A poly-4-methyl-1-pentene resin based on a supported metallocene catalyst and a method for its preparation

Abstract

This invention proposes a poly(4-methyl-1-pentene) resin based on a supported metallocene catalyst and its preparation method. Based on a stepwise loading process using a silanized porous support, by optimizing the type of support (such as SiO2, Al2O3, MCM-41), the amount of support added (3 to 15 times), and the stepwise loading sequence (co-catalyst first, then main catalyst), the catalyst activity, stability, and product performance are synergistically improved, providing an innovative solution for the conversion of supported catalysts into industrial-scale high-efficiency systems.

Description

Technical Field

[0001] This invention belongs to the field of polymer material synthesis technology, specifically relating to a poly(4-methyl-1-pentene) resin based on a supported metallocene catalyst and its preparation method. Background Technology

[0002] Poly(4-methyl-1-pentene) (PMP) is a high-performance polyolefin material with excellent optical transparency, high temperature resistance, low dielectric constant, and chemical inertness, and is widely used in optical thin films, medical devices, and electronic packaging. The industrial production of PMP heavily relies on efficient catalyst systems, especially metallocene catalysts, because they can precisely control the polymer's molecular weight, molecular weight distribution, and stereostructure. However, traditional unsupported metallocene catalysts have significant drawbacks in practical applications, limiting their large-scale industrialization (e.g., Chinese patent applications CN118594541A, CN117943033A, CN116020565A, CN108273514A).

[0003] The unsupported metallocene catalysts used in the preparation of poly-4-methyl-1-pentene resin have the following technical drawbacks:

[0004] 1. Poor thermal stability: Unsupported metallocene catalysts are prone to deactivation of active sites during high-temperature polymerization, resulting in a rapid decline in catalytic efficiency. The reaction needs to be carried out at low temperatures, which leads to high energy consumption and low production efficiency.

[0005] 2. Uncontrollable product morphology: Homogeneous catalysts are prone to polymer particle agglomeration, forming sticky products, causing scale buildup on reactor walls, making post-processing difficult, and making it difficult to obtain uniform powdered resin, which is difficult for industrial continuous production.

[0006] 3. Residual catalyst contamination: Unloaded catalysts are prone to remain in the polymer, requiring additional deashing treatment, increasing production costs, and residual metals may affect the transparency and biocompatibility of the material.

[0007] 4. Wide molecular weight distribution: Insufficient control over the dispersion of active centers in homogeneous catalytic systems leads to large differences in polymer chain length, which can easily result in an excessively wide molecular weight distribution (PDI) (PDI>3.0), affecting material processing performance and end applications, and limiting high-precision processing applications (such as optical thin films).

[0008] To address the aforementioned issues, supported metallocene catalysts have gradually become a research hotspot. By immobilizing the metallocene active centers on the surface of a specific support, the overall performance of the catalytic system can be significantly improved.

[0009] 1. Enhanced thermal stability and activity: The support (such as silica, alumina, etc.) is coordinated with metallocene through surface chemical modification (such as silanization treatment), which stabilizes the active center, delays deactivation, and allows the reaction to be carried out at higher temperatures (such as 70~90℃), thereby improving polymerization efficiency.

[0010] 2. Controllable product morphology: The carrier, as a template, can control the morphology of polymer particles, avoid agglomeration, and obtain a powdered resin with good flowability, which is convenient for continuous industrial production.

[0011] 3. Low residue and easy separation: The supported design allows the catalyst to adhere firmly to the support, reducing the residue of free metal centers, lowering the cost of subsequent purification, and the catalyst can be recycled and reused.

[0012] 4. Narrowing of molecular weight distribution: The carrier confinement effect promotes the uniform distribution of active centers and inhibits chain transfer side reactions. The resulting polymer PDI can be controlled at 1.5~2.5, which meets the requirements of high-precision processing (such as optical-grade thin films).

[0013] Although supported catalysts have shown potential, their performance is still limited by factors such as support selection, loading process, and support-catalyst interactions. For example, untreated supports (such as ordinary SiO2) are prone to having active sites covered due to excessive coordination of hydroxyl groups with metallocenes; one-step loading methods (simultaneous loading of the main catalyst and co-catalyst) can easily lead to uneven distribution of active sites, reducing catalytic efficiency; and the amount of support added lacks optimization, as excessive support may clog pores and reduce the exposure of active sites, while insufficient support will result in incomplete loading. Summary of the Invention

[0014] (a) Technical problems to be solved

[0015] This invention proposes a poly(4-methyl-1-pentene) resin based on a supported metallocene catalyst and its preparation method, in order to solve the technical problem of how to achieve synergistic improvement of catalyst activity, stability and product performance.

[0016] (II) Technical Solution

[0017] To address the aforementioned technical problems, this invention proposes a method for preparing poly-4-methyl-1-pentene resin based on a supported metallocene catalyst, the method comprising the following steps:

[0018] (1) Carrier silanization treatment

[0019] The support was dehydrated, dissolved in toluene, and an activator was added. The support was then silanized under an inert gas atmosphere. After the reaction was completed, the support was washed and dried to obtain the silanized support.

[0020] (2) Catalyst stepwise loading

[0021] A cocatalyst is loaded onto the surface of a silanized support to obtain a support for a pre-loaded cocatalyst; a metallocene main catalyst is loaded onto the surface of the support for the pre-loaded cocatalyst to obtain a supported metallocene catalyst.

[0022] (3) Polymerization reaction

[0023] Hexane, 4-methyl-1-pentene monomer, supported metallocene catalyst and molecular weight regulator were added to a high-pressure reactor to carry out solution polymerization. After the reaction was completed, the mixture was filtered and dried to obtain a white powdery poly4-methyl-1-pentene resin.

[0024] Furthermore, in step (1), the support is silicon dioxide (SiO2), alumina (Al2O3), or mesoporous molecular sieve MCM-41.

[0025] Furthermore, in step (1), the activator is trimethylchlorosilane or hexamethyldisilazane.

[0026] Furthermore, in step (1), the silanization treatment temperature is 80~120℃ and the treatment time is 2~6 hours.

[0027] Further, step (2) specifically includes dissolving the co-catalyst in toluene, adding it to the silanized support, stirring the reaction at 40~60℃ for 2~4 hours, filtering and vacuum drying to obtain the support for the pre-loaded co-catalyst; dissolving the metallocene main catalyst in tetrahydrofuran, adding it to the support for the pre-loaded co-catalyst, stirring the reaction at room temperature for 6~12 hours under inert gas protection; filtering, washing and vacuum drying after the reaction to obtain the supported metallocene catalyst.

[0028] Furthermore, in step (2), the amount of silanization support added is 3 to 15 times that of the metallocene main catalyst.

[0029] Furthermore, in step (2), the co-catalyst is modified methylaluminoxane; the supported metallocene main catalyst is (C5H5)2MCl2, where M = Ti, Zr, and Hf.

[0030] Furthermore, in step (3), when carrying out the solution polymerization reaction, the temperature is raised to 70~90℃, the pressure is maintained at 2~4MPa, and the reaction is stirred for 1~3 hours.

[0031] Furthermore, this invention also proposes a poly-4-methyl-1-pentene resin based on a supported metallocene catalyst prepared by the above method.

[0032] Furthermore, the molecular weight distribution of poly(4-methyl-1-pentene) resin is PDI = 1.5~2.5, and the melt index at 230℃ / 2.16kg is stable at 10~50g / 10min.

[0033] (III) Beneficial Effects

[0034] This invention proposes a poly(4-methyl-1-pentene) resin based on a supported metallocene catalyst and its preparation method. Based on a stepwise loading process using a silanized porous support, by optimizing the type of support (such as SiO2, Al2O3, MCM-41), the amount of support added (3 to 15 times), and the stepwise loading sequence (co-catalyst first, then main catalyst), the catalyst activity, stability, and product performance are synergistically improved, providing an innovative solution for the conversion of supported catalysts into industrial-scale high-efficiency systems.

[0035] The beneficial effects of this invention specifically include:

[0036] 1. Enhanced catalyst performance: Silanized supports reduce the coverage of active sites, and the stepwise loading process improves catalytic activity by 30-50%, while also enhancing thermal stability (allowing for efficient operation above 70℃). The support confinement effect promotes uniform dispersion of active sites, reducing catalyst residue by over 60% and lowering deashing costs.

[0037] 2. Polymer performance optimization: The molecular weight distribution is significantly narrowed (PDI=1.5~2.5), and the melt index (230℃ / 2.16kg) is stabilized at 10~50 g / 10min, meeting the requirements of optical-grade processing. The product is a free-flowing powder without agglomeration, and can be directly used in high-precision molding processes such as injection molding and extrusion.

[0038] 3. Advantages in industrial applications: The process is compatible with continuous production, avoiding reactor scaling problems and reducing energy consumption and operational complexity. The resulting resin is suitable for high-end fields such as medical catheters, optical films, and high-frequency electronic packaging, possessing high value-added market potential. Attached Figure Description

[0039] Figure 1 This is a schematic diagram of the catalyst loading process in this invention;

[0040] Figure 2 This is a flowchart of the polymerization reaction in this invention. Detailed Implementation

[0041] To make the objectives, contents, and advantages of the present invention clearer, the specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples.

[0042] Example 1

[0043] This embodiment proposes a method for preparing poly-4-methyl-1-pentene resin based on a supported metallocene catalyst, which specifically includes the following steps:

[0044] (1) Silanization of the support: The mesoporous molecular sieve MCM-41 (pore size 3.5 nm, specific surface area 1000 m² / g) used as the support was placed in a vacuum drying oven and dehydrated at 110 °C for 2 hours. Subsequently, 1 g of the dehydrated MCM-41 was dissolved in 50 mL of toluene, and 0.5 mL of hexamethyldisilazane (HMDS) as an activator was added. The mixture was refluxed at 100 °C for 4 hours under nitrogen protection. After the reaction was completed, the mixture was washed and dried to obtain the silanized MCM-41 support.

[0045] (2) Supporting the co-catalyst: 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) as a co-catalyst was dissolved in 20 mL of toluene, and 0.8 g of silanized MCM-41 support was added (the amount of support added was 8 times the mass of the subsequent main catalyst). The mixture was stirred at 50 °C for 3 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support for the pre-supported co-catalyst.

[0046] (3) Supporting the main catalyst: 0.1 g of the metallocene main catalyst (C5H5)2ZrCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a support for the pre-supported co-catalyst was added. The reaction was stirred at room temperature for 8 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported metallocene catalyst (denoted as Cat-1).

[0047] (4) Polymerization reaction: In a 2L high-pressure reactor, add 500mL hexane, 50g 4-methyl-1-pentene monomer, 0.05g Cat-1 catalyst, and 0.1MPa hydrogen gas (molecular weight regulator). Heat to 70℃, maintain pressure at 2MPa, and stir for 2 hours. After the reaction is complete, filter and dry to obtain a white powdery poly(4-methyl-1-pentene) resin (denoted as PMP-1).

[0048] Example 2

[0049] In step (1), silicon dioxide (SiO2, particle size 50μm, specific surface area 300m²) is used. 2 The SiO2 support was placed in a vacuum drying oven and dehydrated at 110°C for 2 hours. Then, 1 g of SiO2 was dissolved in 50 mL of toluene, and 0.5 mL of hexamethyldisilazane (HMDS) was added. The mixture was refluxed at 100°C for 4 hours under nitrogen protection. After the reaction, the mixture was washed and dried to obtain the silanized SiO2 support. All other experimental conditions were the same as in Example 1, yielding a poly(4-methyl-1-pentene) resin (denoted as PMP-2).

[0050] Example 3

[0051] In step (1), alumina (Al2O3, particle size 80nm, specific surface area 200m²) is used. 2The silanized Al2O3 support was placed in a vacuum drying oven and dehydrated at 110°C for 2 hours. Then, 1 g of Al2O3 was dissolved in 50 mL of toluene, and 0.5 mL of hexamethyldisilazane (HMDS) was added. The mixture was refluxed at 100°C for 4 hours under nitrogen protection. After the reaction, the mixture was washed and dried to obtain the silanized Al2O3 support. All other experimental conditions were the same as in Example 1, yielding a poly(4-methyl-1-pentene) resin (denoted as PMP-3).

[0052] Example 4

[0053] In step (1), mesoporous molecular sieve MCM-41 (pore size 3.5 nm, specific surface area 1000 m²) is used. 2 The silanized MCM-41 support was placed in a vacuum drying oven and dehydrated at 110°C for 2 hours. Then, 1 g of MCM-41 was dissolved in 50 mL of toluene, and 0.5 mL of trimethylchlorosilane (TMCS) was added. The mixture was refluxed at 100°C for 4 hours under nitrogen protection. After the reaction, the mixture was washed and dried to obtain the silanized MCM-41 support. All other experimental conditions were the same as in Example 1, yielding poly(4-methyl-1-pentene) resin (denoted as PMP-4).

[0054] Example 5

[0055] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 0.8 g of silanized MCM-41 support was added (the amount of support added was 8 times the mass of the subsequent main catalyst). The reaction was stirred at 40 °C for 3 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-5) was obtained.

[0056] Example 6

[0057] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 0.8 g of silanized MCM-41 support was added (the amount of support added was 8 times the mass of the subsequent main catalyst). The reaction was stirred at 60 °C for 3 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-6) was obtained.

[0058] Example 7

[0059] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 0.8 g of silanized MCM-41 support was added (the amount of support added was 8 times the mass of the subsequent main catalyst). The reaction was stirred at 50 °C for 2 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-7) was obtained.

[0060] Example 8

[0061] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 0.8 g of silanized MCM-41 support was added (the amount of support added was 8 times the mass of the subsequent main catalyst). The reaction was stirred at 50 °C for 4 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-8) was obtained.

[0062] Example 9

[0063] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 0.6 g of silanized MCM-41 support was added (the amount of support added was 6 times the mass of the subsequent main catalyst). The reaction was stirred at 50 °C for 3 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-9) was obtained.

[0064] Example 10

[0065] In step (2), 0.1 g of modified methylaluminoxane (MMAO, 10 wt% toluene solution) was dissolved in 20 mL of toluene, and 1 g of silanized MCM-41 support was added (the amount of support added was 10 times the mass of the subsequent main catalyst). The reaction was stirred at 50 °C for 3 hours, filtered, and then vacuum dried at 60 °C for 4 hours to obtain the support with pre-loaded co-catalyst. Other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-10) was obtained.

[0066] Example 11

[0067] In step (3), 0.1 g of the metallocene main catalyst (C5H5)2TiCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a pre-supported carrier was added. The mixture was stirred at room temperature for 8 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported catalyst. All other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-11) was obtained.

[0068] Example 12

[0069] In step (3), 0.1 g of the metallocene main catalyst (C5H5)2HfCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a pre-supported carrier was added. The mixture was stirred at room temperature for 8 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported catalyst. All other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-12) was obtained.

[0070] Example 13

[0071] In step (3), 0.1 g of the metallocene main catalyst (C5H5)2ZrCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a pre-supported carrier was added. The mixture was stirred at room temperature for 6 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported catalyst. All other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-13) was obtained.

[0072] Example 14

[0073] In step (3), 0.1 g of the metallocene main catalyst (C5H5)2ZrCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a pre-supported carrier was added. The mixture was stirred at room temperature for 10 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported catalyst. All other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-14) was obtained.

[0074] Example 15

[0075] In step (3), 0.1 g of the metallocene main catalyst (C5H5)2ZrCl2 was dissolved in 30 mL of tetrahydrofuran (THF), and a pre-supported carrier was added. The mixture was stirred at room temperature for 12 hours under nitrogen protection. After filtration, the catalyst was washed twice with THF and dried under vacuum at 50 °C for 12 hours to obtain the supported catalyst. All other experimental conditions were the same as in Example 1, and poly(4-methyl-1-pentene) resin (denoted as PMP-15) was obtained.

[0076] Comparative Example 1

[0077] The support silanization step in Example 1 was omitted, and the MCM-41 support was used directly. Under the same conditions, the catalyst Cat-C1 and the product PMP-C1 were obtained.

[0078] Comparative Example 2

[0079] The main catalyst (C5H5)2ZrCl2 and the co-catalyst MMAO were simultaneously dissolved in toluene and mixed with the silanized MCM-41 support for reaction. The remaining conditions were the same as in Example 1 to obtain the catalyst Cat-C2 and the product PMP-C2.

[0080] The effects of the embodiments and comparative examples in this invention are shown in Table 1.

[0081] Table 1. Results of Examples and Comparative Examples

[0082] sample <![CDATA[Catalytic activity (×10 5 gPMP / mol Zr h)]]> PDI Melt index (g / 10 min) Residual Zr (ppm) Product morphology PMP-1 8.5 1.8 35 ＜5 uniform white powder PMP-2 7.8 2.0 28 ＜8 uniform white powder PMP-3 6.2 2.6 22 ＜18 Partial clumping PMP-4 7.7 2.3 25 ＜10 uniform white powder PMP-5 6.5 2.4 23 ＜13 Partial clumping PMP-6 8.4 2.0 32 ＜8 uniform white powder PMP-7 6.4 2.6 21 ＜16 Partial clumping PMP-8 7.4 2.2 24 ＜14 uniform white powder PMP-9 6.2 2.5 21 ＞20 Partial clumping PMP-10 6.0 2.9 21 ＞20 Partial clumping PMP-11 5.2 3.1 18 ＞30 Partial clumping PMP-12 7.5 3.0 25 ＞20 Partial clumping PMP-13 6.8 2.6 25 ＜15 A small amount of powder clumps PMP-14 8.0 1.9 33 ＜6 uniform white powder PMP-15 6.4 2.5 20 ＜15 A small amount of powder clumps PMP-C1 4.0 3.2 15 ＞50 viscous lumps PMP-C2 5.8 2.8 25 ＞20 Partial clumping

[0083] As shown in the table, by adjusting the type of catalyst support, the pretreatment method of the support, the amount of support added, the type of main catalyst, and the catalyst loading conditions, this invention yields a process for preparing supported metallocene catalysts. The silanized support (Example 1, Comparative Example 1) significantly improves catalytic activity and product performance, and has a low residual metal content. Compared to the one-step loading method (Example 1, Comparative Example 2), the stepwise loading process (procatalyst first, then main catalyst) increases activity by 40% and reduces PDI by 30%. Optimizing the amount of support added ensures a balance between loading uniformity and active site exposure.

[0084] The catalyst loading process of the present invention is as follows: Figure 1 As shown, the polymerization reaction process is as follows: Figure 2 As shown.

[0085] In terms of catalyst support selection and treatment, silica (SiO2), alumina (Al2O3), or mesoporous molecular sieves (MCM-41, SBA-15) are used as supports, and they are silanized (such as modified with trimethylchlorosilane or hexamethyldisilazane) to reduce the excessive coordination of surface hydroxyl groups to active centers.

[0086] Regarding the control of the amount of support added, the mass of the support is 3 to 15 times (preferably 5 to 10 times) of the metallocene main catalyst, which can balance the exposure of active sites and the uniformity of loading.

[0087] In the stepwise loading process, the loading sequence is as follows: first, the co-catalyst (alkylaluminoxane / MMAO) is loaded, followed by the metallocene main catalyst ((C5H5)2MCl2, M=Ti / Zr / Hf), which ensures efficient anchoring of the active center. The loading conditions are: the co-catalyst is loaded in toluene (reaction at 40~60℃ for 2~4 hours), and the main catalyst is loaded in tetrahydrofuran (reaction under inert gas protection for 6~12 hours).

[0088] In terms of polymerization process optimization, solution polymerization at 70~90℃ and 2~4MPa pressure in the presence of hydrogen molecular weight regulator can achieve synergistic regulation of activity and stability.

[0089] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing poly-4-methyl-1-pentene resin based on a supported metallocene catalyst, characterized in that, The preparation method includes the following steps: (1) Carrier silanization treatment The support was dehydrated, dissolved in toluene, and an activator was added. The support was then silanized under an inert gas atmosphere. After the reaction was completed, the support was washed and dried to obtain the silanized support. (2) Catalyst stepwise loading A cocatalyst is loaded onto the surface of a silanized support to obtain a support for a pre-loaded cocatalyst; a metallocene main catalyst is loaded onto the surface of the support for the pre-loaded cocatalyst to obtain a supported metallocene catalyst. (3) Polymerization reaction Hexane, 4-methyl-1-pentene monomer, supported metallocene catalyst and molecular weight regulator were added to a high-pressure reactor to carry out solution polymerization. After the reaction was completed, the mixture was filtered and dried to obtain a white powdery poly4-methyl-1-pentene resin.

2. The method for preparing poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 1, wherein in step (1), the support is silica, alumina or mesoporous molecular sieve MCM-41.

3. In the preparation method of poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 1, in step (1), the activator is trimethylchlorosilane or hexamethyldisilazane.

4. In the preparation method of poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 1, in step (1), the silanization treatment temperature is 80~120℃ and the treatment time is 2~6 hours.

5. The method for preparing poly-4-methyl-1-pentene resin based on a supported metallocene catalyst as described in claim 1, wherein step (2) specifically includes: dissolving the co-catalyst in toluene, adding a silanized support, stirring at 40-60°C for 2-4 hours, filtering and vacuum drying to obtain a support for the pre-supported co-catalyst; dissolving the metallocene main catalyst in tetrahydrofuran, adding the support for the pre-supported co-catalyst, stirring at room temperature for 6-12 hours under inert gas protection; and filtering, washing and vacuum drying after the reaction to obtain the supported metallocene catalyst.

6. In the preparation method of poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 5, in step (2), the amount of silanization support added is 3 to 15 times that of the metallocene main catalyst.

7. The method for preparing poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 5, wherein in step (2), the co-catalyst is modified methylaluminoxane; the supported metallocene main catalyst is (C5H5)2MCl2, where M = Ti, Zr, Hf.

8. In the preparation method of poly-4-methyl-1-pentene resin based on supported metallocene catalyst as described in claim 1, in step (3), when carrying out solution polymerization, the temperature is raised to 70~90℃, the pressure is maintained at 2~4MPa, and the reaction is stirred for 1~3 hours.

9. A poly-4-methyl-1-pentene resin based on a supported metallocene catalyst, prepared by the method according to any one of claims 1 to 8.

10. The poly-4-methyl-1-pentene resin based on a supported metallocene catalyst as described in claim 9, characterized in that, The poly(4-methyl-1-pentene) resin has a molecular weight distribution (PDI) of 1.5 to 2.5 and a melt index of 10 to 50 g / 10 min at 230°C / 2.16 kg.

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