Supported metallocene catalyst additive, preparation method and application thereof

Abstract

The present invention relates to the technical field of supported metallocene catalysts, and particularly relates to a supported metallocene catalyst additive, a preparation method thereof and an application. The supported metallocene catalyst additive has the following structure: #imgabs0#, wherein R is selected from C1-C10 alkyl groups, R1 and R3 are selected from alkyl groups and adamantyl groups and are in the ortho and para positions of -OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R' is selected from alkyl groups. This additive 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 cocatalyst MAO.

Description

Technical Field

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

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

[0003] Supported metallocene catalysts are the technical core for preparing metallocene polyethylene (mPE) materials. They are catalysts in which active components and cocatalysts are uniformly dispersed and supported on a specially selected carrier. In traditional loading methods, the -OH residues on the surface of the carrier after heat treatment form negatively charged centers, which combine with the cationic metallocene active centers after activation by electrostatic attraction. This overly tight combination method limits the space around the metallocene active centers and cannot accommodate olefin insertion and coordination polymerization, resulting in the inactivation of the active centers (for the loading activation and inactivation principles, see Figure 1 ). Adding the cocatalyst MAO in time can isolate the metallocene from the carrier, expand the space of the metallocene, and thus restore the activity of the metallocene (for the loading activation and inactivation principles, see Figure 1 ). However, at present, the technologies of methylaluminoxane (MAO) and modified methylaluminoxane (MMAO) as cocatalysts are in the hands of Western companies. The high price and production limitations seriously restrict the development of China's high-end polyolefin industry. Therefore, since the last century, the academic community and manufacturers have successively studied and developed alternatives to MAO. Currently, the most successful one is the perfluorobenzeneborate series, but the use of perfluorobenzeneborate 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 dosage of the cocatalyst MAO. Summary of the Invention

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

[0006] The preparation method of the above additive provided by the present invention is simple and 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 realizes the above technical purpose through the following technical solutions:

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

[0011]

[0012] Formula (I)

[0013] Among them, R is selected from C1-C10 alkyl groups, R1 and R3 are selected from alkyl groups and adamantyl groups and are in the ortho and para positions of -OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R' is selected from alkyl groups.

[0014] For the supported metallocene catalyst additive described above, the additive is a compound of C1-C7 as follows:

[0015] C1: ;

[0016] C2: ;

[0017] C3: ;

[0018] C4: ;

[0019] C5: ;

[0020] C6: ;

[0021] C7: .

[0022] The present invention also provides a preparation method of the above supported metallocene catalyst additive, including the following steps:

[0023] (1) The bridged diphenol reacts with alkylaluminum to obtain a phenoxyaluminum compound;

[0024] (2) It is obtained by reacting an aluminum phenoxide compound with an amine having a siloxane at the chain end.

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

[0026] According to the above preparation method, the molar ratio of the bridged diphenol to the alkylaluminum is 1 - 3:1.

[0027] According to the above preparation method, in step (2), under the protection of an inert gas, an amine is added to the product of step (1), and the mixture is refluxed for 10 min - 3 h, and then cooled to collect the precipitate, thus obtaining the compound shown in formula (I).

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

[0029] The present invention also provides a supported metallocene catalyst, which is obtained by refluxing a support and the above additive in a solvent to obtain an anchor chain structure silica - additive conjugate, and then combining the silica - additive conjugate with a metallocene compound.

[0030] According to the above supported metallocene catalyst, the supported metallocene catalyst is obtained by combining a silica - additive conjugate with a cocatalyst MAO and a metallocene compound;

[0031] Wherein: the ratio of the support to the metallocene compound is 1 g of the support corresponding to 10 μmol - 100 μmol of the metallocene compound; 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.

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

[0033] According to the above supported metallocene catalyst, the support is silica.

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

[0035] The present invention also provides a method for catalyzing olefin polymerization, which includes the step of catalyzing by using the above supported metallocene catalyst.

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

[0037] The supported metallocene catalyst additive provided by the present invention can be anchored on the surface of the carrier through a riveting group at one end, and can firmly hold the metallocene compound through electrostatic attraction at the other end, so that the metallocene compound no longer tightly adheres to the surface of the carrier, but suspends on the surface of the carrier, greatly retaining the catalytic activity and copolymerization performance under homogeneous conditions, effectively improving the metal loading and catalytic activity, reducing the dosage of the traditional cocatalyst MAO, and the structure of the additive is controllable, which is more conducive to the research of olefin polymerization. Description of the Drawings

[0038] Figure 1 Schematic diagram of the loading activation and deactivation principle of the metallocene catalyst on the carrier;

[0039] Figure 2 For ligand L during the preparation of C1 additive 1 H2 of 1 1H NMR spectrum;

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

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

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

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

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

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

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

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

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

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

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

[0051] Figure 14 GPC test results of the polymer catalyzed by the supported catalyst FZ7 in Example 7. Detailed implementation manners

[0052] To make the objectives, 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 conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

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

[0054] Formula (I)

[0055] Wherein, R is selected from C1-C10 alkyl groups and phenyl groups, R1 and R3 are selected from alkyl groups and adamantyl groups and are in the ortho and para positions of -OH, R2 is selected from C1-C10 alkyl groups and cycloalkyl groups, and R' is selected from alkyl groups.

[0056] The additive provided by the present invention belongs to a novel 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. The other end can firmly hold the metallocene compound through electrostatic attraction, so that the metallocene compound no longer tightly adheres to the surface of the carrier, but suspends on the surface of the carrier, greatly retaining the catalytic activity and copolymerization performance under homogeneous conditions, effectively improving the metal loading and catalytic activity, and reducing the dosage of the traditional cocatalyst MAO. Compared with the uncertain structure of MAO, the additive of the present invention has a controllable structure. By adjusting the substituents and connecting functional groups on the aromatic ring, the catalytic performance of the catalyst and the microstructure of the polymer can be conveniently adjusted, which is conducive to the study of olefin polymerization using nuclear magnetic resonance, a powerful tool for studying homogeneous reactions.

[0057] In some specific implementation manners, the additive is a C1-C7 compound as follows:

[0058] C1: ;

[0059] C2: ;

[0060] C3: ;

[0061] C4: ;

[0062] C5: ;

[0063] C6: ;

[0064] C7: 。

[0065] The present invention also provides a preparation method of the above supported metallocene catalyst additive, comprising the following steps:

[0066] (1) Reacting a bridged diphenol with an alkylaluminum to obtain a phenoxyaluminum compound;

[0067] (2) Reacting the phenoxyaluminum compound with an amine containing a siloxane at the chain end to obtain the compound shown in formula (I).

[0068] In some specific embodiments, in step (1), under the protection of an inert gas, using an alkane as a solvent, the bridged diphenol reacts with the alkylaluminum at 20 - 90 °C for 10 min - 6 h to obtain the phenoxyaluminum compound. Among them, the molar ratio of the bridged diphenol to the alkylaluminum is 1 - 3:1, preferably 2:1.

[0069] In some specific embodiments, in step (2), under the protection of an inert gas, an amine is added to the product of step (1), and the mixture is refluxed for 10 min - 3 h, and after cooling, the precipitate is collected to obtain the compound shown in formula (I). Among them, the molar ratio of the amine to the alkylaluminum is 0.8 - 1.2:1, preferably 1:1.

[0070] The present invention also provides a supported metallocene catalyst. The supported metallocene catalyst is obtained by refluxing a carrier and the above additive in a solvent to obtain an anchor chain structure silica - additive conjugate, and then combining the silica - additive conjugate with a metallocene compound, and its structure is shown in formula (II). This 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 included, the specific preparation method is to combine the silica - additive combination with the cocatalyst MAO and the metallocene compound to obtain the corresponding supported metallocene catalyst. Among them, the ratio of the support to the metallocene compound is 1 g of support corresponding to 10 μmol - 100 μmol of the metallocene compound, 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 the metallocene catalyst is not restricted. For example, single - center metallocene compounds can be used. The selection of the support is also not restricted, and the selection of the solvent is also not particularly restricted, and conventional reagents in the art can be used. For example, in some specific embodiments, the metallocene catalyst is selected from dimethylsilyl - bridged bis(indenyl)zirconium, ethylidene - bridged bis(indenyl)zirconium or ethylidene - bridged bis(indenyl)zirconium dihydride, the support is silica gel, and the solvent is an alkane or toluene.

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

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

[0077] The following will introduce the additives of the present invention in detail in combination 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 paraldehyde (4.9 g, 37.5 mmol), and then slowly dropwise add 1.0 mL of concentrated sulfuric acid. Place the reaction system at 60 o °C and heat for 3 hours, then adjust the temperature to 90 o °C and heat under reflux for 3 hours, and monitor the reaction by TLC. Extract the reaction solution 3 times with an appropriate amount of ice water and ethyl acetate, combine the organic phases, dry the organic phases with anhydrous sodium sulfate for 2 hours, filter, and rotary evaporate to remove the solvent to obtain a yellow oil. Purify it by column chromatography with a developing agent of PE:EA = 30:1, and finally obtain a pale yellow solid, namely ligand L 1 H2 (8.6 g, 53%). 11H 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 placed in a 100 mL Schlenk flask, and 30 mL of n-hexane was added and stirred until dissolved. Then, a solution of AlMe3 (9.5 mL, 9.5 mmol, 1 mol / L) in n-hexane was slowly added dropwise thereto, and the addition was completed after 5 minutes. The reaction mixture was stirred at room temperature for 30 min, and 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 flask. After reacting for 24 h, the stirring was stopped. After the reaction solution was allowed to stand, a white precipitate was formed. The precipitate was filtered, washed with a n-hexane solution, and the white solid was pumped with liquid nitrogen - cold trap for 2 h and then sealed for storage.

[0083] The preparation method of the C2-7 additive refers to the preparation method of the 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 the supported catalyst FZ1

[0085] Under nitrogen protection, 1.0 g of Grace silica gel activated at 600 °C for 6 h was taken and suspended in 50 mL of toluene. A toluene suspension containing 650 mg of the C1 additive was added, and the mixture was refluxed for 1 h. Then, a mixed solution of a toluene solution containing 21 mg (50 μmol) of ethylidene bridged dihydrindenyl zirconium and a toluene solution of 375 mg (2.5 mmol) of methylaluminoxane (MAO) was added, and the mixture was refluxed for 3 h, 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 the supported catalyst FZ2

[0087] 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 700 mg of C1 additive was added, and the mixture was refluxed for 1 h. Then, a mixed solution of a toluene solution containing 21 mg (50 μmol) of ethylidene bridged bisindenyl zirconium and a toluene solution containing 375 mg (2.5 mmol) of MAO was added, and the mixture was refluxed for 3 hours. After cooling, filtration, and drying by suction, 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 Zr content determined by elemental analysis 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 taken and suspended in 50 mL of toluene. A toluene suspension containing 700 mg of C1 additive was added, and the mixture was refluxed for 1 h. Then, a mixed solution of a toluene solution containing 21 mg (50 μmol) of ethylidene bridged bisindenyl zirconium and a toluene solution containing 750 mg (5 mmol) of MAO was added, and the mixture was refluxed for 3 hours. After cooling, filtration, and drying by suction, 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 Zr content determined by elemental analysis was 0.28%, and the Al content was 8.5%.

[0090] Example 4 Preparation of Supported Catalyst FZ4

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

[0092] Example 5 Preparation of Supported Catalyst FZ5

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

[0094] Example 6 Preparation of Supported Catalyst FZ6

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

[0096] Example 7 Preparation of Supported Catalyst FZ7

[0097] The preparation method is the same as that of Example 1, except that an equivalent amount of C6 is used instead of the C1 additive to obtain a powder with good flowability, which is the 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 the same as that of Example 1, except that no C1 additive is added to obtain a powder with good flowability, which is the catalyst DB1. 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 the same as that of Example 1, except that no C1 additive is added and the MAO dosage is 750 mg (5 mmol) to obtain a solid powder with good flowability, which is the 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 the same as that of Example 1, except that no C1 additive is added and the MAO dosage is 1500 mg (10 mmol) to obtain a solid powder with fluidity, which is the 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 the same as that of Example 1, except that no C1 additive is added and the MAO dosage is (2250 mg, 15 mmol), which is 300 times the amount of the zirconium compound, to obtain a solid powder with fluidity, which is the catalyst DB4. The elemental analysis shows that the Zr content is 0.18% and the Al content is 16.5%.

[0106] Ethylene polymerization experiment: A 200 mL polymerization kettle equipped with a stirring rod and a gas guide tube was dried under vacuum at 100 °C for at least 30 min, cooled down, purged with ethylene gas three times, filled with n-hexane and maintained 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 example or comparative example and 10 mL of hexane was added with a syringe, and the reaction was stirred for 10 min. The ethylene gas cylinder was closed, cooled down to room temperature, soaked in 10% hydrochloric acid ethanol, filtered, and the solid was washed with ethanol until neutral, and then dried under vacuum at 60 °C to constant weight. The mass of the polymer was weighed, and the polymerization activity of the catalyst was calculated. The melting point of the polymer was measured by DSC, and the molecular weight distribution of the polymer was measured by GPC. Among them, the test results are shown in Figure 3-14 As shown. Among them, in the figure of the GPC test results, the blue line is the differential distribution diagram of the molecular weight (corresponding to the ordinate dwt / d(logM)), and the red line is the cumulative distribution diagram of the molecular weight (corresponding to the ordinate 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 activities of the supported catalysts obtained in the examples are significantly better than those in the comparative examples, and the molecular weight distributions of the obtained polymers are narrower. The dosage of MAO in Example 1 is 50 times, compared with 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 examples are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing examples, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions 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 a carrier and the additive described in claim 1 or 2 in a solvent to obtain a carrier-additive combination with an anchor chain structure, and the carrier-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 carrier-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.

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