Supported metallocene catalyst additive as well as preparation method and application thereof

Abstract

The invention relates to the technical field of supported metallocene catalysts, in particular to a supported metallocene catalyst additive as well as a preparation method and application thereof. The supported metallocene catalyst additive has the following structure: # imgabs0 #, R is selected from C1-C10 alkyl groups, R1 and R3 are selected from alkyl groups and adamantyl groups and are located at ortho-para positions of-OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R'is selected from alkyl groups. The additive can greatly retain the catalytic activity and copolymerization performance of a metallocene catalyst, improve the metal loading capacity and catalytic activity, and reduce the dosage of a traditional cocatalyst MAO.

Description

Technical Field

[0001] The invention relates to the technical field of supported metallocene catalysts, and in particular to a supported metallocene catalyst additive and a preparation method and application thereof. Background Art

[0002] Compared with traditional polyethylene materials, metal polyethylene (mPE) has a large molecular weight and a narrow molecular weight distribution, so it has a larger elongation at break and better impact strength, which greatly improves the mechanical properties of mPE film materials. In addition, its excellent low-temperature sealing performance reduces the difficulty of processing and is suitable for high-speed bag production lines. Moreover, the sealing performance, moisture-proof performance, waterproof performance, and anti-aging performance of mPE film are more superior, and can be used in the field of food packaging, such as meat food, convenience food, and frozen food product packaging. In addition, mPE film has good barrier properties to water vapor and high permeability to oxygen. It is also suitable for the packaging of fresh fruits and vegetables. As an agricultural greenhouse film, it has the characteristics of high strength, anti-fogging, anti-drip, aging resistance, and good transparency, and is a good choice in agricultural production. The application range of mPE film is relatively wide. In recent years, the market demand for mPE has increased significantly, which has also driven the research and development and production boom of metallocene catalysts.

[0003] Supported metallocene catalyst is the core technology for preparing metallocene polyethylene (mPE) materials. It is a catalyst composed of active components and co-catalysts uniformly dispersed and supported on a specially selected carrier. In the traditional loading method, the -OH remaining on the surface of the carrier after heat treatment forms a negative charge center, which combines with the activated metallocene active center cation by electrostatic attraction. This too tight binding mode restricts the space around the metallocene active center, making it unable to accommodate olefin insertion and coordination polymerization, resulting in the deactivation of the active center (see the load activation and deactivation principle for details). Figure 1 Timely addition of cocatalyst MAO can isolate the metallocene from the carrier, expand the metallocene space, and thus restore the metallocene activity (see the load activation and deactivation principle for details). Figure 1 ). However, at present, the technology of methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) as co-catalysts is in the hands of Western companies. The high price and production restrictions seriously restrict the development of my country's high-end polyolefin industry. Therefore, since the last century, academia and manufacturers have been researching and developing substitutes for MAO. The most successful one is the perfluorophenylborane series, but the use of perfluorophenylborane salts still has the problem of low activity.

[0004] Therefore, it is of great significance to develop new supported metallocene catalyst additives that can replace or reduce the amount of co-catalyst MAO. Summary of the invention

[0005] The invention provides a supported metallocene catalyst additive, which can greatly retain the catalytic activity and copolymerization performance of the metallocene catalyst, increase the metal loading and catalytic activity, and reduce the dosage of the traditional co-catalyst MAO.

[0006] The preparation method of the additive provided by the present invention has a simple process and is easy to implement.

[0007] The supported metallocene catalyst provided by the present invention has high catalytic activity, excellent copolymerization performance and low cost.

[0008] The olefin polymerization method provided by the present invention can efficiently obtain a polymerization product with a narrow molecular weight distribution.

[0009] The present invention achieves the above technical objectives through the following technical solutions:

[0010] The present invention provides a supported metallocene catalyst additive, wherein the additive has a structure as shown in the following formula (1):

[0011]

[0012] Formula (I)

[0013] Wherein, R is selected from C1-C10 alkyl, 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.

[0014] The supported metallocene catalyst additive described above is a C1-C7 compound as follows:

[0015] C1: ;

[0016] C2: ;

[0017] C3: ;

[0018] C4: ;

[0019] C5: ;

[0020] C6: ;

[0021] C7: .

[0022] The present invention also provides a method for preparing the above-mentioned supported metallocene catalyst additive, comprising the following steps:

[0023] (1) The bridged diphenol reacts with an alkyl aluminum to obtain an aluminum phenolate compound;

[0024] (2) A phenolic aluminum compound is reacted with an amine containing siloxane at the chain end to obtain the product.

[0025] According to the preparation method described above, in step (1), under the protection of inert gas, alkane is used as solvent, and the bridged diphenol reacts with alkyl aluminum at 20-90° C. for 10 min-6 h to obtain an aluminum phenolate compound.

[0026] According to the above-mentioned preparation method, the ratio of the amount of the bridged diphenol to the amount of the alkyl aluminum substance is 1-3:1.

[0027] According to the preparation method described above, in step (2), under the protection of inert gas, amine is added to the product of step (1), and the reaction is refluxed for 10 minutes to 3 hours. The temperature is lowered and the precipitate is collected to obtain the compound represented by formula (I).

[0028] According to the above-mentioned preparation method, the molar ratio of amine to alkyl aluminum is 0.8-1.2:1.

[0029] The present invention also provides a supported metallocene catalyst, wherein the supported metallocene catalyst is obtained by refluxing a carrier and the above-mentioned additive in a solvent to obtain a silica gel-additive combination with an anchor chain structure, and the silica gel-additive combination is then combined with a metallocene compound.

[0030] The supported metallocene catalyst is obtained by combining a silica gel-additive combination with a co-catalyst MAO and a metallocene compound;

[0031] The ratio of the carrier to the metallocene compound is 10 μmol-100 μmol of the metallocene compound per 1 g of the carrier; the molar ratio of the metallocene compound to the cocatalyst MAO is 1:50-1:400; and the molar ratio of the metallocene compound to the additive is 1:10-1:100.

[0032] According to the above-mentioned supported metallocene catalyst, the metallocene compound is a single-center metallocene compound.

[0033] In the above-mentioned supported metallocene catalyst, the carrier is silica gel.

[0034] According to the above-mentioned supported metallocene catalyst, the solvent is alkane or toluene.

[0035] The present invention also provides a method for catalyzing olefin polymerization, comprising the step of using the above-mentioned supported metallocene catalyst for catalysis.

[0036] According to the above-mentioned method for catalytic olefin polymerization, the olefin is ethylene or α-olefin.

[0037] The supported metallocene catalyst additive provided by the present invention can be anchored on the carrier surface through a riveting group at one end, and the other end can firmly hold the metallocene compound through electrostatic attraction, so that the metallocene compound is no longer tightly attached to the carrier surface, but is suspended on the carrier surface, which greatly retains the catalytic activity and copolymerization performance under homogeneous conditions, effectively improves the metal loading and catalytic activity, can reduce the amount of traditional co-catalyst MAO, and the additive structure is controllable, which is more conducive to the study of olefin polymerization. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 Schematic diagram of the activation and deactivation principle of metallocene catalysts loaded on carriers;

[0039] Figure 2 Ligand L in the preparation process of C1 additive 1 H2 1 H NMR spectra;

[0040] Figure 3 The DSC test results of the polymer catalyzed by the supported catalyst FZ1 in Example 1;

[0041] Figure 4 The GPC test results of the polymer catalyzed by the supported catalyst FZ1 in Example 1;

[0042] Figure 5 The DSC test results of the polymer catalyzed by the supported catalyst FZ3 in Example 3;

[0043] Figure 6 The GPC test results of the polymer catalyzed by the supported catalyst FZ3 in Example 3;

[0044] Figure 7 The DSC test results of the polymer catalyzed by the supported catalyst FZ4 in Example 4;

[0045] Figure 8 The GPC test results of the polymer catalyzed by the supported catalyst FZ4 in Example 4;

[0046] Fig. 9 The DSC test results of the polymer catalyzed by the supported catalyst FZ5 in Example 5;

[0047] Fig.10 The GPC test results of the polymer catalyzed by the supported catalyst FZ5 in Example 5;

[0048] Fig.11 The DSC test results of the polymer catalyzed by the supported catalyst FZ6 in Example 6;

[0049] Fig.12 The GPC test results of the polymer catalyzed by the supported catalyst FZ6 in Example 6;

[0050] Fig.13 The DSC test results of the polymer catalyzed by the supported catalyst FZ7 in Example 7;

[0051] Fig.14 This is the GPC test result of the polymer catalyzed by the supported catalyst FZ7 in Example 7. DETAILED DESCRIPTION

[0052] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0053] The present invention provides a supported metallocene catalyst additive, which has a structure as shown in the following formula (1):

[0054] Formula (I)

[0055] 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.

[0056] The additive provided by the present invention belongs to a new type of amine aluminum compound, and its cationic segment contains an alkoxy group, which can react well with the residual -OH on the surface of the carrier to achieve an anchoring effect, and the other end can firmly pull the metallocene compound through electrostatic attraction, so that the metallocene compound is no longer tightly attached to the surface of the carrier, but suspended on the surface of the carrier, which greatly retains the catalytic activity and copolymerization performance under homogeneous conditions, effectively improves the metal loading and catalytic activity, and can reduce the amount of traditional co-catalyst MAO. Compared with the uncertainty of the MAO structure, the additive structure of the present invention is controllable, and the catalytic performance of the catalyst and the microstructure of the polymer can be conveniently adjusted by adjusting the substituent groups and connecting functional groups on the aromatic ring, which is conducive to the use of nuclear magnetic resonance, a powerful tool for studying homogeneous reactions, to study olefin polymerization.

[0057] In some specific embodiments, the additive is the following C1-C7 compound:

[0058] C1: ;

[0059] C2: ;

[0060] C3: ;

[0061] C4: ;

[0062] C5: ;

[0063] C 6: ;

[0064] C7: .

[0065] The present invention also provides a method for preparing the above-mentioned supported metallocene catalyst additive, comprising the following steps:

[0066] (1) The bridged diphenol reacts with an alkyl aluminum to obtain an aluminum phenolate compound;

[0067] (2) A phenolic aluminum compound is reacted with an amine containing siloxane at the chain end to obtain the product.

[0068] In some specific embodiments, step (1) is to react the bridged diphenol with the alkyl aluminum at 20-90° C. for 10 min-6 h under the protection of inert gas with alkane as solvent to obtain the phenol oxide aluminum compound. The ratio of the bridged diphenol to the alkyl aluminum substance is 1-3:1, preferably 2:1.

[0069] In some specific embodiments, step (2) is to add amine to the product of step (1) under the protection of inert gas, reflux for 10 min-3 h, cool and collect the precipitate, and obtain the compound represented by formula (I). The molar ratio of amine to alkyl aluminum is 0.8-1.2:1, preferably 1:1.

[0070] The present invention also provides a supported metallocene catalyst, wherein the supported metallocene catalyst is obtained by reflux of a carrier and the above-mentioned additive in a solvent to obtain a silica gel-additive combination with an anchor chain structure, and the silica gel-additive combination is then combined with a metallocene compound to obtain a structure as shown in formula (II). The supported metallocene catalyst can effectively catalyze the polymerization reaction of olefins.

[0071]

[0072] Formula (II)

[0073] Furthermore, the supported metallocene catalyst also contains a cocatalyst MAO. When the cocatalyst MAO is contained, the specific preparation method is to combine the silica gel-additive combination with the cocatalyst MAO and the metallocene compound to obtain the corresponding supported metallocene catalyst. Among them, the ratio of the carrier to the metallocene compound is 10 μmol-100 μmol of the metallocene compound per 1 g of the carrier, the molar ratio of the metallocene compound to the cocatalyst MAO is 1:50-1:400, and the molar ratio of the metallocene compound to the additive is 1:10-1:100.

[0074] In the present invention, the selection of metallocene catalyst is not limited, for example, a single-center metallocene compound can be used. The selection of carrier is also not limited, and the selection of solvent is also not particularly limited, and conventional reagents in the art can be used. For example, in some specific embodiments, the metallocene catalyst is selected from dimethylsilyl-bridged indene zirconium, ethylene-bridged indene zirconium or ethylene-bridged indene zirconium, the carrier is silica gel, and the solvent is alkane or toluene.

[0075] The present invention also provides a method for catalyzing olefin polymerization, which comprises the step of using the above-mentioned supported metallocene catalyst for catalysis.

[0076] Furthermore, the process is particularly suitable for the polymerization of ethylene or α-olefins.

[0077] The additives of the present invention are described in detail below in conjunction with specific embodiments:

[0078] The preparation method of the C1 additive in the following examples is as follows:

[0079]

[0080]

[0081] Add 2,4-di-tert-butylphenol (10.3 g, 50.0 mmol) to a 250 mL three-necked flask, add 50 mL of benzene and stir to dissolve, slowly add triacetaldehyde (4.9 g, 37.5 mmol), and then slowly drop 1.0 mL of concentrated sulfuric acid. Place the reaction system at 60 o C for 3 hours, then adjust the temperature to 90 o The mixture was heated to reflux at 3 °C for 3 hours and the reaction was monitored by TLC. The reaction solution was extracted with appropriate amounts of ice water and ethyl acetate for 3 times, the organic phases were combined, dried over a sodium sulfate-free water for 2 hours, filtered, and the solvent was removed by rotary evaporation to obtain a yellow oil, which was separated and purified by column chromatography using a developing solvent of PE:EA = 30:1 to obtain a light yellow solid, i.e., ligand L. 1 H2 (8.6 g, 53%). 1H NMR (400 MHz, CDCl3, 298 K): δ 7.25 (d, J = 2.4 Hz, 2H, ArH), 7.21 (d, J = 2.4 Hz, 2H, ArH), 5.52 (s, 2H, OH), 4.46 (q, J = 7.2 Hz, 1H,CHCH3), 1.70 (d, J = 7.2 Hz, 3H, CHCH3), 1.37 (s, 18H), 1.31 (s, 18H).

[0082] Weigh the ligand L 1 H2 (8.2 g, 19.0 mmol) was added to a 100 mL Schlenk bottle, 30 mL of n-hexane was added and stirred to dissolve, and AlMe3 (9.5 mL, 9.5 mmol, 1 mol / L) in n-hexane was slowly added to it, and the solution was added after 5 minutes. Stirring and reacting at room temperature for 30 min, the reaction solution changed from light yellow to dark red. N, N-dimethyl-3-(trimethoxysilyl)propylamine (2.0 mL, 9.5 mmol) was added to the reaction bottle, and stirring was stopped after 24 h of reaction. A white precipitate was precipitated after the reaction solution was allowed to stand. Filter, wash with n-hexane solution, and the white solid was evacuated with liquid nitrogen-cold trap for 2 h and then sealed and stored.

[0083] The preparation method of C2-7 additive refers to the preparation method of C1 additive, except that the substituents of the phenol used are different or the silyl ether composition in the propylamine molecule is different.

[0084] Example 1 Preparation of supported catalyst FZ1

[0085] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600°C for 6 hours was taken and suspended in 50 mL of toluene. A toluene suspension containing 650 mg of C1 additive was added and refluxed for 1 hour. A mixture of a toluene solution containing 21 mg (50 μmol) of ethylene-bridged indenyl zirconium hydride and a toluene solution containing 375 mg (2.5 mmol) of methylaluminoxane (MAO) was added and refluxed for 3 hours. The mixture was cooled, filtered, and dried. The precipitate was washed with toluene and the solvent was removed under reduced pressure to obtain a dark solid powder with good flowability, which was the supported catalyst FZ1. The elemental analysis showed that the Zr content was 0.43% and the Al content was 4.9%.

[0086] Example 2 Preparation of supported catalyst FZ2

[0087] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600°C for 6 hours was suspended in 50 mL of toluene, and a toluene suspension containing 700 mg of C1 additive was added. The mixture was refluxed for 1 hour, and then a mixture of a toluene solution containing 21 mg (50 μmol) of ethylene-bridged indenyl zirconium and a toluene solution containing 375 mg (2.5 mmol) of MAO was added. The mixture was refluxed for 3 hours, cooled, filtered, and dried. The precipitate was washed with toluene, and the solvent was removed under reduced pressure to obtain a dark solid powder with good flowability, which was catalyst FZ2. The elemental analysis showed that the Zr content was 0.29% and the Al content was 4.7%.

[0088] Example 3 Preparation of supported catalyst FZ3

[0089] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600°C for 6 hours was suspended in 50 mL of toluene, and a toluene suspension containing 700 mg of C1 additive was added. The mixture was refluxed for 1 hour, and then a mixture of 21 mg (50 μmol) of ethylene-bridged indenyl zirconium toluene solution and 750 mg (5 mmol) of MAO toluene solution was added. The mixture was refluxed for 3 hours, cooled, filtered, and dried. The precipitate was washed with toluene, and the solvent was removed under reduced pressure to obtain a dark solid powder with good flowability, which was catalyst FZ3. The elemental analysis showed that the Zr content was 0.28%, and the Al content was 8.5%.

[0090] Example 4 Preparation of supported catalyst FZ4

[0091] The preparation method is similar to that of Example 1, except that an equivalent amount of C2 is used instead of the C1 additive to obtain a powder with good flow properties, namely, catalyst FZ4. The elemental analysis shows that the Zr content is 0.3% and the Al content is 5.1%.

[0092] Example 5 Preparation of supported catalyst FZ5

[0093] The preparation method is similar to that of Example 1, except that an equivalent amount of C3 is used instead of the C1 additive to obtain a powder with good flow properties, namely, catalyst FZ5. The elemental analysis shows that the Zr content is 0.34% and the Al content is 5.2%.

[0094] Example 6 Preparation of supported catalyst FZ6

[0095] The preparation method is similar to that of Example 1, except that an equivalent amount of C4 is used instead of the C1 additive to obtain a powder with good flow properties, namely, catalyst FZ6, with an elemental analysis showing a Zr content of 0.25% and an Al content of 4.8%.

[0096] Example 7 Preparation of supported catalyst FZ7

[0097] The preparation method is similar to that of Example 1, except that an equivalent amount of C6 is used instead of the C1 additive to obtain a powder with good flow properties, namely, catalyst FZ7. The elemental analysis shows that the Zr content is 0.27% and the Al content is 5.8%.

[0098] Comparative Example 1 Preparation of supported catalyst DB1

[0099] The preparation method is similar to that of Example 1, except that no C1 additive is added, and a powder with good flowability is obtained, namely, catalyst DB1, and the elemental analysis shows that the Zr content is 0.24% and the Al content is 4.5%.

[0100] Comparative Example 2 Preparation of supported catalyst DB2

[0101] The preparation method is similar to that of Example 1, except that no C1 additive is added, the amount of MAO is 750 mg (5 mmol), and a solid powder with good flowability is obtained, namely, catalyst DB2. The elemental analysis shows that the Zr content is 0.23%, and the Al content is 9.2%.

[0102] Comparative Example 3 Preparation of supported catalyst DB3

[0103] The preparation method is similar to that of Example 1, except that no C1 additive is added, the amount of MAO used is 1500 mg (10 mmol), and a fluid solid powder is obtained, namely, catalyst DB3. The elemental analysis shows that the Zr content is 0.22% and the Al content is 13.5%.

[0104] Comparative Example 4 Preparation of supported catalyst DB4

[0105] The preparation method is similar to that of Example 1, except that no C1 additive is added, and the amount of MAO (2250 mg, 15 mmol) is 300 times the amount of the zirconium compound. A fluid solid powder is obtained, namely, catalyst DB4. The elemental analysis shows that the Zr content is 0.18%, and the Al content is 16.5%.

[0106] Catalytic ethylene polymerization experiment: A 200 mL polymerization kettle with a stirring rod and an air guide tube was vacuum dried at 100°C for at least 30 min, cooled, replaced with ethylene gas 3 times, n-hexane was added and the temperature was kept constant at 80°C, ethylene gas was introduced, and the pressure was maintained at 1.0 MPa. A slurry of 10 mg of the supported catalyst in the embodiment or comparative example and 10 mL of hexane was added with a syringe, stirred and reacted for 10 min, the ethylene gas cylinder was closed, cooled to room temperature, soaked with 10% hydrochloric acid ethanol, filtered, the solid was washed with ethanol until neutral, vacuum dried at 60°C to constant weight, and the mass of the polymer was weighed to calculate the polymerization activity of the catalyst, the melting point of the polymer was tested by DSC, and the molecular weight distribution of the polymer was tested by GPC. The test results are shown in Table 1. Figure 3-14 As shown, in the figure of GPC test results, the blue line is the differential distribution diagram of molecular weight (corresponding to the vertical coordinate dwt / d(logM), and the red line is the cumulative distribution diagram of molecular weight (corresponding to the vertical coordinate Ht). The specific numerical statistics are shown in Table 1 below:

[0107] Table 1

[0108]

[0109] From the above results, it can be seen that the catalytic activity of the supported catalysts obtained in the examples is significantly better than that of the comparative examples, and the molecular weight distribution of the obtained polymer is narrower. The dosage of MAO in Example 1 is 50 times, compared with the dosage of 100 times in Comparative Example 2, 200 times in Comparative Example 3, and 300 times in Comparative Example 4, the supported catalyst in Example 1 has better catalytic activity and a narrower molecular weight distribution, indicating that the additive provided by the present invention has a significant effect on improving the activity of the catalyst and reducing the dosage of MAO.

[0110] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A supported metallocene catalyst additive, characterized in that: The additive has a structure as shown in the following formula (1): Formula (I) Wherein, R is selected from C1-C10 alkyl, 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.

2. The supported metallocene catalyst additive according to claim 1, characterized in that The additive is the following C1-C7 compound: C1： ； C2: ； C3: ； C4： ； C5: ； C 6: ； C7: 。 3. A method for preparing the supported metallocene catalyst additive according to any one of claims 1 to 2, characterized in that: The following steps are involved: (1) The bridged diphenol reacts with an alkyl aluminum to obtain an aluminum phenolate compound; (2) A phenolic aluminum compound is reacted with an amine containing siloxane at the chain end to obtain the product.

4. The preparation method according to claim 3, characterized in that: In step (1), under the protection of inert gas, alkane is used as solvent, and the bridged diphenol and alkyl aluminum are reacted at 20-90° C. for 10 min-6 h to obtain an aluminum phenolate compound; and / or The amount ratio of the bridged diphenol to the alkyl aluminum substance is 1-3:

1.

5. The preparation method according to claim 3, characterized in that: In step (2), under the protection of inert gas, amine is added to the product of step (1), refluxed for 10 min-3 h, cooled and precipitated to obtain the compound of formula (I); and / or The molar ratio of the amine to the alkyl aluminum is 0.8-1.2:

1.

6. A supported metallocene catalyst, characterized in that: The supported metallocene catalyst is obtained by refluxing the carrier and the additive described in claim 1 or 2 in a solvent to obtain a silica gel-additive combination with an anchor chain structure, and the silica gel-additive combination is then combined with a metallocene compound.

7. The supported metallocene catalyst according to claim 6, characterized in that The supported metallocene catalyst is obtained by combining a silica gel-additive combination with a co-catalyst MAO and a metallocene compound; wherein: The ratio of the support to the metallocene compound is 10 μmol-100 μmol of the metallocene compound for 1 g of the support; The molar ratio of the metallocene compound to the cocatalyst MAO is 1:50-1:400; The molar ratio of the metallocene compound to the additive is 1:10-1:

100.

8. The supported metallocene catalyst according to claim 6 or 7, characterized in that The metallocene compound is a single-site metallocene compound; and / or The carrier is silica gel; and / or The solvent is alkane or toluene.

9. A method for catalyzing olefin polymerization, characterized in that: The method comprises the step of using the supported metallocene catalyst according to claim 6 for catalysis.

10. The method for catalyzing olefin polymerization according to claim 9, characterized in that: The olefin is ethylene or an α-olefin.

Images