Active carrier, supported metallocene catalyst, preparation method and application

Abstract

The invention provides an active carrier, a supported metallocene catalyst, a preparation method and application. The invention relates to an active carrier, which is used for loading a metallocene compound to form a loaded metallocene catalyst, and comprises a carrier body and an ether-modified aluminoxane compound loaded on the carrier body, the ether-modified aluminoxane compound is modified with at least one of an alkyl ether having an alkyl carbon chain having 10 or more carbon atoms and a crown ether. The aluminoxane compound is modified by ether, so that the usage amount of the aluminoxane compound when the active carrier is used for preparing the supported metallocene catalyst can be reduced, the preparation cost of the supported metallocene catalyst is further reduced, and the supported metallocene catalyst can maintain relatively high catalytic activity.

Description

[0001] TECHNICAL FIELD

[0002] The present application relates to the technical field of olefin polymerization catalyst synthesis, and in particular to an active carrier, a supported metallocene catalyst, a preparation method and application. BACKGROUND

[0003] Metallocene catalyst is a new generation of olefin polymerization catalyst after Zigeler-Natta catalyst. Due to its high catalytic activity and excellent polymer structure regulation ability, it is widely used in the preparation of polyolefin products, especially in the research and production of linear high / low density polyethylene, polypropylene and polyolefin elastomer. Metallocene catalyst has high application value. Compared with traditional Ziegler-Natta catalyst, metallocene catalyst has a single active catalytic center, so the molecular weight distribution of the polymer is narrow, and the polyethylene prepared by the metallocene catalyst is widely used in the preparation of plastic films with higher strength. In addition, metallocene catalyst can regulate the microstructure of the polymer by adjusting the ligand structure.

[0004] Alkyl aluminoxane is often used as a cocatalyst for supported metallocene catalyst. Alkyl aluminoxane and metallocene complex are supported on a carrier. Alkyl aluminoxane activates the main catalyst (such as Zr, Ti, Hf metallocene complex) through alkylation reaction to generate a transition metal-carbon bond structure with catalytic activity, thereby starting the olefin polymerization chain growth reaction.

[0005] In the prior art, the amount of alkyl aluminoxane required for the supported metallocene catalyst for olefin polymerization is high, which not only increases the production cost of polyolefin, but also limits the supply of high-end polyolefin products due to the serious global shortage of alkyl aluminoxane, and there is a large amount of ash in the polyolefin product. SUMMARY

[0006] The first aspect of the present application provides an active carrier for loading a metallocene compound to form a supported metallocene catalyst, the active carrier comprising a carrier body and an ether-modified aluminoxane compound supported on the carrier body, the ether-modified aluminoxane compound being modified by at least one of an alkyl ether and a crown ether having a carbon number of 10 or more including an alkyl carbon chain.

[0007] In some optional embodiments of the first aspect of the present application, the carrier body is a silica gel carrier, and the active carrier has an Al-C vibration peak at 689±2 cm -1 .

[0008] In some optional embodiments of the first aspect of the present application, the active carrier has an Al-C vibration peak at 1079±2 cm -1 and 459±2 cm -1a vibration peak of the Si-O-Si vibration peak of the carrier body.

[0009] In some optional embodiments of the first aspect of the present application, the mass ratio of the ether-modified aluminoxane compound to the silica carrier is 0.5-10:1-30.

[0010] In some optional embodiments of the first aspect of the present application, the mass ratio of the ether-modified aluminoxane compound to the silica carrier is 0.5-5:10-20.

[0011] The second aspect of the present application provides a supported metallocene catalyst, the supported metallocene catalyst comprising the active carrier as claimed in the first aspect of the present application and a metallocene complex supported on the active carrier, the mass ratio of the metallocene complex to the active carrier being 1:10-1000.

[0012] In some optional embodiments of the second aspect of the present application, the mass ratio of the metallocene complex to the active carrier is 1:10-500.

[0013] The supported metallocene catalyst provided by the second aspect of the present application has high catalytic activity for olefin polymerization and low preparation cost.

[0014] The third aspect of the present application provides a preparation method of a supported metallocene catalyst, comprising:

[0015] Step S10: pretreating the carrier to obtain an active carrier, in an inert atmosphere, mixing a carrier body, a first organic medium and an ether-modified aluminoxane compound to obtain a slurry, stirring the slurry at a first temperature T1 for a first time length t1, after the reaction, performing solid-liquid separation, washing and drying to obtain the active carrier, the first temperature T1 being 20-180°C, and the first time length t1 being 1-24h;

[0016] Step S20: in an inert atmosphere, adding a metallocene complex solution to the active carrier to obtain the supported metallocene catalyst by an impregnation method.

[0017] In some optional embodiments of the third aspect of the present application, in step S10, the carrier body is a silica carrier, and step S10 comprises:

[0018] Step S11: the carrier body is subjected to a thermal activation treatment, the thermal activation treatment comprising, in an inert protective atmosphere, heat treating the carrier body at 100-800°C under normal pressure or 10-10 3 Pa under reduced pressure for 1-36h.

[0019] In some optional embodiments of the third aspect of the present application, the thermal activation treatment temperature is 200-500°C.

[0020] In some optional embodiments of the third aspect of the present application, the particle size of the silica gel carrier is 1.0-80 μm, the pore volume of the silica gel carrier is 1.0-3.0 mL / g, the pore size of the silica gel carrier is 10-30 nm, and the specific surface area of the silica gel carrier is 150-850 m 2 / g.

[0021] In some optional embodiments of the third aspect of the present application, step S10 further comprises:

[0022] In step S12, the ether-modified aluminoxane compound is synthesized by mixing and stirring the aluminoxane compound and the ether compound in an inert atmosphere at a second temperature T2 for a second time length t2 to obtain the ether-modified aluminoxane compound, wherein the second temperature T2 is 0-100 ℃, and the second time length t2 is 1-24 h.

[0023] In some optional embodiments of the third aspect of the present application, in step S12, the mass ratio of the aluminoxane compound to the ether compound is 0.1-20:0.05-0.5.

[0024] In some optional embodiments of the third aspect of the present application, in step S12, the stirring speed is 100-3000 rpm.

[0025] In some optional embodiments of the third aspect of the present application, in step S10, the mass ratio of the ether-modified aluminoxane compound to the carrier body is 0.5-10:1-30, and preferably, the stirring speed of the slurry is 100-3000 rpm.

[0026] In some optional embodiments of the third aspect of the present application, step S10 further comprises:

[0027] In step S13, the carrier body is added with a first organic medium to form a mixture, and the ether-modified aluminoxane compound is added to the mixture to obtain a slurry.

[0028] In some optional embodiments of the third aspect of the present application, in step S20, the metallocene complex solution is added dropwise into the active carrier under the protection of an inert atmosphere to obtain a solid-liquid mixture, and the solid-liquid mixture is stirred at a third temperature T3 for a third time length t3, and then solid-liquid separation, washing and drying are performed to obtain the supported metallocene catalyst;

[0029] In some optional embodiments of the third aspect of the present application, in step S20, the metallocene complex solution is added dropwise into the active carrier under the protection of an inert atmosphere to obtain a solid-liquid mixture, and the solid-liquid mixture is stirred at a third temperature T3 for a third time length t3, and then solid-liquid separation, washing and drying are performed to obtain the supported metallocene catalyst;

[0030] In some optional embodiments of the third aspect of the present application, the mass ratio of the metallocene complex in the metallocene complex solution to the active carrier is 1:10-1000.

[0031] In some optional embodiments of the third aspect of the present application, the aluminoxane compound is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-butylaluminoxane and isopropylaluminoxane.

[0032] In some optional embodiments of the third aspect of the present application, the ether compound includes at least one of an alkyl ether having a carbon number of the alkyl carbon chain of 10 or more and a crown ether.

[0033] In some optional embodiments of the third aspect of the present application, the crown ether is selected from at least one of 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo-15-crown-5, cyclohexano-15-crown-5, cyclohexano-18-crown-6 and dicyclohexano-18-crown-6.

[0034] In some optional embodiments of the third aspect of the present application, the alkyl ether is selected from at least one of n-decyl ether, undecyl ether, dodecyl ether and hexadecyl ether.

[0035] In some optional embodiments of the third aspect of the present application, the first organic medium is selected from at least one of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether and n-hexane.

[0036] In some optional embodiments of the third aspect of the present application, the metallocene complex dissolved in the metallocene complex solution is selected from at least one of bis(cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, rac-ethylenebis(indenyl)zirconium dichloride, bis(tetrahydroindenyl)hafnium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, bis(tetrahydro-1-indenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium difluoride, bis(n-butylcyclopentadienyl)zirconium difluoride, rac-ethylenebis(indenyl)zirconium difluoride, bis(tetrahydroindenyl)hafnium difluoride, dimethylsilylbis(indenyl)zirconium difluoride, bis(tetrahydro-1-indenyl)zirconium difluoride, bis(cyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dimethyl, rac-ethylenebis(indenyl)zirconium dimethyl, bis(tetrahydroindenyl)hafnium dimethyl, dimethylsilylbis(indenyl)zirconium dimethyl and bis(tetrahydro-1-indenyl)zirconium dimethyl.

[0037] The fourth aspect of the present application provides a supported metallocene catalyst, which is prepared by the method for preparing a supported metallocene catalyst provided in the third aspect of the present application.

[0038] The fifth aspect of the present application provides an application of the supported metallocene catalyst of the first aspect of the present application or the supported metallocene catalyst of the fourth aspect of the present application, and the supported metallocene catalyst is used for catalyzing olefin homopolymerization and copolymerization.

[0039] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing olefin homopolymerization, under the protection of an inert atmosphere, a second organic medium is loaded into a reactor, an alkyl aluminum compound is added into the second organic medium as a cocatalyst, the supported metallocene catalyst is added into the second organic medium as a main catalyst, and an olefin polymerization monomer is transported into the reactor to carry out slurry polymerization, gas phase polymerization or solution polymerization to obtain an olefin homopolymer.

[0040] In some optional embodiments of the fifth aspect of the present application, the second organic medium is selected from at least one of n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran and dichloromethane.

[0041] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing ethylene and / or α-olefin polymerization, and the α-olefin is selected from at least one of propylene, 1-butene, 1-octene and 1-octene.

[0042] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing norbornene polymerization.

[0043] In some optional embodiments of the fifth aspect of the present application, the molecular weight of the olefin homopolymer is 500,000-1,400,000, and the molecular weight distribution PDI is 2.0-5.0.

[0044] Advantages:

[0045] The first aspect of the present application provides that the aluminoxane compound is modified by an ether in the active carrier, which can reduce the use amount of the aluminoxane compound when the supported metallocene catalyst is prepared by using the active carrier, and further reduce the preparation cost of the supported metallocene catalyst and is beneficial to keeping the supported metallocene catalyst with high catalytic activity. Moreover, the supported metallocene catalyst prepared by using the active carrier can effectively reduce the ash content in the polyolefin product when the supported metallocene catalyst is used for catalyzing olefin polymerization, and ensure the low-cost sufficient supply of high-end polyolefin products.

[0046] The second aspect of the present application provides the supported metallocene catalyst with high catalytic activity for olefin polymerization and low preparation cost.

[0047] The third aspect of the present application provides a preparation method of the supported metallocene catalyst, which uses ether compounds to modify aluminoxane compounds, so that the supported metallocene catalyst maintains high catalytic activity while reducing the amount of aluminoxane compounds used in the preparation process of the supported metallocene catalyst, thereby reducing the preparation cost of the supported metallocene catalyst, and the preparation method is simple to operate.

[0048] The fourth aspect of the present application provides the supported metallocene catalyst, which has high catalytic activity for olefin polymerization reaction and low preparation cost.

[0049] The fifth aspect of the present application provides an application of the supported metallocene catalyst. The supported metallocene catalyst provided by the second aspect of the present application is used in an olefin polymerization reaction, which can reduce the production cost of polyolefin and reduce the ash content in the polyolefin product. By adjusting the type and content of the ether compounds in the preparation process of the supported metallocene catalyst, the viscosity average molecular weight Mη and the molecular weight distribution PDI of the polyolefin product can be adjusted. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is the infrared spectrum of the active carrier, the silica gel carrier + methyl aluminoxane (MAO) and the silica gel carrier + methyl aluminoxane (MAO) + ether in Example 1 of the present application. DETAILED DESCRIPTION

[0051] The present application will be further described in detail below in combination with examples. It should be understood that the specific examples described herein are only used to explain the present application and not to limit the present application.

[0052] The first aspect of the present application provides an active carrier, which is used to load a metallocene compound to form a supported metallocene catalyst, and the active carrier comprises a carrier body and an ether-modified aluminoxane compound loaded on the carrier body, and the ether-modified aluminoxane compound is modified by at least one of an alkyl ether and a crown ether having a carbon number of 10 or more including an alkyl carbon chain.

[0053] In some optional embodiments of the first aspect of the present application, the carrier body is a silica gel carrier, and the active carrier has an Al-C vibration peak at 689±2 cm -1 .

[0054] In some optional embodiments of the first aspect of the present application, the active carrier has vibration peaks of Si-O-Si vibration peaks of the carrier body at 1079±2 cm -1 and 459±2 cm -1 .

[0055] In some optional embodiments of the first aspect of the present application, the mass ratio of the ether-modified aluminoxane compound to the silica gel carrier is 0.5-10:1-30.

[0056] In some optional embodiments of the first aspect of the present application, the mass ratio of the ether-modified aluminoxane compound to the silica carrier is 0.5-5:10-20.

[0057] The first aspect of the present application provides that the use of ether-modified aluminoxane compounds in active carriers can reduce the amount of aluminoxane compounds used when preparing supported metallocene catalysts using the active carriers, thereby reducing the preparation cost of the supported metallocene catalysts and facilitating the maintenance of high catalytic activity of the supported metallocene catalysts. Moreover, the supported metallocene catalysts prepared using the active carriers can effectively reduce the ash content in polyolefin products when catalyzing the polymerization of olefins, thereby ensuring the low-cost and sufficient supply of high-end polyolefin products.

[0058] The second aspect of the present application provides a supported metallocene catalyst, which comprises an active carrier as claimed in the first aspect of the claims and a metallocene complex supported on the active carrier, and the mass ratio of the metallocene complex to the active carrier is 1:10-1000.

[0059] In some optional embodiments of the second aspect of the present application, the mass ratio of the metallocene complex to the active carrier is 1:10-500.

[0060] The second aspect of the present application provides a supported metallocene catalyst with high catalytic activity for olefin polymerization and low preparation cost.

[0061] The third aspect of the present application provides a preparation method of a supported metallocene catalyst, which comprises:

[0062] Step S10: pretreating the carrier to obtain an active carrier, mixing the carrier body, a first organic medium and an ether-modified aluminoxane compound in an inert atmosphere to obtain a slurry, stirring the slurry at a first temperature T1 for a first time length t1, and obtaining the active carrier through solid-liquid separation, washing and drying after the reaction, wherein the first temperature T1 is 20-180°C, and the first time length t1 is 1-24 h.

[0063] Step S20: adding a metallocene complex solution to the active carrier in an inert atmosphere to obtain a supported metallocene catalyst by an impregnation method.

[0064] The preparation method of the supported metallocene catalyst provided by the third aspect of the present application uses ether compounds to modify aluminoxane compounds, so that the supported metallocene catalyst maintains high catalytic activity while reducing the amount of aluminoxane compounds used in the preparation process of the supported metallocene catalyst, thereby reducing the preparation cost of the supported metallocene catalyst, and the preparation method is simple to operate.

[0065] In some optional embodiments of the third aspect of the present application, in step S10, the carrier body is a silica gel carrier, and step S10 comprises:

[0066] Step S11: subjecting the carrier body to a thermal activation treatment, the thermal activation treatment comprising subjecting the carrier body to a heat treatment at 100-800°C under an inert protective atmosphere at normal pressure or 10-10 3 Pa under reduced pressure for 1-36 h.

[0067] In some optional embodiments of the third aspect of the present application, the thermal activation treatment temperature is 200-500°C.

[0068] In some optional embodiments of the third aspect of the present application, the silica gel carrier has a particle size of 1.0-80 μm, a pore volume of 1.0-3.0 mL / g, a pore size of 10-30 nm, and a specific surface area of 150-850 m 2 / g.

[0069] In some optional embodiments of the third aspect of the present application, step S10 further comprises:

[0070] Step S12: synthesizing an ether-modified aluminoxane compound, the aluminoxane compound and the ether compound being mixed and stirred at a second temperature T2 for a second time period t2 in an inert atmosphere to obtain the ether-modified aluminoxane compound, the second temperature T2 being 0-100°C, and the second time period t2 being 1-24 h.

[0071] In some optional embodiments of the third aspect of the present application, in step S12, the mass ratio of the aluminoxane compound to the ether compound is 0.1-20:0.05-0.5.

[0072] In some optional embodiments of the third aspect of the present application, in step S12, the stirring speed is 100-3000 rpm.

[0073] In some optional embodiments of the third aspect of the present application, in step S10: the mass ratio of the ether-modified aluminoxane compound to the carrier body is 0.5-10:1-30, and preferably, the stirring speed for stirring the slurry is 100-3000 rpm.

[0074] In some optional embodiments of the third aspect of the present application, step S10 further comprises:

[0075] Step S13: adding a first organic medium to the carrier body to form a mixture, and adding the ether-modified aluminoxane compound to the mixture to obtain a slurry.

[0076] In some optional embodiments of the third aspect of the present application, in the step S20, the metallocene complex solution is added dropwise into the active carrier under the protection of an inert atmosphere to obtain a solid-liquid mixture, the solid-liquid mixture is stirred at a third temperature T3 for a third time t3, and after the reaction, solid-liquid separation, washing, and drying are performed to obtain the supported metallocene catalyst;

[0077] The mass ratio of the metallocene complex in the metallocene complex solution to the active carrier is 1:1-10000, the third temperature T3 is 0-100°C, and the third time t3 is 1-48h.

[0078] In some optional embodiments of the third aspect of the present application, the mass ratio of the metallocene complex in the metallocene complex solution to the active carrier is 1:10-1000.

[0079] In some optional embodiments of the third aspect of the present application, the aluminoxane compound is selected from at least one of methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, and isopropylaluminoxane.

[0080] In some optional embodiments of the third aspect of the present application, the ether compound includes at least one of an alkyl ether and a crown ether having a carbon number of the alkyl carbon chain of 10 or more.

[0081] In some optional embodiments of the third aspect of the present application, the crown ether is selected from at least one of 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo-15-crown-5, cyclohexano-15-crown-5, cyclohexano-18-crown-6, and dicyclohexano-18-crown-6.

[0082] In some optional embodiments of the third aspect of the present application, the alkyl ether is selected from at least one of n-decyl ether, undecyl ether, dodecyl ether, and hexadecyl ether.

[0083] In some optional embodiments of the third aspect of the present application, the first organic medium is selected from at least one of tetrahydrofuran, diethyl ether, toluene, benzene, chloroform, dichloromethane, petroleum ether, and n-hexane.

[0084] In some optional embodiments of the third aspect of the present application, the dissolved metallocene complex in the metallocene complex solution is selected from at least one of bis(cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, rac-ethylenebis(indenyl)zirconium dichloride, bis(tetrahydroindenyl)hafnium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, bis(tetrahydro-1-indenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium difluoride, bis(n-butylcyclopentadienyl)zirconium difluoride, rac-ethylenebis(indenyl)zirconium difluoride, bis(tetrahydroindenyl)hafnium difluoride, dimethylsilylbis(indenyl)zirconium difluoride, bis(tetrahydro-1-indenyl)zirconium difluoride, bis(cyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dimethyl, rac-ethylenebis(indenyl)zirconium dimethyl, bis(tetrahydroindenyl)hafnium dimethyl, dimethylsilylbis(indenyl)zirconium dimethyl, and bis(tetrahydro-1-indenyl)zirconium dimethyl.

[0085] The fourth aspect of the present application provides a supported metallocene catalyst, which is prepared by the method for preparing a supported metallocene catalyst provided in the third aspect of the present application.

[0086] The supported metallocene catalyst provided in the fourth aspect of the present application has high catalytic activity for olefin polymerization and low preparation cost.

[0087] The fifth aspect of the present application provides an application of the supported metallocene catalyst of the first aspect of the present application or the supported metallocene catalyst of the fourth aspect of the present application, and the supported metallocene catalyst is used for catalyzing olefin homopolymerization and copolymerization.

[0088] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing olefin homopolymerization, and a second organic medium is loaded into a reactor under protection of an inert atmosphere, an alkyl aluminum compound is added into the second organic medium as a cocatalyst, the supported metallocene catalyst is added into the second organic medium as a main catalyst, and an olefin polymerization monomer is transported into the reactor to perform slurry polymerization, gas phase polymerization or solution polymerization to obtain an olefin homopolymer.

[0089] In some optional embodiments of the fifth aspect of the present application, the second organic medium is selected from at least one of n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran, and dichloromethane.

[0090] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing polymerization of ethylene and / or an α-olefin, and the α-olefin is selected from at least one of propylene, 1-butene, 1-octene, and 1-octene.

[0091] In some optional embodiments of the fifth aspect of the present application, the supported metallocene catalyst is used for catalyzing norbornene polymerization.

[0092] The fifth aspect of the present application provides the use of the supported metallocene catalyst. The use of the supported metallocene catalyst provided by the second aspect of the present application in the polymerization of olefins can reduce the production cost of polyolefins and can reduce the ash content in the polyolefin product. By adjusting the type and content of the ether compound in the preparation process of the supported metallocene catalyst, the viscosity average molecular weight Mη and the molecular weight distribution PDI of the polyolefin product can be adjusted.

[0093] In some optional embodiments provided by the fifth aspect of the present application, the molecular weight of the olefin homopolymer is 500,000-1,400,000, and the molecular weight distribution PDI is 2.0-5.0.

Specific embodiments

[0095] In the following, specific embodiments and comparative examples are given to more specifically illustrate the embodiments of the present application. Various tests and evaluations are carried out according to the following methods. In addition, unless otherwise specified, "parts" and "%" are mass-based.

[0096] I. Preparation of the supported metallocene catalyst

[0097]

Example 1

[0098] S10: Pretreatment of the carrier to obtain an active carrier:

[0099] S11: Place the silica gel carrier in an argon atmosphere furnace at 100°C and calcine for 2h under argon protection to obtain a thermally activated silica gel carrier;

[0100] S12: In an argon atmosphere, add 0.1g n-decyl ether to a 5mL methylaluminoxane solution in toluene (toluene as solvent, methylaluminoxane as solute, the same below), and stir at 30°C for 2h to obtain an ether-modified aluminoxane compound;

[0101] S13: In an argon atmosphere, add 20mL toluene to 10g of the thermally activated silica gel carrier, and then add the ether-modified aluminoxane compound to obtain a slurry solution, and stir at 30°C for 2h. Filter the reaction solution, wash the obtained solid after filtration with n-heptane 3 times, and vacuum dry to obtain an active carrier;

[0102] S20: Dissolve 0.1g bis(cyclopentadienyl)zirconium dichloride in toluene to obtain a metallocene complex solution, and add the metallocene complex solution dropwise to the active carrier under an inert atmosphere. Stir the obtained mixture at 30°C for 2h, stand, filter, and sequentially wash the obtained solid after filtration with toluene (20mL) and n-hexane (20mL) once, and vacuum dry for 2h to obtain the supported metallocene catalyst of Example 1.

[0103] The active support (silica gel + MAO + ether) obtained in step S10 of Example 1, the pure silica gel support, and the support (silica gel + MAO) in Comparative Example 1 below were subjected to infrared characterization. The infrared characterization instrument used was a Fourier transform infrared spectrometer, Spectrum Two, Perkin-Emer, USA. Infrared characterization method: Place the sample on the test platform, set the number of scans to 32, and adjust the resolution to 4 cm -1 .like Figure 1 As shown, at a wave number of 3336 cm -1 The signal peaks are attributed to the vibration peaks of the hydroxyl group OH on the surface of the silica gel carrier. The Si-O-Si vibration peaks of the silica gel carrier are located at 1090 cm -1 and 456cm -1 Generally, the Al-C vibration peak in MAO is located at a wave number of 700 cm -1 During the carrier treatment process, the reaction between MAO and the hydroxyl groups on the silica gel causes the Al-C vibration peak in the silica gel to shift to a lower wave number, with a wave number of 677 cm -1 The signal at 689 cm is attributed to the Al-C vibration peak in silica gel + MAO. -1 The signal at 1083 cm is attributed to the Al-C vibration peak of silica gel + MAO + ether. The Si-O-Si vibration peaks of silica gel + MAO are located at 1083 cm -1 and 457cm -1 The Si-O-Si vibration peaks of the active carrier (i.e. silica gel + MAO + ether) are located at 1079 cm -1 and 459cm -1 There is a vibration peak at the Si-O-Si vibration peak of the carrier body.

[0104] [Example 2]

[0105] S10: Pre-treating the carrier to obtain an active carrier:

[0106] S11: placing the silica gel support in an argon atmosphere furnace and calcining it at 150° C. for 2 h under argon protection to obtain a thermally activated support;

[0107] S12: In an inert atmosphere, 0.2 g of undecyl ether was added to 5 mL of a toluene solution of methylaluminoxane, and the mixture was stirred at 50° C. for 2 h to obtain an ether-modified aluminoxane compound;

[0108] S13: In an inert atmosphere, 20 mL of toluene was added to 10 g of the thermally activated support, and then an ether-modified aluminoxane compound was added to obtain a slurry. The mixture was stirred at 50° C. for 2 h. The reaction solution was filtered, and the solid obtained after filtration was washed three times with n-heptane and dried in vacuo to obtain an active support.

[0109] S20: 0.2 g of bis(n-butylcyclopentadienyl)zirconium dichloride was dissolved in toluene to obtain a metallocene complex solution, the metallocene complex solution was added dropwise into the active carrier under an inert atmosphere, the obtained mixture was stirred at 30°C for 2 h, stood for a while, filtered, the obtained solid was washed once with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 2.

[0110] Example 3

[0111] S10: pretreatment of the carrier to obtain an active carrier:

[0112] S11: the silica gel carrier was placed in an atmosphere furnace with argon gas, calcined at 200°C under argon protection for 2 h to obtain a thermally activated carrier;

[0113] S12: under an argon atmosphere, 0.3 g of dodecyl ether was added to a 10 mL methylaluminoxane solution in toluene, and stirred at 50°C for 2 h to obtain an ether-modified aluminoxane compound;

[0114] S13: under an argon atmosphere, 20 mL of toluene was added to 10 g of the thermally activated carrier, and then the ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 50°C for 2 h; the reaction solution was filtered, and the obtained solid was washed with n-heptane for 3 times and dried under vacuum to obtain an active carrier;

[0115] S20: 0.3 g of rac-ethylene bis(indenyl)zirconium dichloride was dissolved in toluene to obtain a metallocene complex solution, the metallocene complex solution was added dropwise into the active carrier under an inert atmosphere, the obtained mixture was stirred at 40°C for 2 h, stood for a while, filtered, the obtained solid was washed once with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 3.

[0116] Example 4

[0117] S10: pretreatment of the carrier to obtain an active carrier:

[0118] S11: the silica gel carrier was placed in an atmosphere furnace with argon gas, calcined at 250°C under argon protection for 4 h to obtain a thermally activated carrier;

[0119] S12: under an argon atmosphere, 0.4 g of hexadecyl ether was added to a 10 mL methylaluminoxane solution in toluene, and stirred at 60°C for 2 h to obtain an ether-modified aluminoxane compound;

[0120] S13: Under argon atmosphere, 20 mL of toluene was added to 10 g of the thermally activated support, and then an ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 70 °C for 2 h; the reaction solution was filtered, and the obtained solid was washed with n-heptane for 3 times, and dried under vacuum to obtain the active support;

[0121] S20: A metallocene complex solution was prepared by dissolving 0.4 g of bis(tetrahydroindenyl)hafnium dichloride in toluene, and the metallocene complex solution was added dropwise into the active support under inert atmosphere, and the obtained mixture was stirred at 40 °C for 3 h, and then was allowed to stand for a while, and was filtered, and the obtained solid was washed with toluene (20 mL) and n-hexane (20 mL) in sequence, and was dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 4.

[0122]

Example 5

[0123] S10: The support was pretreated to obtain an active support:

[0124] S11: The silica gel support was placed in an atmosphere furnace with argon flowing in, and was calcined at 300 °C under argon protection for 4 h to obtain a thermally activated support;

[0125] S12: Under argon atmosphere, 0.5 g of 12-crown-4 was added to 10 mL of a methylaluminoxane toluene solution, and the mixture was stirred at 70 °C for 3 h to obtain an ether-modified aluminoxane compound;

[0126] S13: Under argon atmosphere, 20 mL of toluene was added to 10 g of the thermally activated support, and then an ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 70 °C for 2 h; the reaction solution was filtered, and the obtained solid was washed with n-heptane for 3 times, and dried under vacuum to obtain the active support;

[0127] S4: A metallocene complex solution was prepared by dissolving 0.5 g of dimethylsilyl bis(indenyl)zirconium dichloride in toluene, and the metallocene complex solution was added dropwise into the active support under inert atmosphere, and the obtained mixture was stirred at 50 °C for 3 h, and then was allowed to stand for a while, and was filtered, and the obtained solid was washed with toluene (20 mL) and n-hexane (20 mL) in sequence, and was dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 5.

[0128]

Example 6

[0129] S10: The support was pretreated to obtain an active support:

[0130] S11: The silica gel support was placed in an atmosphere furnace with argon flowing in, and was calcined at 400 °C under argon protection for 2 h to obtain a thermally activated support;

[0131] S12: Under argon atmosphere, 0.6 g of 15-crown-5 was added into 5 mL of ethylaluminoxane solution in toluene, and the reaction was stirred at 80°C for 3 hours to obtain an ether-modified aluminoxane compound;

[0132] S13: Under argon atmosphere, 20 mL of toluene was added into 10 g of the heat-activated carrier, and then the ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 80°C for 2 hours; the reaction solution was filtered, and the obtained solid was washed with n-heptane for 3 times and dried under vacuum to obtain the active carrier;

[0133] S20: 0.6 g of bis(tetrahydro-1-indenyl)zirconium dichloride was dissolved in toluene to obtain a metallocene complex solution, which was added dropwise into the active carrier under inert atmosphere, and the obtained mixture was stirred at 60°C for 3 hours, and then was allowed to stand for a while, filtered, and the obtained solid was washed with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 hours to obtain the supported metallocene catalyst of Example 6.

[0134]

Example 7

[0135] S10: The carrier was pretreated to obtain an active carrier:

[0136] S11: The silica gel carrier was placed in an argon atmosphere furnace, and was calcined at 500°C under argon protection for 2 hours to obtain a heat-activated carrier;

[0137] S12: Under argon atmosphere, 0.7 g of 18-crown-6 was added into 10 mL of ethylaluminoxane solution in toluene, and the reaction was stirred at 80°C for 3 hours to obtain an ether-modified aluminoxane compound;

[0138] S13: Under argon atmosphere, 20 mL of toluene was added into 10 g of the heat-activated carrier, and then the ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 90°C for 2 hours; the reaction solution was filtered, and the obtained solid was washed with n-heptane for 3 times and dried under vacuum to obtain the active carrier;

[0139] S20: 0.7 g of bis(cyclopentadienyl)zirconium difluoride was dissolved in toluene to obtain a metallocene complex solution, which was added dropwise into the active carrier under inert atmosphere, and the obtained mixture was stirred at 60°C for 3 hours, and then was allowed to stand for a while, filtered, and the obtained solid was washed with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 hours to obtain the supported metallocene catalyst of Example 7.

[0140]

Example 8

[0141] S10: The carrier was pretreated to obtain an active carrier:

[0142] S11: The silica gel carrier was placed in an atmosphere furnace with argon gas, and calcined at 600°C under argon protection for 2h to obtain a thermally activated carrier;

[0143] S12: In an argon atmosphere, 0.7g of benzo-12-crown ether-4 was added to a 20mL solution of ethylaluminoxane in toluene, and stirred at 90°C for 3h to obtain an ether-modified aluminoxane compound;

[0144] S13: In an argon atmosphere, 20mL of toluene was added to 10g of the thermally activated carrier, and then the modified organoaluminum compound was added to obtain a slurry solution, which was stirred at 100°C for 2h. The reaction solution was filtered, and the solid obtained by filtration was washed with n-heptane three times and vacuum dried to obtain an active carrier;

[0145] S20: 0.8g of rac-ethylenebis(indenyl)zirconium difluoride was dissolved in toluene to obtain a metallocene complex solution, which was added dropwise to the active carrier under an inert atmosphere. The resulting mixture was stirred at 60°C for 3h, and then allowed to stand for a while. The solid obtained by filtration was washed with toluene (20mL) and n-hexane (20mL) in sequence, and then dried under vacuum for 2h to obtain the supported metallocene catalyst of Example 8.

[0146]

Example 9

[0147] S10: The carrier was pretreated to obtain an active carrier:

[0148] S11: The silica gel carrier was placed in an atmosphere furnace with argon gas, and calcined at 700°C under argon protection for 2h to obtain a thermally activated carrier;

[0149] S12: In an argon atmosphere, 0.9g of benzo-15-crown ether-5 was added to a 30mL solution of ethylaluminoxane in toluene, and stirred at 90°C for 3h to obtain an ether-modified aluminoxane compound;

[0150] S13: In an argon atmosphere, 20mL of toluene was added to 10g of the thermally activated carrier, and then the ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred at 120°C for 2h. The reaction solution was filtered, and the solid obtained by filtration was washed with n-heptane three times and vacuum dried to obtain an active carrier;

[0151] S20: 0.8 g of bis(tetrahydroindenyl)hafnium difluoride was dissolved in toluene to obtain a metallocene complex solution, the metallocene complex solution was added dropwise into the active carrier under an inert atmosphere, the obtained mixture was stirred and reacted at 60°C for 3 h, stood for a while, filtered, the obtained solid was washed once with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 9.

[0152] [Example 10]

[0153] S10: The carrier was pretreated to obtain an active carrier:

[0154] S11: The silica gel carrier was placed in an argon atmosphere furnace and calcined at 800°C under argon protection for 2 h to obtain a thermally activated carrier;

[0155] S12: In an argon atmosphere, 1.0 g of cyclohexane-15-crown-5 was added to a toluene solution of 40 mL of ethylaluminoxane, and stirred and reacted at 90°C for 3 h to obtain an ether-modified aluminoxane compound;

[0156] S13: In an argon atmosphere, 20 mL of toluene was added to 10 g of the thermally activated carrier, and then the ether-modified aluminoxane compound was added to obtain a slurry solution, which was stirred and reacted at 150°C for 2 h, the reaction solution was filtered, the obtained solid was washed with n-heptane for 3 times, and dried under vacuum to obtain an active carrier;

[0157] S20: 0.8 g of bis(tetrahydroindenyl)hafnium difluoride was dissolved in toluene to obtain a metallocene complex solution, the metallocene complex solution was added dropwise into the active carrier under an inert atmosphere, the obtained mixture was stirred and reacted at 60°C for 3 h, stood for a while, filtered, the obtained solid was washed once with toluene (20 mL) and n-hexane (20 mL) in sequence, and dried under vacuum for 2 h to obtain the supported metallocene catalyst of Example 9.

[0158] [Comparative Example 1]

[0159] Comparative Example 1 differs from Example 1 in that no n-decane ether is added in step S12. The rest is the same as Example 1, and the catalyst of Comparative Example 1 is obtained.

[0160] [Comparative Example 2]

[0161] Comparative Example 2 differs from Comparative Example 1 in that the volume of the methylaluminoxane toluene solution in S12 is adjusted to 50 mL. The rest is the same as Comparative Example 1, and the catalyst of Comparative Example 2 is obtained.

[0162] The raw materials, preparation conditions and yields of the catalysts of the comparative examples and examples are summarized in Table 1.

[0163] Table 1 Summary of raw materials, preparation conditions and yields of supported metallocene catalysts of each comparative example and example

[0164]

[0165]

[0166] *Indicates: the ratio in the comparative example is the mass ratio of aluminoxane compound to silica gel carrier.

[0167] II. Performance test of supported metallocene catalyst

[0168]

Example 1 catalytic olefin polymerization reaction test

[0169] Under nitrogen protection, 350 mL of n-heptane and 0.5 g of triethylaluminum were added to a stainless steel polymerization kettle, the kettle liquid temperature was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 1 was weighed and suspended in n-heptane, then the suspension was added to the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered to obtain a white solid, and the white solid was vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 1 for ethylene homopolymerization reaction was calculated according to the mass of the product polyethylene.

[0170]

Example 2 catalytic olefin polymerization reaction test

[0171] Under nitrogen protection, 350 mL of n-heptane and 0.5 g of triethylaluminum were added to a stainless steel polymerization kettle, the kettle liquid temperature was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 1 was weighed and suspended in n-heptane, then the suspension was added to the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered to obtain a white solid, and the white solid was vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 1 for ethylene homopolymerization reaction was calculated according to the mass of the product polyethylene.

[0172]

Example 3 catalytic olefin polymerization reaction test

[0173] Under nitrogen, 350 mL of n-heptane and 1.0 g of triethylaluminum were added to a stainless steel polymerization kettle. The kettle temperature was adjusted to 70°C and maintained stable. 10.0 mg of the supported metallocene catalyst from Example 3 was weighed and suspended in the n-heptane. The suspension was then added to the reactor. The ethylene pressure was quickly adjusted to 1.0 MPa and a timer was started. The ethylene pressure was kept constant during the polymerization process. After 2 hours of reaction, the ethylene gas was stopped and the ethylene gas in the polymerization kettle was slowly released. The reaction mixture was filtered to obtain a white solid, which was then vacuum-dried to a constant weight to obtain the product polyethylene. The mass, viscosity-average molecular weight (Mη), molecular weight distribution (PDI), and ash content of the product polyethylene were tested, and the catalytic activity of the supported metallocene catalyst from Example 3 for ethylene homopolymerization was calculated based on the mass of the obtained product polyethylene.

[0174] [Example 4 Catalytic Olefin Polymerization Test]

[0175] Under nitrogen, 350 mL of n-heptane and 1.0 g of triethylaluminum were added to a stainless steel polymerization kettle. The kettle temperature was adjusted to 70° C. and maintained stable. 10.0 mg of the supported metallocene catalyst of Example 4 was weighed and suspended in the n-heptane. The suspension was then added to the reactor. The ethylene pressure was quickly adjusted to 1.0 MPa and a timer was started. The ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped and the ethylene gas in the polymerization kettle was slowly released. The reaction mixture was filtered to obtain a white solid, which was then vacuum-dried to a constant weight to obtain the product polyethylene. The mass, viscosity-average molecular weight (Mη), molecular weight distribution (PDI), and ash content of the product polyethylene were tested. The catalytic activity of the supported metallocene catalyst of Example 4 for ethylene homopolymerization was calculated based on the mass of the obtained product polyethylene.

[0176] [Example 5 Catalytic Olefin Polymerization Test]

[0177] Under nitrogen, 350 mL of n-heptane and 1.0 g of triethylaluminum were added to a stainless steel polymerization kettle. The kettle temperature was adjusted to 70°C and maintained stable. 10.0 mg of the supported metallocene catalyst from Example 5 was weighed and suspended in the n-heptane. The suspension was then added to the reactor. The ethylene pressure was quickly adjusted to 1.0 MPa and a timer was started. The ethylene pressure was kept constant during the polymerization process. After 2 hours of reaction, the ethylene gas was stopped and the ethylene gas in the polymerization kettle was slowly released. The reaction mixture was filtered to obtain a white solid, which was then vacuum-dried to a constant weight to obtain the product polyethylene. The mass, viscosity-average molecular weight (Mη), molecular weight distribution (PDI), and ash content of the product polyethylene were tested. The catalytic activity of the supported metallocene catalyst from Example 5 for ethylene homopolymerization was calculated based on the mass of the obtained product polyethylene.

[0178] [Example 6 Catalytic Olefin Polymerization Test]

[0179] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 6 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 6 for ethylene homopolymerization was calculated according to the mass of the product polyethylene.

[0180]

Example 7 catalytic olefin polymerization reaction test

[0181] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 7 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 7 for ethylene homopolymerization was calculated according to the mass of the product polyethylene.

[0182]

Example 8 catalytic olefin polymerization reaction test

[0183] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 8 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 8 for ethylene homopolymerization was calculated according to the mass of the product polyethylene.

[0184]

Example 9 catalytic olefin polymerization reaction test

[0185] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 9 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 9 for ethylene homopolymerization reaction was calculated according to the mass of the product polyethylene.

[0186]

Example 10 catalytic olefin polymerization reaction test

[0187] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 9 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 9 for ethylene homopolymerization reaction was calculated according to the mass of the product polyethylene.

[0188]

Example 10 catalytic olefin polymerization reaction test

[0189] Under nitrogen protection, 350 mL of n-heptane and 1.0 g of trimethylaluminum were added into a stainless steel polymerization kettle, the temperature of the kettle liquid was adjusted to 70°C and kept stable, 10.0 mg of the supported metallocene catalyst of Example 9 was suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization process. After 2 h of reaction, the ethylene gas was stopped, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Example 9 for ethylene homopolymerization reaction was calculated according to the mass of the product polyethylene.

[0190]

Example 10 catalytic olefin polymerization reaction test

[0191] Under nitrogen protection, 350 mL of n-heptane and 0.5 g of triethylaluminum were added into a stainless steel polymerization kettle, the kettle liquid temperature was adjusted to 70°C and kept stable, 10.0 mg of the catalyst of Comparative Example 2 was weighed and suspended in n-heptane, and then the suspension was added into the reaction kettle, the ethylene pressure was quickly adjusted to 1.0 MPa and the timing was started, and the ethylene pressure was kept constant during the polymerization. After 2 h of reaction, the ethylene gas in the polymerization kettle was slowly released, filtered, and white solids were obtained. The white solids were vacuum dried until the weight was constant to obtain the product polyethylene. The mass, viscosity-average molecular weight Mη, molecular weight distribution PDI, and product ash of the product polyethylene were detected, and the catalytic activity of the supported metallocene catalyst of Comparative Example 2 for ethylene homopolymerization was calculated according to the mass of the product.

[0192] The reaction conditions and results of the supported metallocene catalysts of each comparative example and the catalysts of the examples for catalyzing polyethylene were summarized in Table 2.

[0193]

Detection method

[0194] The mass detection method of the product polyethylene: GB / T7724-2023

[0195] The viscosity-average molecular weight Mη detection method: GB / T1632.3-2010

[0196] The molecular weight distribution PDI detection method: SN / T4183-2015

[0197] The polyolefin product ash detection method: GB / T9345.1-2008

[0198] Table 2: Summary of reaction conditions and results of supported metallocene catalysts of each example and catalysts of comparative examples for catalyzing polyethylene

[0199]

[0200] Based on the data in Table 1 and Table 2, the following analysis was made:

[0201] The supported metallocene catalyst of Example 1 was modified by adding an ether compound to modify the aluminoxane compound during preparation, and the catalyst of Comparative Example 1 was not added with an ether compound during preparation. The addition amount of methylaluminoxane of Comparative Example 1 and methylaluminoxane of Example 1 was the same. Under the condition that other preparation steps and olefin polymerization reaction conditions were the same, the activity of the supported metallocene catalyst of Example 1 was significantly higher than that of the catalyst of Comparative Example 1, indicating that the modification of the aluminoxane compound by adding an ether compound could improve the catalytic activity of the supported metallocene catalyst for olefin polymerization reaction.

[0202] The difference between Comparative Example 1 and Comparative Example 2 is that only 5 mL of methylaluminoxane was added to the catalyst of Comparative Example 1 during the preparation process, while 50 mL of methylaluminoxane was added to the catalyst of Comparative Example 2 during the preparation process. The amount of methylaluminoxane added to Comparative Example 2 greatly exceeded the amount of methylaluminoxane added to Comparative Example 1. The catalytic activity of the catalyst of Comparative Example 2 was significantly higher than that of the catalyst of Comparative Example 1. This indicates that adding a large amount of aluminoxane compound during the catalyst preparation process can improve the catalytic activity for olefin polymerization. The catalyst activity of Comparative Example 2 is close to that of the supported metallocene catalyst of Example 1, but the amount of aluminoxane compound used in the supported metallocene catalyst of Example 1 during the preparation process is much lower than that of the catalyst of Comparative Example 2. This indicates that adding an ether compound to modify the aluminoxane compound can maintain a high catalytic activity of the supported metallocene catalyst for olefin polymerization while reducing the amount of aluminoxane compound used in the supported metallocene catalyst, thereby reducing the preparation cost of the supported metallocene catalyst and the production cost of polyolefins.

[0203] The ash content of the product of Example 1 is lower than that of Comparative Example 1, indicating that the addition of ether compounds to modify the alkylaluminoxane so that the supported metallocene catalyst containing the ether-modified aluminoxane compound is used to catalyze olefin polymerization can significantly reduce the ash content in the product.

[0204] The ash content of the product obtained after catalytic olefin polymerization in Comparative Example 2 is greater than that of the products obtained after catalytic olefin polymerization in Comparative Example 1 and Comparative Example 1, and the ash content of the product increases with the increase in the amount of surface aluminoxane compound added.

[0205] Examples 1 to 10 show that by adjusting the type and amount of the ether compound during the preparation of the supported metallocene catalyst and using the supported metallocene catalyst to catalyze olefin polymerization, the viscosity-average molecular weight Mη and molecular weight distribution PDI of the product polyolefin can be adjusted.

[0206] The amount of aluminoxane compound used in Examples 1 to 10 is lower than that in Comparative Example 2. The ash content in the olefin polymerization products catalyzed by each catalyst in Examples 1 to 10 is much lower than that in the olefin polymerization products catalyzed by the catalyst in Comparative Examples 1 and 2.

[0207] It should be noted that, in this article, "include", "comprises" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method or article that includes a series of elements includes not only those elements, but also includes other elements that are not explicitly listed, or also includes elements that are inherent to such process, method or article.

[0208] The various embodiments in the specification are described in a related manner, and the same or similar parts between the various embodiments can be referred to each other, and each embodiment focuses on the difference from other embodiments.

[0209] The above description is merely the preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the principles of the present application shall be included in the scope of protection of the present application.

Claims

1. An active carrier, characterized in that The active support is used to support the metallocene compound to form a supported metallocene catalyst. The active support includes a support body and an ether-modified aluminoxane compound supported on the support body. The ether-modified aluminoxane compound is modified by using at least one of an alkyl ether having an alkyl carbon chain with 10 or more carbon atoms and a crown ether.

2. The active carrier according to claim 1, characterized in that The carrier body is a silica gel carrier, and the active carrier is at 689±2cm -1 There is an Al-C vibration peak at Preferably, the active carrier is at 1079±2cm -1 and 459±2cm -1 There is a vibration peak at the Si-O-Si vibration peak of the carrier body.

3. The active carrier according to claim 2, characterized in that The mass ratio of the ether-modified aluminoxane compound to the silica gel carrier is 0.5-10:1-30; Preferably, the mass ratio of the ether-modified aluminoxane compound to the silica gel carrier is 0.5-5:10-20.

4. A supported metallocene catalyst, characterized in that The supported metallocene comprises the active carrier according to any one of claims 1 to 3 and a metallocene complex supported on the active carrier, the mass ratio of the metallocene complex to the active carrier being 1:10 to 1000; preferably, the mass ratio of the metallocene complex to the active carrier being 1:10 to 500.

5. A method for preparing a supported metallocene catalyst, characterized in that: include: Step S10: Pretreating the carrier to obtain an active carrier, mixing the carrier body, the first organic medium, and the ether-modified aluminoxane compound in an inert atmosphere to obtain a slurry, stirring the slurry at a first temperature T1 for a first time t1, and performing solid-liquid separation, washing, and drying to obtain an active carrier after the reaction, wherein the first temperature T1 is 20° C. to 180° C., and the first time t1 is 1 hour to 24 hours; Step S20: In an inert atmosphere, adding the metallocene complex solution to the active support to obtain a supported metallocene catalyst by an impregnation method.

6. The method for preparing a supported metallocene catalyst according to claim 5, wherein In the step S10, the carrier body is a silica gel carrier, and the step S10 includes: Step S11: The carrier body is subjected to a thermal activation treatment, which includes heating the carrier body in an inert protective atmosphere at 100°C to 800°C, normal pressure or 10 to 10 3 Heat treatment under reduced pressure of Pa for 1h to 36h; Preferably, the thermal activation treatment temperature is 200°C to 500°C; Preferably, the particle size of the silica gel carrier is 1.0 to 80 μm, the pore volume of the silica gel carrier is 1.0 to 3.0 mL / g, the pore size of the silica gel carrier is 10 to 30 nm, and the specific surface area of ​​the silica gel carrier is 150 to 850 m 2 / g.

7. The method for preparing a supported metallocene catalyst according to claim 5, wherein The step S10 further includes: Step S12, synthesizing the ether-modified aluminoxane compound, mixing the aluminoxane compound and the ether compound in an inert atmosphere at a second temperature T2 and stirring for a second time t2 to obtain the ether-modified aluminoxane compound, wherein the second temperature T2 is 0° C. to 100° C. and the second time t2 is 1 hour to 24 hours; Preferably, in the step S12, the mass ratio of the aluminoxane compound to the ether compound is 0.1-20:0.05-0.5; preferably, in the step S12, the stirring speed is 100 rpm to 3000 rpm.

8. The method for preparing a supported metallocene catalyst according to claim 5, wherein In the step S10: the mass ratio of the ether-modified aluminoxane compound to the carrier body is 0.5-10:1-30, and preferably, the stirring speed of the slurry is 100 rpm to 3000 rpm; Preferably, the step S10 further includes: Step S13: In an inert atmosphere, adding a first organic medium to the carrier body to form a mixture, and adding the ether-modified aluminoxane compound to the mixture to obtain the slurry.

9. The method for preparing a supported metallocene catalyst according to claim 5, wherein In the step S20, under the protection of an inert atmosphere, the metallocene complex solution is added dropwise to the active support to obtain a solid-liquid mixture, the solid-liquid mixture is stirred at a third temperature T3 to react for a third time t3, and after the reaction is completed, solid-liquid separation, washing, and drying are performed to obtain the supported metallocene catalyst; The mass ratio of the metallocene complex in the metallocene complex solution to the active carrier is 1:1 to 10000, the third temperature T3 is 0° C. to 100° C., and the third time t3 is 1 hour to 48 hours; Preferably, the mass ratio of the metallocene complex in the metallocene complex solution to the active carrier is 1:10-1000.

10. The method for preparing a supported metallocene catalyst according to claim 5, wherein The preparation method of the supported metallocene catalyst satisfies at least one of the following conditions: (1) The aluminoxane compound is at least one selected from methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-butylaluminoxane and isopropylaluminoxane; (2) The ether compound includes at least one of an alkyl ether having an alkyl carbon chain with 10 or more carbon atoms and a crown ether; preferably, the crown ether is selected from at least one of 12-crown-4, 15-crown-5, 18-crown-6, benzo-12-crown-4, benzo-15-crown-5, cyclohexane-15-crown-5, cyclohexane-18-crown-6 and dicyclohexane-18-crown-6; preferably, the alkyl ether is selected from at least one of n-decyl ether, undecyl ether, dodecyl ether and hexadecyl ether; (3) the first organic medium is selected from at least one of tetrahydrofuran, ether, toluene, benzene, chloroform, dichloromethane, petroleum ether and n-hexane; (4) The metallocene complex dissolved in the metallocene complex solution is selected from bis(cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, rac-ethylenebis(indenyl)zirconium dichloride, bis(tetrahydroindenyl)hafnium dichloride, dimethylsilylbis(indenyl)zirconium dichloride, bis(tetrahydro-1-indenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium difluoride, bis(n-butylcyclopentadienyl)zirconium difluoride, rac-ethylene at least one of bis(indenyl)zirconium difluoride, bis(tetrahydroindenyl)hafnium difluoride, dimethylsilylbis(indenyl)zirconium difluoride, bis(tetrahydro-1-indenyl)zirconium difluoride, bis(cyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)zirconium dimethyl, rac-ethylenebis(indenyl)zirconium dimethyl, bis(tetrahydroindenyl)hafnium dimethyl, dimethylsilylbis(indenyl)zirconium dimethyl, and bis(tetrahydro-1-indenyl)zirconium dimethyl.

11. A supported metallocene catalyst, characterized in that: The supported metallocene catalyst is prepared by the method for preparing a supported metallocene catalyst according to any one of claims 5 to 10.

12. Use of the supported metallocene catalyst according to claim 4 or the supported metallocene catalyst according to claim 11, characterized in that: The supported metallocene catalyst is used for catalyzing olefin homopolymerization and copolymerization.

13. The use of the supported metallocene catalyst according to claim 12, characterized in that: The supported metallocene catalyst is used to catalyze olefin homopolymerization. Under the protection of an inert atmosphere, a reactor is loaded with a second organic medium, an alkyl aluminum compound as a co-catalyst and the supported metallocene catalyst as a main catalyst are added to the second organic medium, and olefin polymerization monomers are fed into the reactor to perform slurry polymerization, gas phase polymerization or solution polymerization to obtain an olefin homopolymer. Preferably, the second organic medium is selected from at least one of n-heptane, n-hexane, petroleum ether, toluene, benzene, tetrahydrofuran, and dichloromethane; Preferably, the supported metallocene catalyst is used to catalyze the polymerization of ethylene and / or α-olefins, wherein the α-olefin is selected from at least one of propylene, 1-butene or 1-octene; Preferably, the supported metallocene catalyst is used to catalyze norbornene polymerization; Preferably, the molecular weight of the olefin homopolymer is 50,000 to 1.4 million, and the molecular weight distribution PDI is 2.0 to 5.0.

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