloride complex (example 4 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 500mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 60 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 950g of polyethylene, and cleaning the polymerization kettle. The catalyst had catalytic activity of 1900g PE/gcat, molecular weight distribution of 6.5 and molecular weight Mw 768520.
Example 10:
polymerization experiment: the catalyst was [ (2-methyl-4-phenyl-indene) (N-phenyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 5 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 450mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 85 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 1100g of polyethylene, and cleaning the polymerization kettle. The catalytic activity of the catalyst is 2445g PE/gcat, the molecular weight distribution is 5.9, and the molecular weight Mw 515110.
Example 11:
polymerization experiment: [ (2-methyl-4-phenyl-indene) (N-methyl-indene [1,2-b ] indole) dimethylsilyl ] zirconium dichloride complex (example 5 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 430mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 65 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 780g of polyethylene, and cleaning the polymerization kettle. Catalyst catalytic Activity 1814g PE/gcat, molecular weight distribution 6.1, molecular weight Mw 267800
Example 12:
polymerization experiment: [ (2-methyl-4-phenyl-indene) (N-methyl- [1,2-b ] indole) dimethylsilyl ] hafnium dichloride complex (example 6 catalyst).
Pretreating a polymerization kettle, and vacuumizing the polymerization kettle at 80 ℃ for replacing nitrogen for three times; at room temperature, under the protection of nitrogen, 2.8Kg of hexane is injected into the polymerization kettle; according to the experimental plan, a quantitative 10% strength by mass solution of triethylaluminum in hexane was added. Then heating to 55 ℃, stirring the polymerization kettle for 15min, and then cooling to room temperature; adding 700mg of catalyst into a polymerization kettle, and washing with 0.2Kg of hexane to ensure that the catalyst is completely added into the polymerization kettle; introducing nitrogen in the polymerization kettle, replacing the nitrogen with ethylene, increasing the stirring speed to 900RPM, setting the polymerization pressure to be 2MPa, ensuring the pressure to control the feeding of ethylene, heating to the polymerization temperature of 85 ℃, starting polymerization, paying attention to the polymerization temperature change and the ethylene consumption rate change in the whole process, reacting for 60 minutes, cooling and discharging 800g of polyethylene, and cleaning the polymerization kettle. Catalyst catalytic activity 1143g PE/gcat, molecular weight distribution 6.3, molecular weight Mw 568800
The polymerization characterization results of examples 7-12 are shown in Table 1 below.
TABLE 1 characterization results for polymerization of examples 7-12
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A supported metallocene catalyst for olefin polymerization, comprising a support and a metallocene compound supported on the support, wherein the metallocene compound has both cis and trans structures in a steric structure, and the metallocene compound has the following formula I or formula II:
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from hydrogen, halogen, alkyl, alkoxy, mercapto, or a salt thereof,Carboxy, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4The same or different from each other, and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl.
2. The supported metallocene catalyst of claim 1, wherein M is an iiib or ivb element of the periodic table of elements; x, equal to or different from each other, are independently selected from halogen; q is the same or different and is independently selected from alkyl; the R is1，R2，R3，R4Is hydrogen, alkyl of C1-C10, alkenyl of C3-C10, alkoxy of C3-C6 or aryl.
3. The supported metallocene catalyst of claim 2, wherein M is zirconium, hafnium or titanium; x is chlorine or bromine; the R is1，R2，R3，R4Independently hydrogen, alkyl of C1-C4, alkenyl of C3-C4, alkoxy of C3-C5 or aryl.
4. The supported metallocene catalyst of claim 3, wherein R is1，R2，R3，R4Independently hydrogen, methyl, isopropyl, butyl, a benzene ring or substituted benzene.
5. A method for preparing a supported metallocene catalyst for olefin polymerization, the supported metallocene catalyst comprising a support and a metallocene compound, the method for preparing the metallocene compound comprising:
step 1, ligands A1 and Q2TA2Preparing an intermediate product 1 through reaction, carrying out lithiation reaction on a ligand A2 and an alkyl lithium reagent to prepare an intermediate product 2, and carrying out salt elimination reaction on the intermediate product 1 and the intermediate product 2 to obtain an intermediate product 3, wherein the formula is shown as the following formula III;
step 2, intermediate 3 with MX4The metallocene compound is obtained by salt elimination reaction, and comprises a cis structure and a trans structure, which are shown in the following formula IV;
wherein M is a transition metal element of IIIB, IVB, VB or VIB in the periodic table of elements; t is a group IVA element; x is independently selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, mercapto, carboxyl, amino, phosphino and OSO2CF3(ii) a Q is independently selected from hydrogen, halogen, alkyl, alkoxy, haloalkyl; e is a group VA element; r1，R2，R3，R4Are the same or different from each other and are independently hydrogen, alkyl, alkoxy, aryl or alkenyl; a is halogen.
6. The method of claim 5, wherein T is C or Si, Q is alkyl, and the ligand A1 is lithiated with an alkyl lithium reagent and then with Q2TA2The salt elimination reaction takes place to give intermediate 1.
7. The method of claim 5, wherein X is a halogen, M is zirconium, hafnium or titanium, and the intermediate product 3 is lithiated with an alkyl lithium reagent and then lithiated with MX4The salt elimination reaction occurs to obtain the metallocene compound.
8. The process for producing a supported metallocene catalyst according to claim 5, wherein the metallocene compounds having a cis-structure and a trans-structure are directly supported on a carrier without separation to obtain a supported metallocene catalyst.
9. A process for the polymerization of ethylene, characterized in that the catalyst used is a supported metallocene catalyst as claimed in any of claims 1 to 4.
10. Ethylene polymerization process according to claim 9, characterized in that it is carried out in a single reactor.
11. A polyethylene produced by the ethylene polymerization process of claim 9 or 10, wherein the polyethylene has a bimodal distribution and/or a molecular weight distribution breadth of from 5 to 7.
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| CN114249775A (en) * | 2021-12-03 | 2022-03-29 | 国家能源集团宁夏煤业有限责任公司 | Metallocene compound, preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof |
| CN114249775B (en) * | 2021-12-03 | 2024-04-16 | 国家能源集团宁夏煤业有限责任公司 | Metallocene compound and preparation method thereof, catalyst composition, supported metallocene catalyst and application thereof |
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