Supported metallocene catalyst additive, and preparation method therefor and use thereof

Abstract

The present application relates to the technical field of supported metallocene catalysts, and specifically relates to a supported metallocene catalyst additive, and a preparation method therefor and the use thereof. The supported metallocene catalyst additive has the structure as shown in Formula I, wherein R is selected from a C1-C10 alkyl; R1 and R3 are selected from an alkyl and adamantyl and are located at ortho- and para-positions of -OH; R2 is selected from a C1-C10 alkyl and a cycloalkyl; and R' is selected from an alkyl. The additive can greatly retain the catalytic activity and copolymerization performance of a metallocene catalyst, increase the metal loading and catalytic activity, and reduce the amount of the traditional cocatalyst MAO.

Description

A supported metallocene catalyst additive, its preparation method and application

[0001] This application claims priority to Chinese Patent Application No. 202411931804.3, filed on December 26, 2024, entitled “Supported Metallocene Catalyst Additives and Preparation Methods Thereof and Applications Thereof”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of supported metallocene catalyst technology, specifically to a supported metallocene catalyst additive, its preparation method, and its application. Background Technology

[0003] Compared to traditional polyethylene materials, metallopolyethylene (mPE) has a larger molecular weight and a narrower molecular weight distribution, resulting in greater elongation at break and better impact strength, significantly improving the mechanical properties of mPE film materials. Furthermore, its excellent low-temperature sealing performance reduces processing difficulty, making it suitable for high-speed bag-making production lines. Moreover, mPE films offer superior sealing, moisture-proof, waterproof, and anti-aging properties, making them suitable for food packaging, such as meat products, convenience foods, and frozen foods. In addition, mPE films have good water vapor barrier properties and high oxygen permeability, making them suitable for packaging fresh fruits and vegetables. As agricultural greenhouse films, they possess high strength, anti-fogging, anti-drip, aging resistance, and good transparency, making them an excellent choice for agricultural production. The wide range of applications for mPE films and the significant increase in market demand in recent years have also driven a surge in the research and development and production of metallocene catalysts.

[0004] Supported metallocene catalysts are the core technology for preparing metallocene polyethylene (mPE) materials. They consist of an active component and a co-catalyst uniformly dispersed and supported on a specially selected support. In traditional supported methods, the residual -OH groups on the surface of the heat-treated support form negative charge centers, which combine with the activated metallocene active center cations via electrostatic attraction. This overly tight binding restricts the space around the metallocene active center, preventing olefin insertion and coordination polymerization, leading to deactivation of the active center (see Figure 1 for the principles of supported activation and deactivation). Timely addition of the co-catalyst MAO can isolate the metallocene from the support, expanding the metallocene space and restoring its activity (see Figure 1 for the principles of supported activation and deactivation). However, currently, the high price and limited production of methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) as co-catalysts severely restrict the development of the high-end polyolefin industry. Therefore, since the last century, academia and manufacturers have been researching and developing alternatives to MAO. The most successful so far are the perfluorophenylborone series, but the use of perfluorophenylborone salts still suffers from low activity.

[0005] Therefore, it is of great significance to develop new supported metallocene catalyst additives that can replace or reduce the amount of MAO cocatalyst. Summary of the Invention

[0006] This application provides a supported metallocene catalyst additive that can greatly retain the catalytic activity and copolymerization performance of the metallocene catalyst, improve the metal loading and catalytic activity, and reduce the amount of traditional co-catalyst MAO.

[0007] The preparation method of the additives provided in this application is simple and easy to implement.

[0008] The supported metallocene catalyst provided in this application has high catalytic activity, excellent copolymerization performance, and low cost.

[0009] The olefin polymerization method provided in this application can efficiently obtain polymer products with a narrow molecular weight distribution.

[0010] This application achieves the above-mentioned technical objectives through the following technical solutions:

[0011] This application provides a supported metallocene catalyst additive, the additive having the structure shown in formula (a):

[0012] Wherein, R is selected from C1-C10 alkyl groups, R1 and R3 are selected from alkyl and adamantyl groups and are located at the ortho-para position of -OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R' is selected from alkyl groups.

[0013] In the above-described supported metallocene catalyst additive, R1 and R3 are selected from at least one of the C1-C10 alkyl groups.

[0014] In the above-described supported metallocene catalyst additive, R1 and R3 are selected from at least one of C1-C10 branched alkyl groups and C3-C10 cycloalkyl groups.

[0015] In the above-described supported metallocene catalyst additive, R2 is selected from one of C1-C10 alkyl groups and C3-C10 cycloalkyl groups.

[0016] In the above-described supported metallocene catalyst additive, R' is selected from C1-C10 alkyl groups.

[0017] The above-described supported metallocene catalyst additives are C1-C7 compounds as follows:

[0018] C1:

[0019] C2:

[0020] C3:

[0021] C4:

[0022] C5:

[0023] C6:

[0024] C7:

[0025] This application also provides a method for preparing the above-mentioned supported metallocene catalyst additive, comprising the following steps:

[0026] (1) Bridged biphenol reacts with alkyl aluminum to give phenoloxyaluminate compounds;

[0027] (2) The phenolic aluminum compound reacts with an amine containing a siloxane at the chain end to obtain the product.

[0028] According to the preparation method described above, in step (1), under the protection of an inert gas, alkane is used as a solvent, and bridged biphenol reacts with alkyl aluminum at 20-90℃ for 10 min-6 h to obtain aluminum phenoloxide compound.

[0029] According to the preparation method described above, the molar ratio of bridged biphenol to alkyl aluminum is 1-3:1.

[0030] According to the preparation method described above, in step (2), under the protection of an inert gas, an amine is added to the product of step (1), the mixture is refluxed for 10 min to 3 h, the precipitate is collected after cooling, and the compound shown in formula (I) is obtained.

[0031] According to the preparation method described above, the molar ratio of amine to alkylaluminum is 0.8-1.2:1.

[0032] This application also provides a supported metallocene catalyst, comprising a support, the above-described supported metallocene catalyst additive or the supported metallocene catalyst additive prepared by the above preparation method, and a metallocene compound.

[0033] The supported metallocene catalysts described above are single-center metallocene compounds.

[0034] The supported metallocene catalyst described above uses silica gel as the support.

[0035] The supported metallocene catalysts described above also include co-catalysts.

[0036] The supported metallocene catalysts described above include MAO as a co-catalyst.

[0037] This application also provides a method for preparing a supported metallocene catalyst, wherein the supported metallocene catalyst is obtained by refluxing a support and the above-mentioned additives or the supported metallocene catalyst additives prepared by the above-mentioned preparation method in a solvent to obtain an anchor chain structured support-additive complex, and the support-additive complex is then combined with a metallocene compound to obtain the catalyst.

[0038] The supported metallocene catalyst prepared by the above method is obtained by combining a support-additive complex with a co-catalyst MAO and a metallocene compound;

[0039] Wherein: the ratio of support to metallocene compound is 10 μmol-100 μmol of metallocene compound per 1 g support; the molar ratio of metallocene compound to cocatalyst MAO is 1:50-1:400; and the molar ratio of metallocene compound to additive is 1:10-1:100.

[0040] The solvent for the supported metallocene catalysts described above is an alkane or toluene.

[0041] This application also provides a method for catalytic polymerization of olefins, including the step of catalysis using the above-described supported metallocene catalyst.

[0042] In the catalytic polymerization method for olefins described above, the olefin is ethylene.

[0043] The supported metallocene catalyst additive provided in this application can be anchored to the support surface at one end by a riveting group, and the metallocene compound can be firmly held by electrostatic attraction at the other end. This allows the metallocene compound to be suspended on the support surface instead of being tightly attached to it, which greatly preserves the catalytic activity and copolymerization performance under homogeneous conditions, effectively improves the metal loading and catalytic activity, reduces the amount of traditional co-catalyst MAO, and the additive has a controllable structure, which is more conducive to the research of olefin polymerization. Attached Figure Description

[0044] Figure 1 is a schematic diagram of the activation and deactivation mechanism of metallocene catalysts loaded on a support;

[0045] Figure 2 shows the ligand L during the preparation of C1 additive. 1 H2 1 H NMR spectrum;

[0046] Figure 3 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ1 in Example 1;

[0047] Figure 4 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ1 in Example 1;

[0048] Figure 5 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ3 in Example 3;

[0049] Figure 6 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ3 in Example 3;

[0050] Figure 7 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ4 in Example 4;

[0051] Figure 8 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ4 in Example 4;

[0052] Figure 9 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ5 in Example 5;

[0053] Figure 10 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ5 in Example 5;

[0054] Figure 11 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ6 in Example 6;

[0055] Figure 12 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ6 in Example 6;

[0056] Figure 13 shows the DSC test results of the polymer catalyzed by the supported catalyst FZ7 in Example 7;

[0057] Figure 14 shows the GPC test results of the polymer catalyzed by the supported catalyst FZ7 in Example 7. Detailed Implementation

[0058] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0059] This application provides a supported metallocene catalyst additive having the structure shown in formula (a):

[0060] Wherein, R is selected from C1-C10 alkyl and phenyl, R1 and R3 are selected from alkyl and adamantyl and are located at the ortho-para position of -OH, R2 is selected from C1-C10 alkyl and cycloalkyl, and R' is selected from alkyl.

[0061] The additive provided in this application is a novel aluminum amine compound. Its cationic segment contains an alkoxy group, which can react effectively with the residual -OH groups on the support surface to achieve an anchoring effect. The other end can firmly hold the metallocene compound through electrostatic attraction, preventing the metallocene compound from being tightly attached to the support surface and instead allowing it to suspend on the support surface. This greatly preserves the catalytic activity and copolymerization performance under homogeneous conditions, effectively improving the metal loading and catalytic activity, and reducing the amount of traditional MAO co-catalyst required. Compared to the uncertainty of the MAO structure, the additive structure of this application is controllable. By adjusting the substituent groups and linking functional groups on the aromatic ring, the catalytic performance and polymer microstructure can be easily adjusted, which is beneficial for using nuclear magnetic resonance (NMR), a powerful tool for studying homogeneous reactions, to study olefin polymerization.

[0062] In the above, alkyl refers to a saturated hydrocarbon group formed by removing a hydrogen atom from an alkane molecule. Its structure contains only carbon-carbon single bonds (CC) and carbon-hydrogen bonds (CH), and it has open-chain or cyclic (such as cycloalkyl) branched or straight-chain forms.

[0063] Alkyl groups (C1-C10) refer to straight-chain, branched, or cyclic groups formed by the loss of a hydrogen atom from straight-chain or branched alkanes consisting of 1 to 10 carbon atoms. Specifically, they include: methyl (CH3-), ethyl (C2H5-), propyl (including n-propyl C3H7- and isopropyl (CH3)2CH-), butyl (including n-butyl C4H9-, isobutyl (CH3)2CHCH2-, sec-butyl CH3CH2CH(CH3)-, and tert-butyl (C4H9)3C-), pentyl, hexyl, heptyl, octyl, nonyl, and decyl, cyclopropyl (-C3H5), cyclobutyl (-C4H7), and cyclohexyl (-C6H5). 11 )wait.

[0064] It should also be noted that all R substituents in this application may be the same or different, two R1s may be the same or different, two R3s may be the same or different, and R1 and R3 may be the same or different.

[0065] In this application, R1 and R3 are located at the ortho / para positions of -OH, where -OH refers to the phenolic hydroxyl group before binding with the Al ion. Specifically, R1 and R3 can be selected from at least one of C1-C10 alkyl groups. Exemplary examples include C1-C10 branched alkyl groups and C3-C10 cycloalkyl groups.

[0066] Specifically, the branched alkyl groups of C1-C10 can be isopropyl (CH3)2CH-, isobutyl (CH3)2CHCH2-, sec-butyl CH3CH2CH(CH3)-, and tert-butyl (C4H9)3C-, etc. The cycloalkyl groups of C3-C10 can be cyclopropyl (-C3H5), cyclobutyl (-C4H7), cyclohexyl (-C6H5), etc. 11 ), adamantyl (-C 10 H 15 )wait.

[0067] Furthermore, R' is selected from C1-C10 alkyl groups. Specifically, it includes: methyl (CH3-), ethyl (C2H5-), propyl (including n-propyl C3H7- and isopropyl (CH3)2CH-), butyl (including n-butyl C4H9-, isobutyl (CH3)2CHCH2-, sec-butyl CH3CH2CH(CH3)- and tert-butyl (C4H9)3C-), pentyl, hexyl, heptyl, octyl, nonyl and decyl, cyclopropyl (-C3H5), cyclobutyl (-C4H7), cyclohexyl (-C6H5), and cyclohexyl (-C6H5). 11 )wait.

[0068] In some specific embodiments, the additive is a C1-C7 compound as follows:

[0069] C1:

[0070] C2:

[0071] C3:

[0072] C4:

[0073] C5:

[0074] C6:

[0075] C7:

[0076] This application also provides a method for preparing the above-mentioned supported metallocene catalyst additive, comprising the following steps:

[0077] (1) Bridged biphenol reacts with alkyl aluminum to give phenoloxyaluminate compounds;

[0078] (2) The phenolic aluminum compound reacts with an amine containing a siloxane at the chain end to obtain the product.

[0079] In some specific embodiments, step (1) involves reacting bridged biphenol with alkyl aluminum at 20-90°C for 10 min-6 h under an inert gas atmosphere, using alkane as a solvent, to obtain an aluminum phenoloxide compound. The molar ratio of bridged biphenol to alkyl aluminum is 1-3:1, preferably 2:1.

[0080] In some specific embodiments, step (2) involves adding an amine to the product of step (1) under an inert gas atmosphere, refluxing for 10 min to 3 h, cooling, and collecting the precipitate to obtain the compound shown in formula (a). The molar ratio of the amine to the alkylaluminum is 0.8-1.2:1, preferably 1:1.

[0081] This application also provides a supported metallocene catalyst, comprising a support, the above-described supported metallocene catalyst additive or the supported metallocene catalyst additive prepared by the above-described preparation method, and a metallocene compound. This supported metallocene catalyst can effectively catalyze the polymerization reaction of olefins.

[0082] In this application, the choice of metallocene catalyst is not limited; for example, a single-center metallocene compound can be used. The choice of support is also not limited, and the choice of solvent is also not particularly restricted; conventional reagents in the art can be used. For example, in some specific embodiments, the metallocene catalyst is selected from dimethylsilyl-bridged diindizium, ethylene-bridged diindizium, or ethylene-bridged dihydroindizium, and the support is silica gel. Exemplarily, its structure is shown in formula (II):

[0083] This application also provides a method for preparing a supported metallocene catalyst, wherein the supported metallocene catalyst is obtained by refluxing a support and the above-mentioned additives in a solvent to obtain an anchor chain structured support-additive complex, and the support-additive complex is then combined with a metallocene compound to obtain the catalyst.

[0084] Furthermore, this supported metallocene catalyst also contains a co-catalyst, MAO. When MAO is present, the specific preparation method involves combining the support-additive complex with the co-catalyst MAO and the metallocene compound to obtain the corresponding supported metallocene catalyst. Specifically, the ratio of support to metallocene compound is 10 μmol-100 μmol of metallocene compound per 1 g of support, the molar ratio of metallocene compound to co-catalyst MAO is 1:50-1:400, and the molar ratio of metallocene compound to additive is 1:10-1:100.

[0085] The solvent is an alkane or toluene.

[0086] This application also provides a method for catalytic polymerization of olefins, the method comprising the step of catalysis using the above-described supported metallocene catalyst.

[0087] Furthermore, this method is particularly suitable for the polymerization of α-olefins (such as ethylene).

[0088] The additives described in this application will be described in detail below with reference to specific embodiments:

[0089] The preparation method of C1 additive in the following examples is as follows:

[0090] 2,4-Di-tert-butylphenol (10.3 g, 50.0 mmol) was added to a 250 mL three-necked flask, followed by 50 mL of benzene and stirring to dissolve. Triacetaldehyde (4.9 g, 37.5 mmol) was slowly added, and then 1.0 mL of concentrated sulfuric acid was slowly added dropwise. The reaction mixture was heated at 60 °C for 3 hours, then refluxed at 90 °C for 3 hours. The reaction was monitored by TLC. The reaction mixture was extracted three times with a suitable amount of ice water and ethyl acetate. The organic phases were combined and dried over sodium sulfate-free solution for 2 hours. The mixture was filtered, and the solvent was removed by rotary evaporation to obtain a yellow oily substance. This substance was purified by column chromatography using PE:EA = 30:1 eluent to obtain a pale yellow solid, namely ligand L. 1 H2 (8.6g, 53%). 1 H NMR (400MHz, CDCl3, 298K): δ7.25(d,J=2.4Hz,2H,ArH),7.21(d,J=2.4Hz,2H,ArH),5.52(s,2H,OH ), 4.46 (q, J = 7.2Hz, 1H, CHCH3), 1.70 (d, J = 7.2Hz, 3H, CHCH3), 1.37 (s, 18H), 1.31 (s, 18H), see Figure 2 for details.

[0091] Weighing ligand L 1 H2 (8.2 g, 19.0 mmol) was dissolved in a 100 mL Schlenk flask by adding 30 mL of n-hexane and stirring. AlMe3 (9.5 mL, 9.5 mmol, 1 mol / L) in n-hexane was then slowly added, with the addition completed after 5 minutes. The reaction mixture was stirred at room temperature for 30 minutes, and the reaction solution changed from pale yellow to deep red, yielding aluminum phenoloxide compound 1a. The NMR characterization results of aluminum phenoloxide compound 1a were: (THF-d8, δ) 1.2–1.5 (s, 72H, tBuH), 1.6 (d, 6H, -CH3), 5.4 (m, 2H, H-CCH3), 6.9–7.5 (m, 8H, ArH).

[0092] N,N-dimethyl-3-(trimethoxysilyl)propylamine (2.0 mL, 9.5 mmol) was added to the reaction flask. After reacting for 24 h, stirring was stopped. A white precipitate (C1) formed after the reaction solution was allowed to stand. The precipitate was filtered, washed with n-hexane solution, and the white solid was sealed and stored under liquid nitrogen in a cold trap for 2 h. The NMR characterization of compound C1 was: (THF-d8, δ) 0.9–2.4 (m, 6H, -CH2). - ), 1.2-1.5 (s, 72H, tBuH), 1.6 (d, 6H, -CH3), 2.15 (s, 6H, -CH2-), 3.65 (s, 9H, OCH3), 5.4 (q, 2H, H-CCH3), 6.9-7.5 (m, 8H, ArH).

[0093] The preparation methods for C2-C7 additives are the same as those for C1 additives, except that the substituents of the phenols used are different or the silyl ether composition in the propylamine molecule is different.

[0094] The C2 characterization results are as follows: (THF-d8, δ) 0.9-2.4 (m, 6H, -CH2) - ), 1.2-1.53(s, 72H, tBuH), 1.25(t, 9H, -OCH2CH3), 1.62(d, 6H, -CH3), 2.15(s, 6H, -CH2-), 3.49 (t, 6H, -OCH2CH3), 5.32 (q, 2H, H-CCH3), 6.9-7.7 (m, 8H, ArH).

[0095] The characterization results for C3 are as follows: 1 H NMR (400MHz, CDCl3, δ) 0.9-2.1 (m, 6H, -CH2 - ), 1.18(d,J=6.1Hz,12H,Ad-H), 1.28(s,12H,Ad-H), 1.41(d,J=3.9Hz,24H,Ad-H), 1.51(s,12H,Ad-H) , 1.6 (d, 6H, -CH3), 2.17 (s, 6H, -CH3), 3.63 (s, 9H, OCH3), 5.4 (q, 2H, H-CCH3), 6.97–6.91 (m, 8H, Ph-H).

[0096] The characterization results for C4 are as follows: 1 H NMR (400MHz, CDCl3, δ) 0.9-2.4 (m, 6H, -CH2 -), 1.18 (d, J = 6.1Hz, 12H, Ad-H), 1.25 (t, 9H, -OCH2CH3), 1.28 (s, 12H, Ad-H), 1.41 (d, J = 3.9Hz, 24H, 1.53 (s, 12H, Ad-H), Ad- H), 12H, Ad-H), 1.6 (d, 6H, -CH3), 2.15 (s, 6H, -CH3), 3.49 (dd, 6H, -OCH2CH3), 5.4 (q, 2H, H-CCH3), 6.97–6.90 (m, 8H, Ph-H).

[0097] The characterization results for C5 are as follows: 1 H NMR (400MHz, CDCl3, δ) 0.9-2.4 (m, 6H, -CH2 - ), 1.18 (d, J=6.1Hz, 6H, Ad-H), 1.28 (s, 6H, Ad-H), 1.42 (d, J=3.9Hz, 12H, Ad-H), 1.52 (s, 6H, Ad-H), 1.61 (d, 6H, - CH3), 2.17 (s, 6H, -CH3), 2.35 (s, 12H, Ar-CH3), 3.67 (s, 9H, OCH3), 5.4 (q, 2H, H-CCH3), 6.95–6.89 (m, 8H, Ph-H).

[0098] The characterization results for C6 are as follows: 1 H NMR (400MHz, CDCl3, δ) 0.9-2.4 (m, 6H, -CH2 - ), 1.18 (d, J = 6.1Hz, 6H, Ad-H), 1.24 (t, 9H, -OCH2CH3), 1.27 (s, 6H, Ad-H), 1.42 (d, J = 3.9Hz, 12H, Ad-H), 1.55 (s, 6H, Ad-H), 1.6 1(d, 6H, -CH3), 2.15 (s, 6H, -CH3), 2.35 (s, 12H, Ar-CH3), 3.49 (dd, 6H, -OCH2CH3), 5.4 (q, 2H, H-CCH3), 6.95–6.89 (m, 8H, Ph-H).

[0099] The characterization results for C7 are: (THF-d8, δ) 0.9-2.4 (m, 6H, -CH2) - ), 1.2-1.5(s, 72H, tBuH), 1.51-2.2(m, 22H, C6H 11 ), 2.15 (s, 6H, -CH3), 3.61 (s, 9H, OCH3), 5.2 (q, 2H, HC), 6.9-7.5 (m, 8H, ArH).

[0100] Example 1: Preparation of supported catalyst FZ1

[0101] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600 °C for 6 hours was suspended in 50 mL of toluene. A toluene suspension containing 650 mg of C1 additive was added, and the mixture was refluxed for another 1 hour. Then, a mixture of toluene solution containing 21 mg (50 μmol) of ethylidene-bridged hydrogenated diindenezirconium and 375 mg (2.5 mmol) of methylaluminoxane (MAO) toluene solution was added, and the mixture was refluxed for another 3 hours. The mixture was then cooled, filtered, dried, and the precipitate was washed with toluene. The solvent was removed under reduced pressure to obtain a dark solid powder with good flow properties, which is the supported catalyst FZ1. Elemental analysis showed that the Zr content was 0.43% and the Al content was 4.9%.

[0102] Example 2 Preparation of supported catalyst FZ2

[0103] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600 °C for 6 hours was suspended in 50 mL of toluene. A toluene suspension containing 700 mg of C1 additive was added, and the mixture was refluxed for another 1 hour. Then, a mixture of toluene solution containing 21 mg (50 μmol) of ethylene-bridged diindene zirconium and 375 mg (2.5 mmol) of MAO toluene solution was added, and the mixture was refluxed for another 3 hours. After cooling, the mixture was filtered, dried under vacuum, and the precipitate was washed with toluene. The solvent was removed under reduced pressure to obtain a dark solid powder with good flow properties, which is catalyst FZ2. Elemental analysis showed that the Zr content was 0.29% and the Al content was 4.7%.

[0104] Example 3 Preparation of supported catalyst FZ3

[0105] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600 °C for 6 hours was suspended in 50 mL of toluene. A toluene suspension containing 700 mg of C1 additive was added, and the mixture was refluxed for another 1 hour. Then, a mixture of 21 mg (50 μmol) of ethylene-bridged diindene zirconium disulfide in toluene solution and 750 mg (5 mmol) of MAO in toluene solution was added, and the mixture was refluxed for another 3 hours. The mixture was cooled, filtered, dried under vacuum, and the precipitate was washed with toluene. The solvent was removed under reduced pressure to obtain a dark solid powder with good flow properties, which is catalyst FZ3. Elemental analysis showed that the Zr content was 0.28% and the Al content was 8.5%.

[0106] Example 4: Preparation of supported catalyst FZ4

[0107] The preparation method is similar to that in Example 1, except that an equivalent amount of C2 is used instead of C1 additive to obtain a powder with good flow properties, which is catalyst FZ4. The elemental analysis shows that the Zr content is 0.3% and the Al content is 5.1%.

[0108] Example 5: Preparation of supported catalyst FZ5

[0109] The preparation method is similar to that in Example 1, except that an equivalent amount of C3 is used instead of C1 additives to obtain a powder with good flow properties, which is catalyst FZ5. The elemental analysis shows that the Zr content is 0.34% and the Al content is 5.2%.

[0110] Example 6 Preparation of supported catalyst FZ6

[0111] The preparation method is similar to that in Example 1, except that an equivalent amount of C4 is used instead of C1 additives to obtain a powder with good flow properties, which is catalyst FZ6. The elemental analysis shows that the Zr content is 0.25% and the Al content is 4.8%.

[0112] Example 7 Preparation of supported catalyst FZ7

[0113] The preparation method is similar to that in Example 1, except that an equivalent amount of C6 is used instead of C1 additive to obtain a powder with good flow properties, which is catalyst FZ7. The elemental analysis shows that the Zr content is 0.27% and the Al content is 5.8%.

[0114] Comparative Example 1: Preparation of Supported Catalyst DB1

[0115] The preparation method is similar to that in Example 1, except that no C1 additive is added, resulting in a powder with good flow properties, which is catalyst DB1. The elemental analysis shows that the Zr content is 0.24% and the Al content is 4.5%.

[0116] Comparative Example 2: Preparation of Supported Catalyst DB2

[0117] The preparation method is similar to that in Example 1, except that no C1 additive is added, and the amount of MAO is 750 mg (5 mmol), resulting in a solid powder with good flow properties, which is catalyst DB2. The elemental analysis shows that the Zr content is 0.23% and the Al content is 9.2%.

[0118] Comparative Example 3: Preparation of Supported Catalyst DB3

[0119] The preparation method is similar to that in Example 1, except that no C1 additive is added, and the amount of MAO is 1500 mg (10 mmol), resulting in a free-flowing solid powder, which is catalyst DB3. The elemental analysis shows that the Zr content is 0.22% and the Al content is 13.5%.

[0120] Comparative Example 4: Preparation of Supported Catalyst DB4

[0121] The preparation method is similar to that in Example 1, except that no C1 additive is added, and the amount of MAO (2250 mg, 15 mmol) is 300 times that of the zirconium compound, resulting in a free-flowing solid powder, which is catalyst DB4. The elemental analysis shows that the Zr content is 0.18% and the Al content is 16.5%.

[0122] Catalytic ethylene polymerization experiment: A 200mL polymerization reactor equipped with a stirrer and gas inlet tube was vacuum dried at 100℃ for at least 30min. The reactor was then cooled, purged three times with ethylene gas, and n-hexane was added and kept at 80℃. Ethylene gas was introduced, maintaining a pressure of 1.0MPa. A slurry of 10mg of the supported catalyst from the example or comparative example and 10mL of hexane was added using a syringe. The mixture was stirred for 10min, the ethylene gas cylinder was closed, and the reactor was cooled to room temperature. The polymer was soaked in 10% hydrochloric acid-ethanol solution, filtered, and the solid was washed with ethanol until neutral. It was then vacuum dried at 60℃ to constant weight. The mass of the polymer was measured, and the catalyst polymerization activity, the melting point of the polymer (DSC), and the molecular weight distribution (GPC) were calculated. The test results are shown in Figure 3-14. In the GPC test results, the differential molecular weight distribution corresponds to the vertical axis dwt / d(logM), and the cumulative molecular weight distribution corresponds to the vertical axis Ht. Specific numerical statistics are shown in Table 1 below.

[0123] Table 1

[0124] The results above show that the supported catalysts (FZ1, FZ4, FZ5, FZ6, FZ7) prepared by adding the additives of this application (C1, C2, C3, C4, C6) and 50 times the amount of MAO significantly improved their catalytic activity compared with the supported catalyst (DB1) prepared by adding only 50 times the amount of MAO in Comparative Example 1. In Example 1, the amount of MAO used was 50 times the amount used, which, compared to 100 times the amount used in Comparative Example 2, 200 times the amount used in Comparative Example 3, and 300 times the amount used in Comparative Example 4, resulted in better catalytic activity and a narrower molecular weight distribution in the supported catalyst. This indicates that the additives provided in this application have a significant effect on improving catalyst activity and reducing the amount of MAO required.

[0125] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

Claims

1. A supported metallocene catalyst additive, wherein, The additive has a structure shown in the following formula (I): Wherein, R is selected from C1-C10 alkyl groups, R1 and R3 are selected from alkyl and adamantyl groups and are located at the ortho-para position of -OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R' is selected from alkyl groups.

2. The supported metallocene catalyst additive of claim 1, wherein, R1 and R3 are selected from at least one of the C1-C10 alkyl groups.

3. The supported metallocene catalyst additive of claim 2, wherein, R1 and R3 are selected from at least one of C1-C10 branched alkyl groups and C3-C10 cycloalkyl groups.

4. The supported metallocene catalyst additive according to any one of claims 1 to 3, wherein, R2 is selected from one of C1-C10 straight-chain alkyl groups and C3-C10 cycloalkyl groups.

5. The supported metallocene catalyst additive according to any one of claims 1 to 4, wherein, R' is selected from C1-C10 alkyl groups.

6. The supported metallocene catalyst additive of claim 1, wherein, The additive is a C1-C7 compound as follows: C1： C2: C3: C4： C5: C6: C7:

7. A process for the preparation of the supported metallocene catalyst additive of any one of claims 1 to 6, wherein, Includes the following steps: (1) Bridged biphenol reacts with alkyl aluminum to give phenoloxyaluminate compounds; (2) The phenolic aluminum compound reacts with an amine containing a siloxane at the chain end to obtain the product.

8. The production method according to claim 7, wherein In step (1), under inert gas protection, using alkanes as solvents, bridged biphenols react with alkylaluminum at 20-90℃ for 10 min-6 h to obtain aluminum phenoloxide compounds; and / or The molar ratio of bridged biphenol to alkyl aluminum is (1-3):

1.

9. The production method according to claim 7 or 8, wherein In step (2), under inert gas protection, an amine is added to the product of step (1), the mixture is refluxed for 10 min to 3 h, and the precipitate is collected after cooling to obtain the compound shown in formula (I); and / or The molar ratio of amine to alkylaluminum is (0.8-1.2):

1.

10. A supported metallocene catalyst, wherein, It includes a support, a supported metallocene catalyst additive as described in any one of claims 1-6, or a supported metallocene catalyst additive and a metallocene compound prepared by the preparation method described in any one of claims 7-9.

11. The supported metallocene catalyst of claim 10, wherein, Metallocene compounds are single-center metallocene compounds.

12. The supported metallocene catalyst of claim 10 or 11, wherein, The carrier is silicone.

13. The supported metallocene catalyst according to any one of claims 10-12, wherein, Supported metallocene catalysts also include co-catalysts.

14. The supported metallocene catalyst according to claim 13, wherein, The co-catalyst includes MAO.

15. A process for the preparation of the supported metallocene catalyst of any one of claims 10 to 14, wherein, The supported metallocene catalyst is obtained by refluxing a support and an additive prepared by any one of claims 1-6 or any one of claims 7-9 in a solvent to obtain an anchor-chain structured support-additive complex, which is then combined with a metallocene compound.

16. The method of preparing a supported metallocene catalyst according to claim 15, wherein, The supported metallocene catalyst is obtained by combining a support-additive complex with a co-catalyst MAO and a metallocene compound; wherein: The ratio of support to metallocene compound is 1g support to 10μmol-100μmol of metallocene compound; The molar ratio of metallocene compound to cocatalyst MAO is 1:50-1:400; The molar ratio of metallocene compounds to additives is 1:10 to 1:

100.

17. The method of preparing a supported metallocene catalyst according to claim 15 or 16, wherein, The solvent is an alkane or toluene.

18. A process for catalyzing the polymerization of olefins, wherein, The step includes catalysis using the supported metallocene catalyst according to any one of claims 10-14 or the supported metallocene catalyst prepared by the preparation method according to any one of claims 15-17.

19. The method of catalyzing the polymerization of olefins according to claim 18, wherein, The olefin is ethylene.

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