CN109384866A - The preparation method of metallocene polypropylene catalyst - Google Patents
The preparation method of metallocene polypropylene catalyst Download PDFInfo
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- CN109384866A CN109384866A CN201710652485.6A CN201710652485A CN109384866A CN 109384866 A CN109384866 A CN 109384866A CN 201710652485 A CN201710652485 A CN 201710652485A CN 109384866 A CN109384866 A CN 109384866A
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- metallocene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- -1 polypropylene Polymers 0.000 title claims abstract description 43
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 37
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 230000004913 activation Effects 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 28
- 239000000741 silica gel Substances 0.000 claims description 26
- 229910002027 silica gel Inorganic materials 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 16
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000012876 carrier material Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 4
- 150000008040 ionic compounds Chemical class 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 229910052735 hafnium Chemical group 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000037048 polymerization activity Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000008030 elimination Effects 0.000 abstract description 4
- 238000003379 elimination reaction Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000007812 deficiency Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 123
- 239000007787 solid Substances 0.000 description 26
- 238000003756 stirring Methods 0.000 description 24
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 20
- FLFNHHSXSLXYQB-UHFFFAOYSA-L CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 Chemical group CC1=CC(C(=CC=C2)C=3C=CC=CC=3)=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C(C)=CC2=C1C=CC=C2C1=CC=CC=C1 FLFNHHSXSLXYQB-UHFFFAOYSA-L 0.000 description 14
- 230000000737 periodic effect Effects 0.000 description 13
- 125000005842 heteroatom Chemical group 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000002015 acyclic group Chemical group 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 2
- 108091006230 SLC7A3 Proteins 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000010076 replication Effects 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VFYUVMGJOFRPRT-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-dimethyl-nonylazanium Chemical compound CCCCCCCCC[N+](C)(C)C1CC(C)(C)N([O])C(C)(C)C1 VFYUVMGJOFRPRT-UHFFFAOYSA-N 0.000 description 1
- 102100029272 5-demethoxyubiquinone hydroxylase, mitochondrial Human genes 0.000 description 1
- 101100219344 Arabidopsis thaliana CAT7 gene Proteins 0.000 description 1
- 101100494447 Arabidopsis thaliana CAT9 gene Proteins 0.000 description 1
- 101150013917 CAT8 gene Proteins 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- 101000770593 Homo sapiens 5-demethoxyubiquinone hydroxylase, mitochondrial Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000009566 Mao-to Substances 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002907 osmium Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003906 silylidene group Chemical group [H][Si]([H])=* 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
- C08F4/025—Metal oxides
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of preparation methods of metallocene polypropylene catalyst, porous catalyst carrier are carried out high-temperature activation under inert gas conditions, activation temperature is 200-900 DEG C, and activation time is 0.5-48 hours.The present invention improves propylene polymerization activity, can overcome the deficiencies in the prior art, catalysis in olefine polymerization with higher activity reduces the production cost of polymerization product.The dosage of MAO is substantially reduced, while reducing β-H elimination, the relative molecular mass of polymer is improved, reduces production cost.
Description
Technical Field
The invention relates to a preparation method of a metallocene polypropylene catalyst, belonging to the field of catalysts.
Background
In industrial production, it is desired to increase the activity of metallocene polypropylene catalysts to reduce the production cost of olefin polymerization. Generally, one or more catalytic components can be supported on a porous support. Usually the metallocene is deposited onto the support in solution. Simultaneously, or separately, an activator, preferably Methylaluminoxane (MAO) and/or an alkylaluminum compound and/or an ionizing activator, is also deposited onto the support. The catalyst may be dissolved in one or more liquid monomers or in a solvent containing one or more monomers. The monomers used are capable of undergoing polymerization during impregnation of the support or evaporation of the solvent.
CN101146836B provides a method for preparing metallocene polypropylene catalyst, weighing silica gel carrier pretreated at high temperature, suspending in 30ml toluene at 0 deg.C, adding metered MAO through dropping funnel, then returning to room temperature and stirring for 2 hours. The solvent was removed with a filter and washed again with solvent, repeated 3 times. The residue was suspended in 20ml of toluene at 15 ℃ and the metallocene active site loading was slowly added and, after completion of loading, dried in a high vacuum chamber. The patent states that the catalyst support can be calcined and activated at 200-1000 c, but does not describe the specific activation temperature and what effect on the catalyst performance would be preferred.
The industrialization of metallocene polypropylene catalyst creates conditions for producing polypropylene resin with obviously improved physical and mechanical properties, and can preferably produce isotactic polypropylene with ultrahigh rigidity, syndiotactic polypropylene with high transparency, blend of isotactic polypropylene and syndiotactic polypropylene, polypropylene impact copolymer with ultrahigh performance and the like. However, metallocene polypropylene catalysts require the addition of a large amount of MAO to increase polymerization activity, which greatly increases the production cost of polypropylene products and limits their industrial applications. The invention provides a preparation method of metallocene polypropylene catalyst, which is different from the preparation method of metallocene polypropylene catalyst in the prior art, and the preparation process of catalyst carrier is optimized, so that the polymerization activity of the catalyst body is improved, and the production cost is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a metallocene polypropylene catalyst, which improves the polymerization activity of propylene, can overcome the defects of the prior art, has higher catalytic activity of olefin polymerization, reduces the production cost of a polymerization product, greatly reduces the consumption of MAO, reduces β -H elimination, improves the relative molecular mass of a polymer and reduces the production cost.
The preparation method of the metallocene polypropylene catalyst of the invention activates the catalyst porous carrier at high temperature under the condition of inert gas, wherein the activation temperature is 200-900 ℃, and the activation time is 0.5-48 hours.
The preparation method of the metallocene polypropylene catalyst comprises the following steps:
(a) carrying out high-temperature activation on the catalyst porous carrier under the condition of inert gas;
(b) adding a porous carrier material into a solvent for dispersion under the protection of nitrogen;
(c) reacting the cocatalyst with the porous carrier material at-20-200 ℃ for 0.1-48 h, and then washing the reactant by using a solvent;
(d) dissolving a metallocene compound in a solvent, reacting the metallocene compound with a porous carrier material at the temperature of-20-200 ℃ for 0.1-48 h, washing reactants by using the solvent, and drying the catalyst.
After full drying, the catalyst with good fluidity is obtained, and the catalyst is obtained in the presence of N2And (5) protecting for standby.
In the step (a), the activation temperature is 200-900 ℃, and the activation time is 0.5-48 hours. Preferably 300 ℃ and 800 ℃ for 1-8 hours. More preferably, the activation temperature is 400 ℃, and the activation time is 4-6 hours; the activation temperature is 600 ℃, the activation time is 3-4 hours or the activation temperature is 800 ℃, and the activation time is 2-3 hours.
The contacting vessel of the present invention is preferably under agitation to ensure good homogeneity of the system.
The term "porous support" is intended to mean any support material, preferably a porous material.
The porous carrier is inorganic oxide, inorganic chloride or organic load material. The organic supporting material is preferably a resinous material, and the resinous material is preferably a polyolefin or a prepolymer. The inorganic oxide is preferably silica gel. The inorganic chloride is preferably magnesium chloride.
The support material is not active in olefin polymerization. Moreover, they can be partially or fully dehydrated.
The average particle size of the carrier is in the range of 10-1000 μm, and the surface area is in the range of 1-500m2Between/g, the porosity ranges between 0.1 and 2ml/g, the porosity excluding macropores, i.e. pores with a diameter greater than 10 μm. The support pore size, expressed as the average diameter of the pores, ranges between 0.01 and 2 μm.
When the inorganic oxide is silica gel or alumina, the porosity is 0.9-1.7 ml/g. When a porous prepolymer is used as support material, the porosity is preferably higher than 0.3 ml/g. The prepolymer having a higher numerical porosity is preferably greater than 0.7ml/g, more preferably greater than 1.5 ml/g.
The porous support is heat treated to remove adsorbed water. This drying treatment is carried out at 80-300 deg.C, preferably at 100-200 deg.C. Drying is preferably carried out under reduced pressure and/or under an inert gas, preferably nitrogen or neon. The porous support was treated at 200-1000 ℃ to adjust the concentration of OH groups on the surface.
The active component Zr of the catalyst porous carrier accounts for 0.01-10% of the weight of the porous carrier.
The cocatalyst is a compound that can form a cation. The cation-forming compound is preferably an aluminoxane, a strong uncharged Lewis acid, an ionic compound with Lewis-acid cations or an ionic compound with a Bronsted acid as cation. The cation-forming compounds are also referred to as metallocene cation-forming compounds.
The cation-forming compound can react with the metallocene compound to convert the metallocene compound to a cationic compound.
The cocatalyst is preferably MAO solution.
The alumoxanes are preferably those described in WO 00/31090.
The aluminoxane is an open-chain or cyclic aluminoxane compound or a modified aluminoxane compound of the formula (1) or (2):
wherein,
R21is C1-C4Alkyl, preferably methyl or ethyl, and m is an integer from 5 to 30, preferably from 10 to 25.
These oligomeric aluminoxane compounds are usually prepared by reacting a trialkylaluminum solution with water. The oligomeric aluminoxane compounds obtained in this way are mixtures of linear and cyclic chain molecules of various lengths, so that m is an average value. The aluminoxane compounds can also be present in admixture with other metal alkyls.
Wherein part of the hydrocarbon groups or hydrogen atoms in the alkylaluminum compound are replaced by alkoxy groups, aryloxy groups, siloxy groups or amide groups to form a modified alkylaluminum compound.
Wherein the atomic ratio of the aluminum atom in the aluminoxane compound to the transition metal of the metallocene compound is 10:1 to 1000:1, preferably 20:1 to 700:1, more preferably 30:1 to 500: 1.
The structure of the metallocene compound is shown in a formula (3).
Wherein M is a transition metal belonging to groups III, IV, V, VI of the periodic Table of the elements, the lanthanide series or the osmium series; preferably M is titanium, zirconium or hafnium;
x, which may be identical OR different, are a hydrogen atom, a halogen atom, R, OR, OSO2CF3、OCOR、SR、NR2Or PR2Group, wherein R is a linear or branched, cyclic or acyclic C1-C40Alkyl radical, C2-C40Alkenyl radical(alkenyl)、C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group; preferably containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; preferably R is a straight or branched chain C1-C20An alkyl group; OR two X can optionally form a substituted OR unsubstituted butadienyl group OR an OR 'O group, wherein R' is selected from C1-C40Alkylene radical, C6-C40Arylene radical, C7-C40Alkylarylene or C7-C40A divalent radical of an arylalkylene group; preferably X is a hydrogen atom, a halogen atom or an R group; more preferably X is chlorine or Cl-C10An alkyl group; preferably methyl or ethyl.
L is a divalent C optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements1-C40A hydrocarbon group or a divalent silylene group (silylidene) containing up to 5 silicon atoms; preferably L is a divalent bridging group which is C1-C40Alkylene radical, C3-C40Cycloalkylene radical, C6-C40Arylene radical, C7-C40Alkylarylene or C7-C40Arylalkylene optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements, and silylene groups containing up to 5 silicon atoms, preferably SiMe2，SiPh2(ii) a Preferably L is a group (Z (R')2)nWherein Z is a carbon or silicon atom, n is 1 or 2, R' is C optionally containing a heteroatom belonging to groups 13-17 of the periodic Table of the elements1-C20A hydrocarbyl group; preferably R' is a linear or branched, cyclic or acyclic C1-C20Alkyl radical, C2-C20Alkenyl radical C2-C20Alkynyl, C6-C20Aryl radical, C7-C20Alkylaryl or C7-C20Arylalkyl optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; more preferably (Z (R')2)nThe radical being Si (CH)3)2，SiPh2，SiPhMe，SiMe(SiMe3)、CH2，(CH2)2And C (CH)2)2(ii) a More preferably ((Z (R')2)nIs Si (CH)3)2。
R1And R5Is C optionally containing a heteroatom belonging to groups 13-17 of the periodic Table of the elements1-C40A hydrocarbon group; preferably R1And R5Is straight-chain, branched, cyclic or acyclic C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group; optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; more preferably, R1And R5Is straight or branched, saturated or unsaturated C1-C20An alkyl group.
R2、R3And R4Equal to or different from each other, is a hydrogen atom or C optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements1-C40A hydrocarbyl group; preferably, R2、R3And R4Is a hydrogen atom or a linear, branched, cyclic or acyclic C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group; optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; more preferably, R2、R3And R4Is a hydrogen atom or C1-C20An alkyl group.
R6、R7、R8、R9And R10Equal to or different from each other, is a hydrogen atom or C optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements1-C40A hydrocarbyl group; preferably, R6、R7、R8、R9And R10Equal to or different from each other, are hydrogen atoms or linear or branched, cyclicOr acyclic C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group; optionally containing heteroatoms belonging to groups 13-17 of the periodic Table of the elements; more preferably, R6、R7、R8、R9And R10C in which at least one is a heteroatom of groups 13 to 17 of the periodic Table of the elements1-C40A hydrocarbyl group; preferably R6、R7、R8、R9And R10 is a hydrogen atom, preferably R8 is Cl-C40 alkyl, more preferably R8 is Cl-C40 alkyl, wherein the atom at the α -position is a secondary or tertiary carbon, preferably isopropyl or tert-butyl.
The metallocene polypropylene catalyst is preferably dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride.
The metallocene polypropylene catalyst is fixed on a carrier to obtain a supported metallocene polypropylene catalyst, and the active centers cannot be close to each other, so bimolecular association inactivation cannot occur, the consumption of MAO is greatly reduced, β -H elimination is reduced, the relative molecular mass of the polymer is improved, and the production cost is reduced.
On the other hand, slurry polymerization and gas phase polymerization are carried out after the catalyst is supported, and the existing olefin polymerization industrial equipment can be fully utilized.
In addition, since the carrier has a good particle morphology, the polymer prepared by the replication phenomenon also has a good morphology and a large bulk density. The amorphous and porous silica gel has high specific surface area, good mechanical property and reaction inertia, is an ideal carrier for loading the metallocene polypropylene catalyst, and the loading mechanism of the amorphous and porous silica gel is shown as a formula (4):
the present invention is an improved support of catalyst components on porous materials.
The preparation method of the metallocene polypropylene catalyst comprises the following steps:
(a) the catalyst porous silica gel carrier is activated at high temperature of 900 ℃ under the condition of inert gas, the activation temperature is 200 ℃ and the activation time is 0.5-48 hours. Preferably 300 ℃ and 800 ℃ for 1-8 hours. More preferably, the activation temperature is 400 ℃, the activation time is 4-6 hours, or the activation temperature is 600 ℃, the activation time is 3-4 hours, or the activation temperature is 800 ℃, and the activation time is 2-3 hours.
(b) Adding the porous silica gel carrier material into a contact container under the protection of nitrogen, and adding a certain amount of solvent to disperse the porous silica gel carrier material;
(c) adding a cocatalyst into a contact container, reacting with a porous silica gel carrier material at-20-200 ℃ for 0.1-48 h, and washing reactants for 3 times by using a solvent;
(d) dissolving a metallocene compound in a solvent, adding the solution into a contact container, reacting the solution with a porous silica gel carrier material at the temperature of-20-200 ℃ for 0.1-48 h, washing the reactant for 3 times by using the solvent, and drying the catalyst.
After full drying, the catalyst with good fluidity is obtained, and the catalyst is obtained in the presence of N2And (5) protecting for standby.
The polymerization conditions for preparing propylene by using the catalyst of the present invention are-60-300 ℃ and 0.5-3000 bar pressure. Preference is given to temperatures of from 50 to 200 ℃ and in particular from 60 to 100 ℃ and pressures of from 5 to 100 bar, more preferably from 15 to 70 bar. The mean residence time is from 0.5 to 5 hours, preferably from 0.5 to 3 hours. The molar mass regulator used is preferably hydrogen and the additive is preferably an antistatic.
The process of the invention results in a catalyst system with high activity without adversely affecting the polymer morphology.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the metallocene polypropylene catalyst of the invention improves the polymerization activity of propylene, can overcome the defects of the prior art, has higher catalytic activity of olefin polymerization, reduces the production cost of polymerization products, greatly reduces the dosage of MAO, simultaneously reduces β -H elimination, improves the relative molecular mass of polymers, reduces the production cost, on the other hand, carries out slurry and gas phase polymerization after the catalyst is loaded, can fully utilize the prior olefin polymerization industrial device, in addition, because the carrier has better particle shape, the polymers prepared by replication phenomenon also have better shape and larger bulk density, amorphous and porous silica gel has high specific surface area, good mechanical property and reaction inertia,
Detailed Description
The present invention will be further described with reference to the following examples.
The polymerization evaluation method used in the following examples was:
the polymerization was carried out in a 4L polymerization kettle. Nitrogen purge before polymerization. Adding an impurity removing agent under the protection of nitrogen, adding the impurity removing agent into a reaction kettle together with propylene, then adding a catalyst into the reaction kettle, heating to a specified temperature, starting a polymerization reaction, and polymerizing for 2 hours. The polymerization activity is expressed in grams of polymer/(grams of catalyst per hour) (gPP. gcat-1. h-1).
The manufacturer of D955 is Grace.
Comparative example 1
20g of D955 silica gel is activated at 400 ℃ for 1 hour under nitrogen.
1g of activated silica gel was weighed accurately, 27mmol of MAO solution was added, stirred at 50 ℃ for 2h, and then the solid portion was washed 3 times with 20ml of toluene to obtain MAO-modified SiO 2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, and the mixture was stirred at room temperature for 2 hours, and the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT1 (amount of supported zirconium: 5mgZr/gSiO 2).
Comparative example 2
20g of D955 silica gel is activated at 400 ℃ for 2 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT2 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Comparative example 3
20g of D955 silica gel is activated at 400 ℃ for 3 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT3 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 1
20g of D955 silica gel is activated at 400 ℃ for 4 hours under nitrogen.
1g of activated silica gel was weighed accurately, 27mmol of MAO solution was added, stirred at 50 ℃ for 2h, and then the solid portion was washed 3 times with 20ml of toluene to obtain MAO-modified SiO 2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, and the mixture was stirred at room temperature for 2 hours, and the solid portion was washed with 20ml of toluene 3 times, and dried at room temperature to remove the solvent, whereby CAT4 (amount of supported zirconium: 5mgZr/gSiO2) as a supported catalyst was obtained.
Example 2
20g of D955 silica gel is activated at 400 ℃ for 5 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT5 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 3
20g of D955 silica gel is activated at 400 ℃ for 6 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT6 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Comparative example 4
20g of D955 silica gel is activated at 600 ℃ for 1 hour under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solutionThe solution was stirred at 50 ℃ for 2h, and then the solid portion was washed 3 times with 20ml toluene to give MAO-modified SiO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT7 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Comparative example 5
20g of D955 silica gel is activated at 600 ℃ for 2 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT8 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 4
20g of D955 silica gel is activated at 600 ℃ for 3 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT9 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 5
20g of D955 silica gel is activated at 600 ℃ for 4 hours under nitrogen.
Accurately weighing living thingsDissolving silica gel 1g, adding 27mmol MAO solution, stirring at 50 deg.C for 2h, and washing the solid part with 20ml toluene 3 times to obtain MAO modified SiO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT10 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Comparative example 6
20g of D955 silica gel is activated at 800 ℃ for 1 hour under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT11 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 6
20g of D955 silica gel is activated at 800 ℃ for 2 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT12 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Example 7
20g of D955 silica gel is activated at 800 ℃ for 3 hours under nitrogen.
Accurately weighing 1g of activated silica gel, adding 27mmol of MAO solution, stirring at 50 ℃ for 2h, and washing the solid part with 20ml of toluene for 3 times to obtain SiO modified by MAO2. 20ml of toluene was added, then dimethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium dichloride was added, stirring was carried out at room temperature for 2 hours, the solid portion was washed with 20ml of toluene 3 times, and the solvent was removed at room temperature to obtain a supported catalyst CAT13 (amount of supported zirconium: 5 mgZr/gSiO)2)。
Polymerisation process
Comparative examples 1-6, examples 1-7 catalysts were evaluated for performance according to the polymerization method described below.
10mmol TEA and 1200g of liquid propylene were charged to a 4L stainless steel jacketed kettle equipped with a magnetically driven stirrer and catalyst feeder. After stirring for 10 minutes, a total of 100mg of CAT3 was added via a catalyst feeder, and then polymerization was carried out at a constant temperature of 60 ℃ for 2 hours while controlling the polymerization temperature. Then the stirring was discontinued, the pressure in the kettle was vented and the polymer collected. The polymer was dried in a vacuum oven at 70 ℃ under vacuum.
The polymerization evaluation results are preferably shown in Table 1.
TABLE 1 polymerization evaluation results
Claims (10)
1. A process for preparing the metallocene polypropylene catalyst includes high-temp activating the porous carrier of catalyst at 200-900 deg.C for 0.5-48 hr under the action of inert gas.
2. The method for preparing a metallocene polypropylene catalyst according to claim 1, wherein the porous support is an inorganic oxide, an inorganic chloride or an organic supporting material.
3. The method for preparing a metallocene polypropylene catalyst according to claim 2, wherein the organic supporting material is a resin material, the inorganic oxide is preferably silica gel, and the inorganic chloride is preferably magnesium chloride.
4. The method for preparing a metallocene polypropylene catalyst according to claim 1, wherein the porous support has an average particle size ranging from 10 to 1000 μm and a surface area ranging from 1 to 500m2Between/g, the porosity ranges between 0.1 and 2 ml/g.
5. The method for preparing a metallocene polypropylene catalyst according to claim 1, comprising the steps of:
(a) carrying out high-temperature activation on the catalyst porous carrier under the condition of inert gas;
(b) under the protection of nitrogen, a porous carrier material is added;
(c) reacting the cocatalyst with the porous carrier material at-20-200 ℃ for 0.1-48 h, and then washing the reactant by using a solvent;
(d) dissolving a metallocene compound in a solvent, reacting the metallocene compound with a porous carrier material at the temperature of-20-200 ℃ for 0.1-48 h, washing reactants by using the solvent, and drying the catalyst.
6. The process for preparing a metallocene polypropylene catalyst according to claim 5, wherein the cocatalyst is an aluminoxane, a strong uncharged Lewis acid, an ionic compound with a Lewis acid cation or an ionic compound with a Bronsted acid as cation.
7. The method for preparing metallocene polypropylene catalyst according to claim 6, wherein the aluminoxane is represented by the formula (1)
An open-chain or cyclic aluminoxane compound or modified aluminoxane compound of (1) or (2):
wherein,
R21is C1-C4Alkyl, preferably methyl or ethyl, and m is an integer from 5 to 30.
8. The method for preparing a metallocene polypropylene catalyst according to claim 7, wherein the atomic ratio of the aluminum atom in the aluminoxane compound to the transition metal in the metallocene compound is 10:1 to 1000: 1.
9. The method of claim 1, wherein the metallocene polypropylene catalyst is prepared by metallocene polymerization
The structure of the compound is shown in formula (3).
Wherein M is titanium, zirconium or hafnium;
x is hydrogen atom, halogen atom, R, OR, OSO2CF3、OCOR、SR、NR2Or PR2A group.
L is a divalent bridging group which is C1-C40Alkylene radical, C3-C40Cycloalkylene radical, C6-C40Arylene radical, C7-C40Alkylarylene or C7-C40An arylalkylene group;
R1and R5Is C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group;
R2、R3and R4Is a hydrogen atom or C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group;
R6、R7、R8、R9and R10Is a hydrogen atom or C1-C40Alkyl radical, C2-C40Alkenyl radical, C1-C40Alkynyl, C6-C40Aryl radical, C7-C40Alkylaryl or C7-C40An arylalkyl group; r8Is Cl-C40Alkyl, wherein the atom at position α -is a secondary or tertiary carbon, preferably isopropyl or tert-butyl.
10. The method for preparing a metallocene polypropylene catalyst according to claim 1, wherein the polymerization conditions for preparing propylene using the metallocene polypropylene catalyst are-60 to 300 ℃ and 0.5 to 3000 bar.
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