Multi-component complex catalyst system for high temperature solution polymerization and its application in preparation of high-end polyolefins

Abstract

This invention relates to a multi-component composite catalyst system for high-temperature solution polymerization and its application in the preparation of high-end polyolefins. The composite catalyst system includes a main catalyst, a co-catalyst, and functional auxiliaries. The main catalyst is a metallocene compound or a non-metallocene transition metal compound, the co-catalyst is an organoaluminum compound and / or an organoboron compound, and the functional auxiliaries include antistatic agents, scale inhibitors, and electronic stabilizing agents. Compared with existing technologies, this invention achieves highly efficient olefin polymerization at high temperatures of 150-220℃ through the synergistic effect of the main catalyst, co-catalyst, and functional auxiliaries, and achieves comprehensive control over the polymer molecular weight distribution and comonomer distribution.

Description

Technical Field

[0001] This invention belongs to the field of polyolefin catalytic materials technology, and relates to a multi-component composite catalyst system for high-temperature solution polymerization and its application in the preparation of high-end polyolefins. Background Technology

[0002] High-end polyolefins refer to high-performance, high-value-added polyolefin materials, including polyolefin elastomers (POE), polyolefin plastisols (POP), linear low-density polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE), and polypropylene (PP). Among them, polyolefin elastomers (POE), as a high-performance thermoplastic elastomer, combine the processability of plastics with the high elasticity of rubber, and are widely used in photovoltaic module encapsulation, lightweight automotive components, medical devices, and high-end packaging. Especially in the photovoltaic industry, photovoltaic encapsulation films made from high-end polyolefins (such as POE) are indispensable core encapsulation materials, playing a decisive role in the weather resistance, moisture barrier properties, and service life of photovoltaic modules.

[0003] High-temperature solution polymerization is the mainstream process for producing high-end polyolefins (especially ethylene-α-olefin copolymers). Dow Chemical was the first to industrialize POE in the 1990s, using the INSITE high-temperature continuous solution polymerization process with restricted geometry metallocene catalysts (CGC) to catalyze the copolymerization of ethylene and α-olefins, synthesizing POE products under the trade names ENGAGE and AFFINITY. Subsequently, international companies such as ExxonMobil, Mitsui Chemicals, and LG Chem also launched their own high-end polyolefin products, including polyolefin elastomers and plastomers.

[0004] In the field of catalyst technology, current research mainly focuses on the development of metallocene catalyst systems. For example, the China National Chemical Research Institute recently developed a novel metallocene catalyst system characterized by high catalytic activity, few side reactions, and a wide operating temperature range. Wanhua Chemical has applied for a patent for a solution polymerization method (publication number CN202410277074.3), which, through the introduction of impurity removal agents and other improvement measures, can prepare olefin polymers with narrow molecular weight distribution and uniform comonomer distribution. In addition, domestic and foreign research institutions have also conducted extensive research on novel catalytic systems such as non-metallocene catalysts and binuclear catalysts, aiming to achieve precise control over the microstructure of polyolefins.

[0005] Current high-temperature solution polymerization catalysts face the following bottlenecks: First, a single catalyst system cannot simultaneously meet the multiple requirements of high activity, high temperature stability, and tunable product structure. Under high-temperature (150-220℃) solution polymerization conditions, the catalyst is prone to deactivation, side reactions increase, resulting in a wider polymer molecular weight distribution and uneven distribution of comonomers.

[0006] Secondly, reactor scaling is a significant problem during polymerization. At high temperatures, polymers easily deposit on the reactor walls and agitators, which not only affects heat and mass transfer efficiency but also shortens the unit's operating cycle, increasing the frequency and cost of shutdowns for cleaning.

[0007] Third, the means of controlling polymer molecular weight distribution are limited. Existing technologies mostly rely on complex bifunctional catalysts or external electron donors to control molecular weight distribution, which are complex, costly, and have limited control range. For example, the preparation of olefin block copolymers (OBCs) using chain shuttle polymerization requires two catalysts and one chain shuttle agent, resulting in a complex system, and the control of soft and hard segment lengths and block numbers remains limited.

[0008] Fourth, the uniformity of comonomer distribution is difficult to guarantee. During batch or semi-batch polymerization, the time-varying concentration of reactants easily leads to compositional drift, resulting in uneven distribution of comonomers between polymer chains. This affects the mechanical and optical properties of the product, limiting the application of high-end polyolefins in demanding fields such as optics and electronics.

[0009] To address the aforementioned issues, research institutions such as Zhejiang University have conducted studies on comb-like polyolefin elastomers (CPOEs), achieving chain structure control through cascade polymerization. However, this method still involves multi-step reactions and complex catalyst systems. Therefore, developing a catalyst system that is simple in process, low in cost, and allows for flexible control of product performance is of great significance for promoting the domestic production of high-end polyolefins and meeting the needs of high-end manufacturing fields such as photovoltaics, wires and cables, and medical devices. Summary of the Invention

[0010] The purpose of this invention is to provide a multi-component compound catalyst system for high-temperature solution polymerization and its application in the preparation of high-end polyolefins. It can overcome the defects of existing high-temperature solution polymerization catalysts, such as single function, complex process, and difficulty in product performance control. It can achieve efficient olefin polymerization at high temperatures of 150-220℃ and achieve comprehensive control over the distribution of polymer molecular weight and comonomers.

[0011] The objective of this invention can be achieved through the following technical solutions: In a first aspect, the present invention provides a multi-component composite catalyst system for high-temperature solution polymerization, comprising a main catalyst, a co-catalyst, and functional additives, wherein the main catalyst is a metallocene compound or a non-metallocene transition metal compound, the co-catalyst is an organoaluminum compound and / or an organoboron compound, and the functional additives include antistatic agents, scale inhibitors, molecular weight regulators, and electronic stabilizing agents.

[0012] Furthermore, the metallocene compound is selected from bridged or non-bridged zirconium dichlorodi ... The non-ceramic transition metal compound is selected from pyridine imine or salicylaldehyde imine complexes of the iron, nickel, or vanadium series. For example, it can be a pyridine imine iron complex [2,6-(2,6-Me2C6H3N=CMe)2C5H3N]FeCl2, etc.

[0013] Furthermore, the organoaluminum compound is selected from methylaluminoxane (MAO), modified methylaluminoxane (MMAO), trimethylaluminum, triethylaluminum, or triisobutylaluminum; The organoboron compound is selected from tris(pentafluorophenyl)boron or tetra(pentafluorophenyl)borate compounds.

[0014] Furthermore, the antistatic agent is selected from ethoxylated amines or alkyl sulfonates; The anti-scaling agent is selected from polyisobutylene or ethylene-propylene copolymer; The electronically stabilized additive is selected from tetrahydrofuran, diethyl ether, or silane compounds.

[0015] Furthermore, the molar ratio of the main catalyst to the co-catalyst is 1:10 to 10000, and can be selected as 1:100 to 1000. For example, it can be 1:10, 1:50, 1:100, 1:500, 1:1000, 1:2000, 1:10000, etc. The total amount of the functional additives added accounts for 0.1% to 5% of the total weight of the catalyst system; The molar ratio of the electronically stabilized additive to the main catalyst is 1~100:1, optionally 10~80:1, for example, 10:1, 50:1, etc., used to adjust the molecular weight distribution of the polymer and the insertion selectivity of the comonomer. The amount of the antistatic agent added accounts for 0.1% - 3.0% of the total weight of the catalyst system, preferably 0.3% - 2.0%, and more preferably 0.5% to 1.5%.

[0016] The amount of the scale inhibitor added accounts for 0.05% - 2.0% of the total weight of the catalyst system, preferably 0.1% - 1.5%, and more preferably 0.3% to 1.0%.

[0017] The molecular weight regulator is hydrogen, and its partial pressure accounts for 0.5% to 15% of the total pressure of the reaction system, preferably 1% to 10%, and more preferably 2% to 8%.

[0018] In a second aspect, the present invention provides an application of a multi-component composite catalyst system for high-temperature solution polymerization in the preparation of high-end polyolefins.

[0019] In a third aspect, the present invention provides a method for preparing high-end polyolefins, comprising the following steps: S1. The multi-component compound catalyst system, mixed solvent, and one or more long-chain α-olefins described in the first aspect above are added into a high-pressure polymerization reactor, heated to the reaction temperature, and ethylene is introduced to carry out the polymerization reaction. S2. After the reaction is complete, the reaction is terminated, and the resulting reaction product is devolatilized and granulated to obtain high-end polyolefin products.

[0020] In the preparation process described above, thanks to the synergistic effect of the main catalyst, co-catalyst, and functional auxiliaries in the composite catalyst system, the method of this invention still exhibits excellent catalytic activity under high-temperature polymerization conditions. Experiments show that the catalyst activity can reach 20~50×10⁻⁶. 4 g-POE / g-cat (i.e., each gram of catalyst can produce 200-500 kg of polyolefin polymer), which is more than 50% higher than that of traditional metallocene catalyst systems. Even under harsh temperature conditions above 200°C, the catalyst system of this invention can still maintain high activity (activity retention rate >70% at 180°C), significantly extending the operating cycle of the unit and reducing catalyst consumption per unit.

[0021] Furthermore, in S1, the polymerization reaction temperature is 150~220℃, the time is 5~60min, and the ethylene feed rate is sufficient to maintain the reaction pressure at 1.0-6.0MPa; The long-chain α-olefin is one or more of 1-butene, 1-hexene, 1-octene, 1-decene, dodecene, and tetradecene, and its molar percentage in the polymerization raw materials is 10%-70%.

[0022] Furthermore, in S1, the mixed solvent is formed by mixing an inert alkane or aromatic hydrocarbon organic solvent A with an organic solvent B containing polar functional groups at a volume ratio of 5 to 10:1. The organic solvent A is selected from one of n-hexane, cyclohexane, n-heptane, toluene, or xylene, and the organic solvent B is selected from one of tetrahydrofuran, dioxane, ethyl acetate, or acetone.

[0023] Furthermore, in S1, hydrogen gas, a molecular weight regulator, is added during the polymerization reaction to control the molecular weight of high-end polyolefin products.

[0024] Furthermore, by adjusting the ratio of organic solvent A to organic solvent B in the mixed solvent, as well as the type and amount of functional additives, the molecular weight distribution of high-end polyolefins can be flexibly controlled, with a weight-average molecular weight (Mw) of 50,000-300,000 g / mol and an adjustable range of molecular weight distribution Mw / Mn of 2.0-5.0.

[0025] Compared with the prior art, the present invention has the following advantages: (1) High catalytic activity and good stability: Through the synergistic effect of the main catalyst, co-catalyst and functional additives, the catalyst system of the present invention maintains high catalytic activity under high temperature conditions of 150-220℃, significantly suppresses high temperature side reactions, and overcomes the defect of easy deactivation of single catalyst.

[0026] (2) Simple process and low cost: No complex bifunctional catalyst or external electron donor is required. The polymerization process can be controlled by introducing functional additives. The catalyst cost is low and the polymerization process is simple.

[0027] (3) Long reactor operation cycle: The introduction of antistatic agents and scale inhibitors effectively improves the dispersion stability of the catalyst in high temperature solution, inhibits the deposition of polymer on the reactor wall and agitator, and extends the continuous operation time of the device.

[0028] (4) Molecular weight distribution can be flexibly controlled: By adjusting the ratio of organic solvent A to B in the mixed solvent and combining the synergistic effect of functional additives, Mw / Mn can be flexibly controlled in the range of 2.0-5.0 to meet the needs of different application scenarios for material processing performance and mechanical properties.

[0029] (5) Uniform distribution of comonomers: It overcomes the compositional drift problem caused by the time-varying concentration of reactants in traditional batch polymerization. The uniformity index of the distribution of high-end polyolefin comonomers is greater than 95%, which ensures the stability of product performance. Attached Figure Description

[0030] Figure 1 GPC spectrum of polyethylene elastomer prepared in Example A1; Figure 2 The GPC spectrum of the polyethylene elastomer prepared in Example A2; Figure 3 GPC spectrum of polyethylene elastomer prepared in Example B10; Figure 4 Carbon NMR spectrum of polyethylene elastomer prepared for Example A1; Figure 5 The carbon NMR spectrum of polyethylene elastomer was prepared for Example A2. Detailed Implementation

[0031] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0032] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0033] As used herein, the terms "and / or," "or / and," and "and / or" encompass any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected using at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that, in this application, the technical solution undoubtedly includes solutions connected by "logical AND," and also undoubtedly includes solutions connected by "logical OR."

[0034] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0035] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0036] This document only specifically discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0037] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows temperature fluctuations within the precision range controlled by the instrument, such as ±5°C, ±4°C, ±3°C, ±2°C, or ±1°C.

[0038] In this document, the term "suitable" as used in phrases such as "suitable combination," "suitable method," and "any suitable method" refers to the ability to implement the technical solution of this application, solve the technical problem of this application, and achieve the expected technical effect of this application.

[0039] In this application, terms such as "further," "even further," and "particularly" are used to describe purposes and indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0040] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it means that it is selected from either "with" or "without." If there are multiple "optional" entries in a technical solution, unless otherwise specified, and there are no contradictions or mutual constraints, each "optional" entry shall be independent.

[0041] In the description of the application, "multiple" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0042] Unless otherwise specified, all preparations and tests described herein took place at 25°C.

[0043] The terms “comprising,” “including,” “containing,” “having,” “comprising,” or other variations thereof are intended to cover non-closed inclusion, and no distinction is made between these terms. The term “comprising” means that other steps and ingredients may be added without affecting the final result. The compositions and methods / processes of the present invention comprise, consist of, and substantially consist of the essential elements and limitations described herein, as well as any additional or optional ingredients, components, steps, or limitations described herein. No distinction is made between the terms “efficacy,” “performance,” “effect,” and “potency” herein.

[0044] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions. Unless otherwise specified, all technical features and optional technical features of this application can be combined to form new technical solutions.

[0045] Unless otherwise specified, all steps of this application may be performed sequentially or randomly, but sequentially is preferred.

[0046] To overcome the shortcomings of existing high-temperature solution polymerization catalysts, such as limited functionality, complex processes, and difficulty in controlling product performance, this invention provides a method for preparing high-end polyolefins based on a multi-component composite catalyst system, as detailed below: First, the catalyst system is prepared: a main catalyst, a co-catalyst, and functional additives are compounded, wherein the functional additives consist of antistatic agents, scale inhibitors, and electronic stabilizing agents; Polymerization reaction: The prepared catalyst system, mixed solvent, and long-chain α-olefin are added to a high-pressure polymerization reactor, heated, and ethylene is introduced to carry out the polymerization reaction. During the polymerization reaction, hydrogen can also be introduced simultaneously as a molecular weight regulator to control the molecular weight of the polyolefin product. After the reaction is completed, a quencher is added to terminate the reaction. After devolatilization and granulation, high-end polyolefin products are obtained.

[0047] The preparation method described above will be explained in more detail below with reference to specific embodiments.

[0048] The specific sources of each raw material component are as follows: The pyridineimine iron complex [2,6-(2,6-Me2C6H3N=CMe)2C5H3N]FeCl2 can be prepared by referring to the method of Example 1 in Patent 201880077621.6.

[0049] Method for testing comonomer insertion rate: Weigh 60 mg of elastic polyethylene sample and add it to an NMR tube. Add 0.5 mL of 1,2,4-trichlorobenzene to completely dissolve it into a homogeneous transparent / semi-transparent solution. Measure the 13C-NMR using an NMR spectrometer at 125℃. Instrument settings: pulse angle 30°, relaxation time 5 s, 13000 scans, sampling time 0.65 seconds. The acquired data were Fourier transformed, and the 5-55 ppm peaks were normalized. Then, each peak was assigned and integrated, and the comonomer content was calculated based on the integrated area.

[0050] Uniformity index test method: The molecular weight of elastic polyethylene was tested according to ASTM D 6474-1999, "Standard Test Method for Determining Molecular Weight Distribution and Molecular Weight Averages of Polyolefins by High Temperature Gel Permeation Chromatography". 3.2 mg of sample was weighed and dissolved completely in 8 mL of 1,2,4-trichlorobenzene to form a homogeneous, transparent solution with a concentration of 0.4 mg / mL. The test was then conducted at 150°C.

[0051] Haze Test Method: According to ASTM D1003, this method includes the flux of scattered light deviating more than 2.5 degrees from the incident light direction in the haze calculation; scattered light less than 2.5 degrees is not included. This definition ensures the comparability and repeatability of test results. Haze and transmittance are two independent optical parameters: transmittance measures the proportion of light passing through a material, while haze characterizes the loss of clarity due to scattering. Both must be used together to comprehensively evaluate the transparency of a material.

[0052] Example A1: Zirconium / MAO basic system (synergistic effect of three additives) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 15 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 8.7 g), with the Al / Zr molar ratio controlled at 150:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stabilizing agent: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio (i.e., the molar ratio of electronic stabilizing agent to Zr atoms) = 2:1; Total weight of catalyst system: approximately 8.85 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, 30% molar percentage (relative to the total amount of ethylene + comonomer); Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa (continuous replenishment to maintain constant pressure); Reaction time: 30 minutes; Reactor: 5 L high-pressure stainless steel reactor, stirring speed 800 rpm; (3) Aggregation results: Polymer yield: 2180 g; Catalyst activity: 24.6 × 10 4 g-POE / g-cat (i.e., 246 kg of polymer is produced per gram of catalyst); Product performance: Mw=79,700 g / mol, Mw / Mn=2.2, comonomer insertion rate 17.9%, uniformity index 97%, melt index (190℃, 2.16kg)=8.2 g / 10min, haze 3.2%; It is evident that, through the synergistic effect of the three functional additives, the activity reached 24.6 × 10⁻⁶. 4 The g-POE / g-cat ratio is significantly higher than the average level (approximately 15~20×10⁻⁶) of metallocene catalysts reported in the literature (Mehdiabadi S, João BP Soares. Quantifying the Copolymerization Kinetics of Ethylene and 1-Octene Catalyzed with rac-Et(Ind)₂ZrCl₂ in a Solution Reactor[J]. Macromolecules, 2016.DOI:10.1021 / acs.macromol.5b02755.). 4 ).

[0053] Example A2: Optimized system with high Al / Zr ratio (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 40 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 23.2 g), Al / Zr molar ratio = 400:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 23.35 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa; Reaction time: 30 minutes; (3) Aggregation results: Polymer yield: 7660 g; Catalyst activity: 32.8 × 10 4 g-POE / g-cat (i.e., 328 kg of polymer is produced per gram of catalyst); Product performance: Mw=77,600 g / mol, Mw / Mn=2.1, comonomer insertion rate 18.1%, uniformity index 98%, melt index 15.6 g / 10min, haze 2.8%. It is evident that when the Al / Zr ratio is increased to 400:1, the number of active sites increases, and the activity is improved by 33% compared to Example A1, further reaching 32.8 × 10⁻⁶. 4 The excellent performance of g-POE / g-cat.

[0054] Example A3: Dual co-catalyst system (organoaluminum + organoboron) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g) Cocatalyst A: Triethylaluminum (TEA) 8 mmol (1.0 M hexane solution, 8 mL), Al / Zr molar ratio = 80:1; Co-catalyst B: tris(pentafluorophenyl)boron (B(C6F5)3) 0.15 mmol (approximately 0.077 g), B / Zr molar ratio = 1.5:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 8.22 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, 30% molar percentage (relative to the total amount of ethylene + comonomer); Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa (continuous replenishment to maintain constant pressure); Reaction time: 30 minutes; Reactor: 5 L high-pressure stainless steel reactor, stirring speed 800 rpm; (3) Aggregation results: Polymer yield: 2890 g; Catalyst activity: 35.2 × 10⁻⁶ 4 g-POE / g-cat (i.e., 352 kg of polymer is produced per gram of catalyst); Product performance: Mw=132,000 g / mol, Mw / Mn=2.4, comonomer insertion rate 27%, uniformity index 98%, melt index=12.8 g / 10min, haze 2.9%.

[0055] It is evident that when organoboron and organoaluminum are combined as a cocatalyst, a more stable cationic active center is formed, and the activity is increased by 43% compared to Example A1, reaching 35.2 × 10⁻⁶. 4 g-POE / g-cat, while the product has a narrower molecular weight distribution.

[0056] Example A4: High Electronic Stability Additive Ratio System (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 15 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 8.7 g), Al / Zr = 150:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.5 mmol (approximately 0.036 g), ED / Zr molar ratio = 5:1; Total weight of catalyst system: approximately 8.87 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, 30% molar percentage (relative to the total amount of ethylene + comonomer); Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa (continuous replenishment to maintain constant pressure); Reaction time: 30 minutes; Reactor: 5 L high-pressure stainless steel reactor, stirring speed 800 rpm; (3) Aggregation results: Polymer yield: 2530 g; Catalyst activity: 28.5 × 10 4g-POE / g-cat (i.e., 285 kg of polymer is produced per gram of catalyst); Product performance: Mw=108,000 g / mol, Mw / Mn=2.2, comonomer insertion rate 29%, uniformity index 99%, melt index=22.3 g / 10min, haze 2.5%.

[0057] It is evident that by increasing the ratio of electronic stabilizer to 5:1 and adjusting the electronic effect of the active center, the activity can be maintained at 28.5 × 10⁻⁶. 4 The level is high, while the comonomer insertion rate is increased to 29% and the uniformity reaches 99%.

[0058] Example A5: Silicon-bridged metallocene system (1) Preparation of catalyst system: Main catalyst: 0.10 mmol (approximately 0.058 g) of dimethylsilyl-bridged bis(indyl)zirconium dichloride (rac-Me2Si(Ind)2ZrCl2); Co-catalyst: 20 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 11.6 g), Al / Zr = 200:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stabilizing agent: cyclohexylmethyldimethoxysilane (CHMDMS) 0.25 mmol (approximately 0.058 g), ED / Zr = 2.5:1; Total weight of catalyst system: approximately 11.80 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, 30% molar percentage (relative to the total amount of ethylene + comonomer); Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa (continuous replenishment to maintain constant pressure); Reaction time: 30 minutes; Reactor: 5 L high-pressure stainless steel reactor, stirring speed 800 rpm; (3) Aggregation results: Polymer yield: 3550 g; Catalyst activity: 30.1 × 10 4 g-POE / g-cat (i.e., 301 kg of polymer is produced per gram of catalyst) Product performance: Mw=148,000 g / mol, Mw / Mn=2.5, comonomer insertion rate 25%, uniformity index 98%, melt index=9.6 g / 10min, haze 3.1%.

[0059] As can be seen, the silicon-bridged, aspherical metal structure provides more open active centers, achieving an activity of 30.1 × 10⁻⁶. 4 The product has excellent overall performance.

[0060] Example A6: Polar Solvent Optimization System (1) Catalyst system preparation: Same as in Example A1; (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 3:1 (volume ratio, to increase the proportion of polar solvent), total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa; Reaction time: 30 minutes; (3) Aggregation results: Polymer yield: 2370 g; Catalyst activity: 26.8 × 10 4 g-POE / g-cat (i.e., 268 kg of polymer is produced per gram of catalyst); Product performance: Mw=142,000 g / mol, Mw / Mn=2.4, comonomer insertion rate 28%, uniformity index 98%, melt index=11.2 g / 10min, haze 2.9%. It is evident that increasing the proportion of polar solvent can improve catalyst solubility and active site dispersion, while maintaining the activity at 26.8 × 10⁻⁶. 4 High level, with comonomer insertion rate increased to 28%.

[0061] Example A7: Non-ferrocene catalyst system (1) Preparation of catalyst system: Main catalyst: pyridineimine iron complex [2,6-(2,6-Me2C6H3N=CMe)2C5H3N]FeCl2 0.15 mmol (approximately 0.095 g); Co-catalyst: 18 mmol of modified methylaluminoxane (MMAO) (7 wt% heptane solution, approximately 15.4 g), Al / Fe molar ratio = 120:1; Antistatic agent: Alkyl sulfonate compound (Hostastat HS-1) 0.06 g; Scale inhibitor: 0.04 g of ethylene-propylene copolymer (EPM, Mn=2000); Electronic stabilizing agent: Dimethoxydimethylsilane (DMDMS) 0.3 mmol (approximately 0.040 g), ED / Fe = 2:1; Total weight of catalyst system: approximately 15.64 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-hexene, 40% molar percentage; Polymerization temperature: 160℃ (suitable temperature for iron-based catalysts); Ethylene pressure: 3.5 MPa; Reaction time: 40 minutes; (3) Aggregation results: Polymer yield: 3480 g; Catalyst activity: 22.3 × 10 4 g-POE / g-cat (i.e., 223 kg of polymer is produced per gram of catalyst); Product performance: Mw=178,000 g / mol, Mw / Mn=3.0, comonomer insertion rate 30%, uniformity index 97%, melt index=5.6 g / 10min, haze 3.5%.

[0062] It can be seen that the non-ferrocene catalyst still maintains a strength of 22.3 × 10⁻⁶ at lower temperatures. 4 It exhibits high activity and excellent α-olefin insertion ability (30%).

[0063] Example A8: High Temperature and High Pressure Extreme System (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 15 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 8.7 g), Al / Zr molar ratio = 150:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 8.85 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Polymerization temperature: 200℃ (higher than the normal operating temperature); Ethylene pressure: 5.0 MPa (increase pressure); Reaction time: 20 minutes (reaction time is shortened at high temperatures); (3) Aggregation results: Polymer yield: 3420 g; Catalyst activity: 38.6 × 10 4 g-POE / g-cat (i.e., 386 kg of polymer is produced per gram of catalyst, the highest in this series); Product performance: Mw=98,000 g / mol, Mw / Mn=2.3, comonomer insertion rate 29%, uniformity index 96%, melt index=28.5 g / 10min, haze 2.6%.

[0064] It is evident that the mass transfer rate increases under high temperature and high pressure, and the activity reaches 38.6 × 10⁻⁶. 4 The peak level demonstrates that the compound catalyst can still perform excellently under harsh conditions.

[0065] Example A9: Mixed Comonomer System (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 15 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 8.7 g), Al / Zr molar ratio = 150:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 8.85 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Mixed comonomers: 1-hexene (15% molar percentage) + 1-octene (20% molar percentage), total molar percentage 35%; Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa; Reaction time: 30 minutes; (3) Aggregation results: Polymer yield: 2270 g; Catalyst activity: 25.7 × 10 4 g-POE / g-cat (i.e., 257 kg of polymer is produced per gram of catalyst); Product performance: Mw=158,000 g / mol, Mw / Mn=2.7, total monomer insertion rate 27% (hexene 12% + octene 15%), uniformity index 98%, melt index = 8.9 g / 10min, haze 3.3%.

[0066] It can be seen that the catalyst activity remains at 25.7 × 10⁻⁶ under mixed comonomer conditions. 4 The uniformity index of 98% proves that the catalyst has good copolymerization ability for a variety of comonomers.

[0067] Example A10: Synergistic System of Electronic Stabilizing Agent + Hydrogen (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 15 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 8.7 g), Al / Zr = 150:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.4 mmol (approximately 0.029 g), ED / Zr molar ratio = 4:1; Total weight of catalyst system: approximately 8.86 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Molecular weight regulator: hydrogen gas, partial pressure 0.03 MPa (introduced into the reactor). Polymerization temperature: 180℃; Ethylene pressure: 4.0 MPa (total pressure of ethylene and hydrogen). Reaction time: 30 minutes; (3) Aggregation results: Polymer yield: 2590 g; Catalyst activity: 29.3 × 10 4 g-POE / g-cat (i.e., 293 kg of polymer is produced per gram of catalyst); Product performance: Mw=86,000 g / mol, Mw / Mn=2.1, comonomer insertion rate 28%, uniformity index 99%, melt index=38.2 g / 10min, haze 2.4%.

[0068] It can be seen that, based on the synergistic effect of electronically stable additives and hydrogen, while maintaining 29.3 × 10⁻⁶, 4 While exhibiting high activity, it also achieves precise molecular weight control (Mw / Mn=2.1), resulting in excellent product processing performance.

[0069] To further highlight the synergistic effect of the composite system of the main catalyst, co-catalyst and functional additives of the present invention, the following examples B1 to B10 are further provided.

[0070] Example B1: Reference System (No Additives) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; No functional additives are added (no antistatic agents, scale inhibitors, or electronic stabilizers). Total weight of catalyst system: approximately 5.85 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1060 g, activity 12.0 × 10⁻⁶ 4 (Benchmark); Polymerization at 180℃: Polymer yield 500 g, activity 5.7 × 10⁻⁶ 4 ; Activity retention rate: 47.5% (5.7 / 12.0×100%); Product at 180℃: Mw=186,000 g / mol, Mw / Mn=3.8, uniformity index 84%, reactor shows obvious scaling; It is evident that the activity of the additive-free system is reduced by more than half at 180℃, with a retention rate of only 47.5%.

[0071] Example B2: Adding an antistatic agent (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); No scale inhibitors, no electronic stabilizers; Total weight of catalyst system: approximately 5.90 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1150 g, activity 13.0 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 640 g, activity 7.2 × 10⁻⁶ 4 ; Activity retention rate: 55.4% (7.9% higher than B1); 180℃ product: Mw=172,000 g / mol, Mw / Mn=3.4, uniformity index 89%, and reduced scaling.

[0072] It is evident that adding an antistatic agent alone can increase the activity retention rate to 55.4%, demonstrating that the antistatic agent improves catalyst dispersion and reduces local overheating deactivation.

[0073] Example B3: Adding a scale inhibitor (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; No antistatic agents, no electronic stabilizing agents; Total weight of catalyst system: approximately 5.88 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1120 g, activity 12.7 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 600 g, activity 6.8 × 10⁻⁶ 4 ; Activity retention rate: 53.5% (6.0% higher than B1); 180℃ product: Mw=178,000 g / mol, Mw / Mn=3.6, uniformity index 87%, and reduced scaling.

[0074] It is evident that when the scale inhibitor is added alone, the activity retention rate can be increased to 53.5%. The scale inhibitor inhibits polymer deposition and maintains heat transfer efficiency.

[0075] Example B4: Addition of electronic stability aid (THF) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr = 2:1; No antistatic agents, no scale inhibitors; Total weight of catalyst system: approximately 5.87 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1250 g, activity 14.2 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 790 g, activity 9.0 × 10⁻⁶ 4 ; Activity retention rate: 63.4% (15.9% higher than B1); 180℃ product: Mw=152,000 g / mol, Mw / Mn=2.9, uniformity index 94%, slight scaling.

[0076] Advantages: The effect of adding electronic stabilizer alone is the most significant, with the activity retention rate increasing to 63.4%, proving the key role of electronic stabilizer in stabilizing cationic active centers and inhibiting high-temperature deactivation.

[0077] Example B5: Synergistic effect of antistatic agent and scale inhibitor (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Antistatic agent: 0.057g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.037 g; No electronic steady-state additives Total weight of catalyst system: approximately 5.93 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same. (3) Aggregation results: Polymerization at 140℃: Polymer yield 1190 g, activity 13.4 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 740 g, activity 8.3 × 10⁻⁶ 4 ; Activity retention rate: 61.9% (14.4% higher than Example B1); 180℃ product: Mw=162,000 g / mol, Mw / Mn=3.2, uniformity index 92%, and scale formation is significantly reduced.

[0078] It is evident that when the antistatic agent and the scale inhibitor are synergistically combined, the retention rate is 61.9%, which is higher than that of adding them alone (55.4% and 53.5%), proving that the synergy between the two can improve dispersion and scale prevention to a certain extent.

[0079] Example B6: Synergistic effect of antistatic agent and electronic stabilizing agent (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Antistatic agent: 0.075 g of ethoxylated amine compound (Atmer 163); Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.019 g), ED / Zr = 2:1; No scale inhibitor; Total weight of catalyst system: approximately 5.92 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1340 g, activity 15.1 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 910 g, activity 10.3 × 10⁻⁶ 4 ; Activity retention rate: 68.2% (20.7% higher than Example B1); 180℃ product: Mw=142,000 g / mol, Mw / Mn=2.6, uniformity index 96%, slight scaling.

[0080] It can be seen that when the antistatic agent and the electronic stabilizing agent are synergistically compounded, the retention rate is 68.2%, which is higher than that of adding the electronic stabilizing agent alone (63.4%) and the antistatic agent alone (55.4%).

[0081] Example B7: Synergistic effect of scale inhibitor and electronic stabilizing agent (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.07 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.024 g), ED / Zr = 2:1; No antistatic agent; Total weight of catalyst system: approximately 5.90 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1300 g, activity 14.7 × 10⁻⁶4 ; Polymerization at 180℃: Polymer yield 870 g, activity 9.8 × 10⁻⁶ 4 ; Activity retention rate: 66.7% (19.2% higher than Example B1); 180℃ product: Mw=148,000 g / mol, Mw / Mn=2.8, uniformity index 95%, slight scaling.

[0082] It is evident that when the scale inhibitor and the electronic stabilizing agent are synergistically combined, the retention rate is 66.7%, which is also better than adding them alone.

[0083] Example B8: Synergistic effect of three functional adjuvants (optimal ratio) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1450 g, activity 16.3 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 1070 g, activity 12.0 × 10⁻⁶ 4 ; Activity retention rate: 73.6% (26.1% higher than Example B1); 180℃ product: Mw=132,000 g / mol, Mw / Mn=2.5, comonomer insertion rate 19.3%, uniformity index 97%, haze 2.6%, almost no scaling; It is evident that when the three additives are synergistically compounded, the polymerization activity and anti-scaling effect are significantly improved, and the activity retention rate can be increased to 73.6%, which is 26.1 percentage points higher than the baseline system, demonstrating the synergistic effect of multi-component compounding. Example B9: Synergistic effect of three additives + high Al / Zr ratio (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 30 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 17.4 g), Al / Zr = 300:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr = 2:1; Total weight of catalyst system: approximately 17.55 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 2680 g, activity 15.3 × 10⁻⁶ 4 (Based on total catalyst amount); Polymerization at 180℃: Polymer yield 2000 g, activity 11.4 × 10⁻⁶ 4 ; Activity retention rate: 74.5% (27.0% higher than Example B1); 180℃ product: Mw=118,000 g / mol, Mw / Mn=2.3, uniformity index 98%, no scaling.

[0084] As can be seen, the retention rate at a high Al / Zr ratio is 74.5%, comparable to Example B8, but the absolute activity is higher (11.4 × 10⁻⁶ at 180°C). 4 This demonstrates that high adjuvant dosage and adjuvant synergistic compatibility are demonstrated.

[0085] Example B10: Synergistic effect of three additives + dual co-catalysts (optimal system) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst A: Triethylaluminum (TEA) 8 mmol (1.0 M hexane solution, 8 mL); Co-catalyst B: tris(pentafluorophenyl)boron (B(C6F5)3) 0.15 mmol (approximately 0.077 g), B / Zr = 1.5:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr = 2:1; Total weight of catalyst system: approximately 8.22 g (including solvent); (2) Polymerization reaction conditions (two sets of parallel experiments): Mixed solvent: n-hexane:tetrahydrofuran = 5:1, total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Temperature group 1: 140℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; Temperature group 2: 180℃, ethylene pressure 4.0 MPa, reaction time 30 minutes; All other conditions are the same; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1980 g, activity 24.1 × 10⁻⁶ 4 ; Polymerization at 180℃: Polymer yield 1580 g, activity 19.2 × 10⁻⁶ 4 ; Activity retention rate: 79.7% (32.2% higher than B1); 180℃ product: Mw=101,300 g / mol, Mw / Mn=2.4, uniformity index 98%, no scaling.

[0086] As can be seen, when using a dual co-catalyst and three functional additives in synergy, the activity retention rate reaches as high as 79.7%, an improvement of 32.2 percentage points compared to the baseline system, making it the best in this series. This demonstrates the excellent stability of the multi-component composite catalyst under harsh conditions.

[0087] Comparative Example B11: Comparison of Antistatic Agents (Atmer 163 replaced with Glycerylmonostearate) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: Glyceryl monostearate (GMS, Hostat FE 1) 0.05 g (replaces Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Mixed solvent: n-hexane:tetrahydrofuran = 5:1 (volume ratio), total solvent volume 2 L; Comonomer: 1-octene, molar percentage 30%; Polymerization temperatures: 140℃ and 180℃ (two groups were used to measure activity retention rate); Ethylene pressure: 4.0 MPa; Reaction time: 30 minutes; (3) Aggregation results: Polymerization at 140℃: Polymer yield 1320 g, activity 15.0 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 850 g, activity 9.7 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 64.7% (8.9% lower than 73.6% in Example B8); Product performance at 180℃: Mw=158,000 g / mol, Mw / Mn=2.9, comonomer insertion rate 20.5%, uniformity index 94.2%, melt index = 8.2 g / 10min, haze 4.5%; Scaling: Slight polymer buildup on the reactor wall, with stirring current fluctuations of approximately 5%.

[0088] The comparison shows that when the antistatic agent Atmer 163 was replaced with conventional GMS, the activity retention rate at 180℃ decreased by nearly 9 percentage points, the product uniformity index decreased, and the haze increased. This indicates that the unique ethoxylated structure of Atmer 163 has better dispersion stability and synergistic effect at high temperatures.

[0089] Comparative Example B12: Comparison of Antistatic Agents (Atmer 163 replaced with the permanent antistatic agent Irgastat P18) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: Irgastat P18 0.05 g (replace Atmer 163) - a permanent antistatic agent. Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0090] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1180 g, activity 13.4 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 680 g, activity 7.7 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 57.5% (a decrease of 16.1% compared to 73.6% in Example B8); Product performance at 180℃: Mw=168,000 g / mol, Mw / Mn=3.3, comonomer insertion rate 18.2%, uniformity index 91.5%, melt index 6.5 g / 10min, haze 6.2%; Scaling: There is obvious polymer buildup on the reactor wall, and the stirring current fluctuates by about 10%.

[0091] Comparative analysis shows that Irgastat P18, a high-molecular-weight permanent antistatic agent, may occupy active sites or affect mass transfer in the polymerization system, leading to a significant decrease in catalytic activity and poor product uniformity. Atmer 163, as a migratory small-molecule antistatic agent, is more suitable for this compound system.

[0092] Comparative Example B13: Comparison of Scale Inhibitor Types (PIB replaced with ethylene-propylene copolymer EPM) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: 0.03 g of ethylene-propylene copolymer (EPM, Mn=2000) (replacing PIB); Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0093] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1280 g, activity 14.5 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 800 g, activity 9.1 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 62.8% (10.8% lower than 73.6% in Example B8); Product performance at 180℃: Mw=162,000 g / mol, Mw / Mn=3.0, comonomer insertion rate 19.8%, uniformity index 93.5%, melt index 7.8 g / 10min, haze 5.1%; Scaling: Moderate polymer deposits were observed on the reactor walls, and the stirring current fluctuated by approximately 8%.

[0094] Comparative analysis shows that although EPM is also a polyolefin scale inhibitor, its molecular chain contains an ethylene structure. Compared with the pure hydrocarbon structure of PIB, it has a weaker ability to protect the reactor wall at high temperatures, resulting in a decrease in scale prevention effect. Consequently, its activity retention rate and product uniformity are lower than those of the PIB system.

[0095] Comparative Example B14: Comparison of Scale Inhibitor Types (PIB replaced with polyisobutylene succinimide) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene succinimide 0.03 g (replacing PIB); Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0096] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1080 g, activity 12.3 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 620 g, activity 7.0 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 56.9% (a decrease of 16.7% compared to 73.6% in Example B8); Product performance at 180℃: Mw=172,000 g / mol, Mw / Mn=3.5, comonomer insertion rate 17.2%, uniformity index 89.5%, melt index 5.8 g / 10min, haze 7.5%; Scaling: Severe polymer adhesion was observed on the reactor wall, and the stirring current fluctuated by approximately 15%.

[0097] Comparative analysis shows that although polyisobutylene succinimide is derived from the PIB framework, the introduced nitrogen-containing polar groups coordinate with the metallocene active center, severely inhibiting catalytic activity, while the scale prevention effect is not improved. This indicates that the pure hydrocarbon structure of PIB has the least interference with the active center, making it the best choice for scale inhibitors.

[0098] Comparative Example B15: Comparison of Electronic Stabilizing Agents (THF replaced by diethyl ether) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stabilizing agent: 0.2 mmol (approximately 0.015 g) of diethyl ether (replacing THF), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0099] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1350 g, activity 15.3 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 780 g, activity 8.9 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 58.2% (a decrease of 15.4% compared to 73.6% in Example B8); Product performance at 180℃: Mw=148,000 g / mol, Mw / Mn=3.1, comonomer insertion rate 20.2%, uniformity index 92.8%, melt index 9.2 g / 10min, haze 5.8%; Scaling: Slight scaling is present on the reactor wall.

[0100] Comparative analysis shows that diethyl ether has an open-chain structure, and its electron-donating ability and coordination stability are weaker than those of cyclic THF. At high temperatures, diethyl ether easily dissociates from the active center, leading to accelerated deactivation of the active center. Its activity retention rate and comonomer uniformity are significantly lower than those of the THF system.

[0101] Comparative Example B16: Comparison of Electronic Stabilizing Agents (THF replaced by dimethoxydimethylsilane DMDMS) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stabilizing agent: Dimethoxydimethylsilane (DMDMS) 0.2 mmol (approximately 0.027 g) (replacing THF), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.96 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0102] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1420 g, activity 16.1 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 820 g, activity 9.3 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 57.8% (a decrease of 15.8% compared to 73.6% in Example B8); Product performance at 180℃: Mw=152,000 g / mol, Mw / Mn=2.8, comonomer insertion rate 21.5%, uniformity index 94.5%, melt index = 8.5 g / 10min, haze 4.2%; Scaling status: No scale buildup on the reactor wall.

[0103] Comparative analysis shows that DMDMS has a stronger electron-donating ability and higher initial activity, but its macromolecular structure has large steric hindrance at high temperatures, poor stability of the active center, fast activity decay rate, and lower high-temperature retention rate than the THF system.

[0104] Comparative Example B17: No electronic stability additives added (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (10 wt% toluene solution, approximately 5.8 g), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic steady-state additives: None added; Total weight of catalyst system: approximately 5.93 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0105] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1180 g, activity 13.4 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 620 g, activity 7.0 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 52.2% (21.4% lower than 73.6% in Example B8); Product performance at 180℃: Mw=182,000 g / mol, Mw / Mn=3.6, comonomer insertion rate 16.5%, uniformity index 86.5%, melt index = 6.2 g / 10min, haze 7.2%; Scaling: There is obvious polymer adhesion on the reactor wall, and the stirring current fluctuates by about 12%.

[0106] Comparative analysis shows that without the addition of electronic stabilizing agents, the high-temperature activity retention rate is only 52.2%, and the comonomer insertion rate and uniformity index decrease significantly. This demonstrates that electronic stabilizing agents play an indispensable role in stabilizing active centers, inhibiting high-temperature deactivation, and improving the uniformity of comonomer insertion.

[0107] Comparative Example B18: The dual co-catalyst system was replaced with a single MAO catalyst. (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: 10 mmol of methylaluminoxane (MAO) (replacing TEA+B(C6F5)3), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.95 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0108] (3) Aggregation results: Polymerization at 140℃: Polymer yield 1420 g, activity 16.1 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 1020 g, activity 11.6 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 72.0% (7.7% lower than 79.7% in Example B10); Product performance at 180℃: Mw=128,000 g / mol, Mw / Mn=2.4, comonomer insertion rate 24.5%, uniformity index 97.2%, melt index 13.5 g / 10min, haze 3.1%; Scaling status: No scale buildup on the reactor wall.

[0109] Comparative analysis shows that when the dual co-catalyst (TEA+B(C6F5)3) in Example B10 was replaced with a single MAO, the high-temperature activity retention rate decreased from 79.7% to 72.0%, proving that the more stable cationic active center formed by the dual co-catalyst has better high-temperature stability.

[0110] Comparative Example B19: Using only TEA as a cocatalyst (without adding organoboron) (1) Preparation of catalyst system: Main catalyst: Bridged zirconium dichlorodichlorodicyclopentadiene (rac-Et(Ind)2ZrCl2) 0.10 mmol (approximately 0.052 g); Co-catalyst: Triethylaluminum (TEA) 10 mmol (without organoboron), Al / Zr molar ratio = 100:1; Antistatic agent: 0.05 g of ethoxylated amine compound (Atmer 163); Scale inhibitor: Polyisobutylene (PIB, Mn=1300) 0.03 g; Electronic stability aid: Tetrahydrofuran (THF) 0.2 mmol (approximately 0.014 g), ED / Zr molar ratio = 2:1; Total weight of catalyst system: approximately 5.15 g (including solvent); (2) Polymerization reaction conditions: Same as comparative example B11.

[0111] (3) Aggregation results: Polymerization at 140℃: Polymer yield 320 g, activity 3.6 × 10⁻⁶ 4 g-POE / g-cat; Polymerization at 180℃: Polymer yield 150 g, activity 1.7 × 10⁻⁶ 4 g-POE / g-cat; Activity retention rate: 47.2%; Product performance at 180℃: Mw=198,000 g / mol, Mw / Mn=4.5, comonomer insertion rate 12.5%, uniformity index 78.5%, melt index = 2.1 g / 10min, haze 12.5%; Scaling condition: Severe scaling on the reactor wall, with stirring current fluctuations >20%.

[0112] Comparative analysis shows that using TEA alone cannot effectively activate metallocene catalysts, resulting in extremely low polymerization activity and poor product performance. This demonstrates that organoboron co-catalysts (or MAO) are necessary for the formation of cationic active centers, and high activity and high-temperature stability can only be achieved when combined with TEA.

[0113] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A multi-component complex catalyst system for high temperature solution polymerization, characterized in that, It includes a main catalyst, a co-catalyst, and functional additives, wherein the main catalyst is a metallocene compound or a non-metallocene transition metal compound, the co-catalyst is an organoaluminum compound and / or an organoboron compound, and the functional additives include antistatic agents, scale inhibitors, molecular weight regulators, and electronic stabilizing agents.

2. A multi-component catalyst system for high temperature solution polymerization according to claim 1, characterized in that, The metallocene compound is selected from bridging or non-bridging dichlorozirconia compounds; The non-ceramic transition metal compound is selected from pyridine imine or salicylaldehyde imine complexes of the iron, nickel, or vanadium series.

3. The multi-component catalyst system for high temperature solution polymerization according to claim 1, wherein The organoaluminum compound is selected from methylaluminoxane (MAO), modified methylaluminoxane (MMAO), trimethylaluminum, triethylaluminum, or triisobutylaluminum; The organoboron compound is selected from tris(pentafluorophenyl)boron or tetra(pentafluorophenyl)borate compounds.

4. The multi-component catalyst system for high temperature solution polymerization according to claim 1, wherein The antistatic agent is selected from ethoxylated amines or alkyl sulfonates; The anti-scaling agent is selected from polyisobutylene or ethylene-propylene copolymer; The electronically stabilized additive is selected from tetrahydrofuran, diethyl ether, or silane compounds.

5. The multi-component composite catalyst system for high-temperature solution polymerization according to claim 1, characterized in that, The molar ratio of the main catalyst to the co-catalyst is 1:10~10000; The total amount of the functional additives added accounts for 0.1% to 10% of the total weight of the catalyst system; The molar ratio of the electronically stabilized additive to the main catalyst is 1~100:1; The amount of the antistatic agent added accounts for 0.1% - 3.0% of the total weight of the catalyst system; The amount of the scale inhibitor added is 0.05% - 2.0% of the total weight of the catalyst system; The molecular weight regulator is hydrogen, and its partial pressure accounts for 0.5%-15% of the total pressure of the reaction system.

6. The application of a multi-component composite catalyst system for high-temperature solution polymerization as described in any one of claims 1-5 in the preparation of high-end polyolefins.

7. A method for preparing high-end polyolefins, characterized in that, Includes the following steps: S1. The multi-component compound catalyst system as described in any one of claims 1-5, the mixed solvent, and one or more long-chain α-olefins are added to a high-pressure polymerization reactor, heated to the reaction temperature, and ethylene is introduced to carry out the polymerization reaction. S2. After the reaction is complete, the reaction is terminated, and the resulting reaction product is devolatilized and granulated to obtain high-end polyolefin products.

8. The method for preparing high-end polyolefins according to claim 7, characterized in that, In S1, the polymerization reaction temperature is 150~220℃, the time is 5~60min, and the ethylene feed rate is sufficient to maintain the reaction pressure at 1.0-6.0MPa. The long-chain α-olefin is one or more of 1-butene, 1-hexene, 1-octene, 1-decene, dodecene, and tetradecene, and its molar percentage in the polymerization raw materials is 10%-70%.

9. The method for preparing high-end polyolefins according to claim 7, characterized in that, In S1, the mixed solvent is formed by mixing organic solvent A and organic solvent B in a volume ratio of 5 to 10:

1. Organic solvent A is selected from one of n-hexane, cyclohexane, n-heptane, toluene, or xylene, and organic solvent B is selected from one of tetrahydrofuran, dioxane, ethyl acetate, or acetone.

10. The method for preparing high-end polyolefins according to claim 7, characterized in that, In S1, hydrogen gas, a molecular weight regulator, is added during the polymerization reaction to control the molecular weight of high-end polyolefin products.

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