Polyethylene catalysts and methods for their preparation and ultra-high molecular weight polyethylene and methods for their preparation

Abstract

This invention relates to the field of catalysts, specifically to a polyethylene catalyst and its preparation method, as well as ultra-high molecular weight polyethylene and its preparation method. The method includes the following steps: (1) under diluent conditions, a magnesium halide precursor, an alcohol compound, and a first internal electron donor undergo a first contact reaction to obtain a first reaction solution; (2) a second internal electron donor is added to the first reaction solution to undergo a second contact reaction to obtain a second reaction solution; (3) a titanium precursor is added to the second reaction solution to undergo a third contact reaction to obtain a third reaction solution; (4) a haloalkane is added to the third reaction solution, followed by a third internal electron donor to undergo a fourth contact reaction. The catalyst prepared by this invention exhibits good catalytic performance.

Description

Technical Field

[0001] This invention relates to the field of catalysts, specifically to a polyethylene catalyst and its preparation method, as well as ultra-high molecular weight polyethylene and its preparation method. Background Technology

[0002] Polyethylene is a widely used plastic, applied across various industries and sectors. Polyethylene catalysts are crucial raw materials in polyethylene production, playing an irreplaceable role in the production of high-quality polyethylene. The selection and use of catalysts have a vital impact on the control of the polymerization reaction and the structure and properties of the polymer. The main functions of polyethylene catalysts in the polymerization reaction include promoting the polymerization of monomer molecules, accelerating the connection of structural units, and controlling molecular structure and properties, thereby significantly influencing the performance of the polymerized material.

[0003] Existing technologies widely employ methods to improve the polymerization performance of catalysts by adjusting the type and structure of the catalyst support or changing the type of internal electron donor, thereby obtaining products with excellent performance. CN110407966A discloses an ultra-high molecular weight polyethylene catalyst, which uses a titanium-containing compound supported on spherical graphene oxide treated with a surfactant as the main catalyst component. The resulting polymer exhibits good antistatic properties, but does not improve mechanical properties and has a low viscosity-average molecular weight. CN107417812A discloses a supported ultra-high molecular weight polyethylene catalyst, which requires the mixing and ball milling of three types of molecular sieves during preparation. The preparation process is complex, and the polymerization product exhibits severe entanglement, which is detrimental to subsequent processing. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of complex preparation process of polyethylene catalysts in the prior art, and low viscosity-average molecular weight and poor mechanical properties of the polymer products prepared. This invention provides a polyethylene catalyst and its preparation method, as well as ultra-high molecular weight polyethylene and its preparation method. The catalyst has good catalytic performance, and the polyethylene products prepared using the catalyst have the characteristics of high viscosity-average molecular weight, good bulk density and high impact strength.

[0005] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a polyethylene catalyst, the method comprising the following steps: (1) under diluent conditions, a magnesium halide precursor, an alcohol compound and a first internal electron donor are subjected to a first contact reaction to obtain a first reaction solution; (2) a second internal electron donor is added to the first reaction solution to conduct a second contact reaction to obtain a second reaction solution; (3) a titanium precursor is added to the second reaction solution to conduct a third contact reaction to obtain a third reaction solution; (4) a haloalkane is added to the third reaction solution, and then a third internal electron donor is added to conduct a fourth contact reaction.

[0006] A second aspect of the present invention provides a polyethylene catalyst, said catalyst being prepared by the method described in the first aspect.

[0007] A third aspect of the present invention provides a method for preparing ultra-high molecular weight polyethylene, the method comprising: under solvent conditions, contacting ethylene, alkylaluminum and a catalyst to carry out a polymerization reaction; wherein the catalyst is the polyethylene catalyst described in the second aspect.

[0008] The fourth aspect of the present invention provides an ultra-high molecular weight polyethylene, which is prepared by the method described in the third aspect.

[0009] Through the above technical solution, the present invention has the following advantages: The catalyst prepared by the method of this invention has good catalytic performance; Applying the catalyst of this invention to the preparation of ultra-high molecular weight polyethylene can improve the molecular weight, bulk density and impact strength of polyethylene products. Detailed Implementation

[0010] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0011] This invention provides a method for preparing a polyethylene catalyst, the method comprising the following steps: (1) under diluent conditions, a magnesium halide precursor, an alcohol compound and a first internal electron donor are subjected to a first contact reaction to obtain a first reaction solution; (2) a second internal electron donor is added to the first reaction solution to conduct a second contact reaction to obtain a second reaction solution; (3) a titanium precursor is added to the second reaction solution to conduct a third contact reaction to obtain a third reaction solution; (4) a haloalkane is added to the third reaction solution, and then a third internal electron donor is added to conduct a fourth contact reaction.

[0012] The catalyst prepared by the method of this invention has good catalytic performance.

[0013] According to a preferred embodiment of the present invention, the first, second, and third internal electron donors each independently include at most two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0014] According to a preferred embodiment of the present invention, the titanium precursor is titanium halide.

[0015] According to a preferred embodiment of the present invention, when the first, second, and third internal electron donors each independently include at most two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors, the molar content of any one type of internal electron donor in each of the first, second, and third internal electron donors is 10-100%, for example, it can be 20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90%.

[0016] According to a preferred embodiment of the present invention, when the first, second, and third internal electron donors each independently include at least two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors, one of which is an ester-based internal electron donor. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0017] According to a preferred embodiment of the present invention, when the first, second, and third internal electron donors each independently include at least two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors, and one of them is an ester-based internal electron donor, the molar content of any one type of internal electron donor in each of the first, second, and third internal electron donors is 20-50%, for example, it can be 25%, 30%, 35%, 40%, and 45%.

[0018] According to a preferred embodiment of the present invention, the first, second, and third internal electron donors are at least two types of internal electron donors selected from ester-based internal electron donors, ether-based internal electron donors, and organosiloxane-based internal electron donors. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0019] According to a preferred embodiment of the present invention, when the first, second, and third internal electron donors are two types of internal electron donors selected from ester-based internal electron donors, ether-based internal electron donors, and organosiloxane-based internal electron donors, the molar content of any one type of internal electron donor is 10-90%, for example, it can be 20%, 30%, 40%, 50%, 60%, 70%, and 80%.

[0020] According to a preferred embodiment of the present invention, when the first internal electron donor, the second internal electron donor, and the third internal electron donor are three types of internal electron donors selected from ester internal electron donors, ether internal electron donors, and organosiloxane internal electron donors, the molar content of any one type of internal electron donor is 10-80%, for example, it can be 20%, 30%, 40%, 50%, 60%, and 70%.

[0021] According to a preferred embodiment of the present invention, the titanium precursor is titanium tetrachloride.

[0022] According to a preferred embodiment of the present invention, the first internal electron donor, the second internal electron donor, and the third internal electron donor are all different. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0023] In this invention, any ester-based internal electron donor commonly used in the art can be applied to achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the ester-based internal electron donor can be selected from at least one of monoester-based internal electron donors, diester-based internal electron donors, and imine ester-based internal electron donors. The internal electron donor of monoesters may be selected from at least one of ethyl silicate, methyl benzoate, ethyl benzoate, propyl benzoate, and butyl benzoate; the internal electron donor of diesters may be selected from at least one of dimethyl phthalate, dibutyl phthalate, di(2-ethylhexyl) phthalate, diethyl terephthalate, diisobutyl phthalate, dimethyl 2-cyanosuccinate, dicarboxylate, dimethyl succinate, and dimethyl adipate phthalate; the internal electron donor of imine esters may be selected from at least one of 4-(N-maleimidemethyl)cyclohexane-1-carboxylic acid succinimide ester (SMCC), 3-maleimide propionic acid hydroxysuccinimide ester, dodecanetetraacetic acid-succinimide ester, and azadibenzocyclooctyl succinate imide ester.

[0024] In this invention, any ether-based internal electron donor commonly used in the art can be applied as long as it achieves the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the ether-based internal electron donor can be a diether-based internal electron donor. The diether-based internal electron donor can be selected from at least one of fluorene diether, 1,2-dimethoxybenzene, 1,2,4-trimethoxybenzene, 1,2-diethoxybenzene, 2,3-dimethoxytoluene, 1-allyl-3,4-dimethoxybenzene, 1,2-dimethoxyethane, 1,2-dimethoxycyclohexane, 1,2-dimethoxypropane, 1,2-dimethoxybutane, and 2,3-dimethoxybutane.

[0025] In this invention, any organosiloxane internal electron donor commonly used in the art can be applied to achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the organosiloxane internal electron donor can be selected from at least one of 3-chloropropyltriethoxysilane, phenyltriethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, dicyclohexyldimethoxysilane, dipiperidinedimethoxysilane, pyridinemethyldiethoxysilane, dipyridinedioxymethylsilane, cyclohexylphenyldimethoxysilane, and cyclopentylphenyldiethoxysilane.

[0026] To further improve the catalytic performance of the catalyst, according to a preferred embodiment of the present invention, the electron donor within the ester is selected from at least one of 4-(N-maleimidemethyl)cyclohexane-1-carboxylic acid succinimide ester (SMCC), azadibenzocyclooctyl succinate imide ester, dibutyl phthalate, ethyl benzoate, dimethyl 2-cyanobutylsuccinate, ethyl silicate, di(2-ethylhexyl) phthalate, dimethyl succinate, and diethyl terephthalate.

[0027] To further improve the catalytic performance of the catalyst, according to a preferred embodiment of the present invention, the electron donor in the ether is selected from at least one of 2,3-dimethoxybutane, 1-allyl-3,4-dimethoxybenzene, and fluorene diether.

[0028] To further improve the catalytic performance of the catalyst, according to a preferred embodiment of the present invention, the internal electron donor of the organosiloxane is selected from 3-chloropropyltriethoxysilane and / or cyclohexylphenyldimethoxysilane.

[0029] According to a preferred embodiment of the present invention, the temperature of the first contact reaction is 10–40°C higher than the temperature of the fourth contact reaction. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0030] According to a preferred embodiment of the present invention, the temperature of the fourth contact reaction is 20–80°C higher than the temperature of the second contact reaction. By adopting the aforementioned preferred embodiment, the catalytic performance of the catalyst can be further improved.

[0031] According to a preferred embodiment of the present invention, the conditions for the first contact reaction include a temperature of 130–140°C.

[0032] In this invention, as long as the purpose of this invention can be achieved, there is no special requirement for the time of the first contact reaction. The time of the first contact reaction can be adjusted accordingly with the change of the temperature of the first contact reaction. For example, the time of the first contact reaction is 2 to 4 hours.

[0033] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the way the raw materials of the first contact reaction are added. The following is an illustrative description, but it does not limit the scope of this invention. For example, under diluent conditions, the magnesium halide precursor and alcohol compound can be added first at 10-30°C, and then the temperature can be raised to 40-80°C to add the first internal electron donor and keep warm for 30-60 minutes.

[0034] According to a preferred embodiment of the present invention, the conditions for the second contact reaction include a temperature of 40–80°C.

[0035] In this invention, as long as the purpose of this invention can be achieved, there is no special requirement for the time of the second contact reaction. The time of the second contact reaction can be adjusted accordingly with the change of the temperature of the second contact reaction. For example, the time of the second contact reaction is 30 to 60 minutes.

[0036] According to a preferred embodiment of the present invention, the conditions for the third contact reaction include a temperature of -5 to -15°C.

[0037] In this invention, as long as the purpose of this invention can be achieved, there is no special requirement for the time of the third contact reaction. The time of the third contact reaction can be adjusted accordingly with the change of the temperature of the third contact reaction. For example, the time of the third contact reaction is 2 to 3 hours.

[0038] According to a preferred embodiment of the present invention, the conditions for the fourth contact reaction include a temperature of 100–120°C.

[0039] In this invention, as long as the purpose of this invention can be achieved, there is no special requirement for the time of the fourth contact reaction. The time of the fourth contact reaction can be adjusted accordingly with the change of the temperature of the fourth contact reaction. For example, the time of the fourth contact reaction is 1 to 3 hours.

[0040] In this invention, as long as the purpose of this invention can be achieved, the type of diluent can be a conventional choice in the art. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the diluent is a C9 to C11 alkane, such as at least one of nonane, decane and undecane, preferably decane.

[0041] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the type of magnesium halide precursor. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the magnesium halide precursor is selected from at least one of magnesium dihalide compounds, alkoxy magnesium halide compounds, and alkyl magnesium halide compounds, preferably magnesium dihalide compounds.

[0042] In this invention, any commonly used magnesium dihalide compound can be used as long as it can achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the magnesium dihalide compound is at least one of magnesium chloride, magnesium bromide and magnesium iodide, preferably magnesium chloride.

[0043] In this invention, any commonly used alkoxy magnesium halide compounds can be used as long as they can achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the alkoxy magnesium halide compound is at least one of methoxy magnesium chloride, methoxy magnesium bromide, methoxy magnesium iodide, ethoxy magnesium chloride, ethoxy magnesium bromide, ethoxy magnesium iodide, and butoxy magnesium chloride.

[0044] In this invention, any commonly used alkyl magnesium halide compound can be used as long as it can achieve the purpose of this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the alkyl magnesium halide compound is at least one of methyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, and propyl magnesium iodide.

[0045] In this invention, there are no particular requirements for the type of alcohol compound. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the alcohol compound is a C5 to C8 alcohol compound, such as at least one of isoamyl alcohol, n-hexanol, octanol and isooctanol, preferably isooctanol.

[0046] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the method of adding the titanium precursor. Commonly used methods in the art can be applied to this invention. The titanium precursor is added by dripping. There are no special requirements for the dripping speed, which will not be described in detail in this invention. The initial speed is 10 ml / h, and the speed is increased by 5 ml / h every 10 minutes until the dripping speed is 25 ml / h. If the dripping is not completed within the third contact reaction time, it is added quickly at the end.

[0047] According to a preferred embodiment of the present invention, the haloalkane is a halocycloalkane.

[0048] In this invention, the type of halocycloalkanes can be any conventional choice in the art as long as the purpose of this invention can be achieved. This invention will not elaborate on this in detail. This invention uses halocyclohexane as an example to illustrate the advantages of this invention.

[0049] In this invention, the molar ratio of the alcohol compound to the magnesium halide precursor can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar ratio of the alcohol compound to the magnesium halide precursor is 2.5 to 3.

[0050] In this invention, the molar ratio of the diluent to the magnesium halide precursor can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar ratio of the diluent to the magnesium halide precursor is 9 to 11.

[0051] According to a preferred embodiment of the present invention, the molar ratio of the first internal electron donor to the magnesium halide precursor is 0.05 to 0.2.

[0052] According to a preferred embodiment of the present invention, the molar ratio of the second internal electron donor to the magnesium halide precursor is 0.05 to 0.2.

[0053] According to a preferred embodiment of the present invention, the molar ratio of the third internal electron donor to the magnesium halide precursor is 0.1 to 0.4.

[0054] According to a preferred embodiment of the present invention, the total molar amount of the first internal electron donor and the second internal electron donor is not greater than the molar amount of the third internal electron donor.

[0055] In this invention, as long as the objective of this invention can be achieved, the molar ratio of the titanium precursor to the magnesium halide precursor can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the molar ratio of the titanium precursor to the magnesium halide precursor is 7 to 11.

[0056] In this invention, as long as the objective of this invention can be achieved, the range of selectable molar ratios of the halohydrocarbon to the magnesium halide precursor is relatively wide. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the molar ratio of the halohydrocarbon to the magnesium halide precursor is 3 to 4.

[0057] According to a preferred embodiment of the present invention, the method further includes: performing a drying process after the fourth contact reaction.

[0058] In this invention, the drying process is a conventional technique in the field and will not be described in detail. This invention will use drying under nitrogen conditions in a nitrogen drying oven as an example for illustration.

[0059] In this invention, a washing process is required before drying after the fourth contact reaction. The washing conditions have a wide range of options, and commonly used washing conditions in the art can be applied to this invention. The following is an illustrative description, but it does not limit the scope of this invention. For example, the washing conditions include: a washing temperature of 60-90°C and 6-10 washing cycles.

[0060] This invention provides a polyethylene catalyst, which is prepared by the method described above.

[0061] Applying the catalyst of this invention to the preparation of ultra-high molecular weight polyethylene can improve the molecular weight, bulk density and impact strength of polyethylene products.

[0062] This invention provides a method for preparing ultra-high molecular weight polyethylene, the method comprising: under solvent conditions, contacting ethylene, alkyl aluminum and a catalyst to carry out a polymerization reaction; wherein the catalyst is the polyethylene catalyst described above in this invention.

[0063] In this invention, the range of selectable conditions for the polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the conditions for the polymerization reaction include a temperature of 70 to 75°C.

[0064] In this invention, there are no special requirements for the polymerization reaction time. The polymerization reaction time is adjusted accordingly with the change of temperature to ensure that the reaction is complete. According to a preferred embodiment of this invention, the polymerization reaction time is 1 to 2 hours.

[0065] In this invention, the pressure range of the polymerization reaction is relatively wide. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the conditions of the polymerization reaction include a pressure of 0.7 to 0.8 MPa.

[0066] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the mass ratio of the alkylaluminum to the catalyst. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the mass ratio of the alkylaluminum to the catalyst is 1:10 to 20.

[0067] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the type of solvent, and it can be a conventional choice in the field. This invention will not elaborate on this in detail, but will use hexane as an example for illustration.

[0068] In this invention, as long as the purpose of this invention can be achieved, there are no special requirements for the type of alkyl aluminum, and it can be a conventional choice in the field. This invention will not elaborate on this in detail, but will use triethylaluminum as an example for illustration.

[0069] This invention provides an ultra-high molecular weight polyethylene, which is prepared by the aforementioned method for preparing ultra-high molecular weight polyethylene.

[0070] According to a preferred embodiment of the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 4.4 million to 5 million.

[0071] According to a preferred embodiment of the present invention, the bulk density of the ultra-high molecular weight polyethylene is 0.38–0.45 g / cm³. 3 .

[0072] According to a preferred embodiment of the present invention, the notched impact strength of the ultra-high molecular weight polyethylene is 90-110 KJ / m². 2 .

[0073] The present invention will be described in detail below through embodiments. The following embodiments include: The molecular weight of ultra-high molecular weight polyethylene (UHMWPE) was determined using GB / T 1632.3-2010 Plastics - Determination of Viscosity of Dilute Solutions of Polymers Using Capillary Viscometer - Part 3: Polyethylene and Polypropylene. In the experiment, decahydronaphthalene was used as a solvent to dissolve the UHMWPE resin. After complete dissolution for 2 hours, the solution was added to an Ubbelohde viscometer in a 135°C constant temperature bath, and the outflow time was repeatedly measured until three consecutive readings differed from their average value by less than 0.2 seconds. The molecular weight of UHMWPE was calculated using a formula based on the outflow time. The bulk density of ultra-high molecular weight polyethylene (UHMWPE) products is determined using the "GB / T 1636 Test Method for Apparent Density of Molding Plastics". In the experiment, the bulk density of the product is calculated by testing the mass of UHMWPE products in a 100mL container. The notched impact strength of ultra-high molecular weight polyethylene (UHMW) products was determined using GB / T 21461.2-2008 Plastics UHMW Molding and Extrusion Materials Part 2: Specimen Preparation and Performance Determination. A pendulum with an energy of 50J was used in the experiment. The specimen size was 120mm*15mm*10mm, the cutting angle was 14°±2°, and notches were machined on both sides of the specimen. The notches were located in the middle of the specimen, and the depth of the notches was 3mm. Magnesium halide and titanium chloride, which involve molar ratio parameters, are all calculated based on the metallic elements magnesium and titanium. The method for adding TiCl4 is as follows: the initial speed is 10 ml / h, and the speed is increased by 5 ml / h every 10 minutes until the speed is 25 ml / h. If the addition is not completed within the time limit, it is added quickly at the end. In each addition of internal electron donors, the molar ratio between different types of internal electron donors is 1. The method for small-scale evaluation using the prepared catalyst includes: reaction in a 2L polymerization reactor at 70℃, 0.7MPa, and 120 minutes; the catalyst mass in the reactor is 30mg; and triethylaluminum (concentration 1.09mol / L) is added in 3mL. Slurry polymerization is used, with hexane as the solvent (1L added) and ethylene continuously fed. Unless otherwise specified, all raw materials are commercially available.

[0074] Example 1 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.98 million and a bulk density of 0.44 g / cm³. 3 The notched impact strength of a simply supported beam is 99 kJ / m. 2 .

[0075] Example 2 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 40°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then increased to 130°C and kept at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 40°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 3 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.96 million and a bulk density of 0.44 g / cm³. 3 The impact strength of a simply supported beam with a notched diameter is 101 kJ / m.2 .

[0076] Example 3 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 80°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then increased to 130°C and kept at this temperature for 2 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 1 hour. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.68 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of a simply supported beam is 95 kJ / m. 2 .

[0077] Example 4 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 70°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 70°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2.5 hours. The temperature was then decreased to 65°C, and the catalyst was washed eight times by decantation. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.77 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 96 kJ / m. 2 .

[0078] Example 5 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -15°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 11 over 3 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the reaction was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 10 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.7 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of the simply supported beam is 96 kJ / m. 2 .

[0079] Example 6 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -5°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 7 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was washed six times by decantation. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.85 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of a simply supported beam is 99 kJ / m. 2 .

[0080] Example 7 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (MgCl2) electron donor was added at a molar ratio of 0.1 to the support MgCl2, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and SMCC electron donor was added at a molar ratio of 0.1 to the support MgCl2, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 7 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the support MgCl2. The temperature was then increased to 110°C, and SMCC electron donor was added at a molar ratio of 0.2 to the support MgCl2, and the reaction was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.49 million and a bulk density of 0.40 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0081] Example 8 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and dibutyl phthalate (DBP) was added as an electron donor at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and DBP was added as an electron donor at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 7 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and DBP was added as an electron donor at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.41 million and a bulk density of 0.38 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0082] Example 9 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and 3-chloropropyltriethoxysilane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and 3-chloropropyltriethoxysilane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 7 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and held at this temperature for 2 hours. The mixture was then decreased to 65°C, and the solution was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.47 million and a bulk density of 0.38 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0083] Example 10 At 25°C, 0.05 mol magnesium bromide, 0.14 mol n-hexanol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC and 3-maleimide propionic acid hydroxysuccinimide ester electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate and ethyl silicate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 105°C, and 3-chloropropyltriethoxysilane electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The catalyst was cooled to 65℃ and washed eight times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.61 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of the simply supported beam is 94 KJ / m. 2 .

[0084] Example 11 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane, dimethyl succinate, and fluorene diether electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.55 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of the simply supported beam is 93 KJ / m. 2 .

[0085] Example 12 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 80°C, and dodecanetetraacetic acid-succinimide ester electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then increased to 130°C and kept at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and 1,2-dimethoxybenzene electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The mixture was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.62 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of the simply supported beam is 92 kJ / m. 2 .

[0086] Example 13 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 50°C, and ethyl silicate and ethyl benzoate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and diethyl terephthalate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -15°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 10 over 3 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 1,2-dimethoxypropane and dicyclopentyldimethoxysilane electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 1 hour. The catalyst was cooled to 65℃ and washed eight times by decanting. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.73 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 94 KJ / m. 2 .

[0087] Example 14 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 70°C, and azidocyclooctyne succinate imine ester, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and kept at this temperature for 40 minutes. The temperature was then increased to 130°C and kept at this temperature for 2.5 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and 2,3-dimethoxybutane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 9 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and ethyl benzoate, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and kept at this temperature for 2 hours. The mixture was then decreased to 65°C and decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.81 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0088] Example 15 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 80°C, and SMCC (a 0.1 molar ratio of MgCl2 to the support) was added as an electron donor and held at this temperature for 30 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 50°C, and dibutyl phthalate (DBP) was added as an electron donor at a 0.1 molar ratio of MgCl2 to the support and held at this temperature for 30 minutes. The temperature was then decreased to -8°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 10 over 2 hours. After the titanium addition was complete, cyclohexane chloroprene was added at a 3.3 molar ratio of MgCl2 to the support. The temperature was then increased to 110°C, and SMCC and 3-chloropropyltriethoxysilane (a 0.2 molar ratio of MgCl2 to the support) were added and reacted at this temperature for 3 hours. The mixture was then decreased to 65°C and decanted and washed 9 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.9 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0089] Example 16 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and dodecanetetraacetic acid-succinimide ester electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 50 minutes. The temperature was then increased to 130°C and kept at this temperature for 2.5 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 70°C, and carbamate diester electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 40 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and SMCC electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the reaction was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.56 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of the simply supported beam is 92 kJ / m. 2 .

[0090] Example 17 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and azidocyclooctyl succinate imine ester, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 45 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and 1,2-dimethoxyethane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 9 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloroprene was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and dibutyl phthalate, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and reacted at this temperature for 1 hour. The mixture was then decreased to 65°C, and the solution was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.75 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0091] Example 18 At 25°C, 0.05 mol of methyl magnesium chloride, 0.14 mol of isooctanol, and 0.513 mol of nonane were mixed in a catalyst preparation vessel. The mixture was heated to 75°C, and 1,2-dimethoxypropane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 40 minutes. The temperature was then increased to 130°C and held at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 40°C, and methyl benzoate, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 60 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 7 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 115°C, and 3-chloropropyltriethoxysilane, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and reacted at this temperature for 2 hours. The mixture was then decreased to 65°C, and the solution was decanted and washed 7 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.59 million and a bulk density of 0.40 g / cm³. 3 The notched impact strength of the simply supported beam is 93 KJ / m. 2 .

[0092] Example 19 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 40°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3.5 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the reaction was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.86 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0093] Example 20 At 25°C, 0.05 mol of magnesium methoxychloride, 0.14 mol of octanol, and 0.513 mol of decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and 1,2-dimethoxycyclohexane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and diisobutyl phthalate, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then decreased to -12°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8.5 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloroprene was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and phenyltriethoxysilane, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and reacted at this temperature for 2 hours. The mixture was then decreased to 65°C and decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.52 million and a bulk density of 0.39 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0094] Example 21 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol undecane were mixed in a catalyst preparation vessel. The mixture was heated to 50°C, and SMCC and fluorene diether electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and dibutyl phthalate and ethyl silicate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The mixture was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.55 million and a bulk density of 0.40 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0095] Example 22 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and 3-chloropropyltriethoxysilane and SMCC electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dicyclohexyldimethoxysilane and bispiperidinedimethoxysilane electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and bispyridinedioxymethylsilane electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 3 hours. The catalyst was cooled to 65℃ and washed eight times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.74 million and a bulk density of 0.40 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0096] Example 23 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 70°C, and 1,2-diethoxybenzene and 2,3-dimethoxytoluene, electron donors, were added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 70°C, and cyclopentylcyclohexyldimethoxysilane, electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and pyridinemethyldiethoxysilane, electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and reacted at this temperature for 3 hours. The mixture was then decreased to 65°C and decanted and washed 9 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.75 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 94 KJ / m. 2 .

[0097] Example 24 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and dodecanetetraacetic acid-succinimide ester electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then increased to 130°C and kept at this temperature for 2 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and propyl benzoate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and cyclopentylphenyldiethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.45 million and a bulk density of 0.38 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0098] Example 25 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and 1,2,4-trimethoxybenzene electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and methyl phthalate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and pyridinemethyldiethoxysilane electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.63 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of the simply supported beam is 94 KJ / m. 2 .

[0099] Example 26 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methacrylic acid precipitate) was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dimethyl 2-cyanosuccinate and ethyl silicate were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 10 over a period of 2.5 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and cyclohexylphenyl dimethoxysilane was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.56 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of a simply supported beam is 99 kJ / m. 2 .

[0100] Example 27 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC and 1-allyl-3,4-dimethoxybenzene electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and di(2-ethylhexyl) phthalate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloroprene was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane and dimethyl succinate electron donors were added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The catalyst was cooled to 65℃ and washed eight times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.84 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0101] Example 28 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and 3-chloropropyltriethoxysilane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 40 minutes. The temperature was then increased to 130°C and held at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and diethyl terephthalate, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and held at this temperature for 30 minutes. The temperature was then decreased to -12°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and fluorene diether, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and reacted at this temperature for 1 hour. The mixture was then decreased to 65°C, and the solution was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.78 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0102] Example 29 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 45 minutes. The temperature was then decreased to -6°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 1.5 hours. The temperature was then decreased to 65°C, and the catalyst was washed 8 times by decantation. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.88 million and a bulk density of 0.43 g / cm³. 3 The notched impact strength of the simply supported beam is 98 kJ / m. 2 .

[0103] Example 30 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 50°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 50 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 75°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 11 over 3 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the reaction was kept at this temperature for 3 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.66 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of the simply supported beam is 93 KJ / m. 2 .

[0104] Example 31 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and dimethyl adipate (DMA) was added as an electron donor at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 60 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and dibutyl phthalate (DAB) was added as an electron donor at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloroform was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and phenyltriethoxysilane (PTH) was added as an electron donor at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 1 hour. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation. The polymer product had a molecular weight of 4.56 million and a bulk density of 0.38 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0105] Example 32 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was then heated to 60°C, and azidocyclooctyne succinate imine ester, fluorene diether, and ethyl silicate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and held at this temperature for 50 minutes. The temperature was then increased to 130°C and held at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and diisobutyl phthalate, bispyridinedioxymethylsilane, and SMCC electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and held at this temperature for 50 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 9 over a period of 2 hours. After titanium addition, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was raised to 110℃, and electron donors 3-chloropropyltriethoxysilane, methyl benzoate, and 1,2,4-trimethoxybenzene were added at a molar ratio of 0.2 to the MgCl2 support. The reaction was carried out at this temperature for 3 hours. The temperature was then lowered to 65℃, and the catalyst was decanted and washed 10 times. The washed catalyst was dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation. The polymer product had a molecular weight of 4.5 million and a bulk density of 0.38 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0106] Example 33 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was then heated to 80°C, and SMCC, 1,2-dimethoxyethane, and butyl benzoate electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and held at this temperature for 60 minutes. The temperature was then increased to 130°C and held at this temperature for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 80°C, and dibutyl phthalate, dodecanetetraacetic acid-succinimide, and phenyltriethoxysilane electron donors were added at a molar ratio of 0.1 to the MgCl2 support, and held at this temperature for 60 minutes. The temperature was then decreased to -12°C, and TiCl4 was added dropwise at a titanium-magnesium ratio of 10 over a period of 2.5 hours. After titanium addition, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was raised to 110℃, and electron donors 3-chloropropyltriethoxysilane, fluorene diether, and dimethyl phthalate were added at a molar ratio of 0.2 to the MgCl2 support. The reaction was maintained at this temperature for 3 hours. The temperature was then lowered to 65℃, and the catalyst was decanted and washed 10 times. The washed catalyst was dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.45 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0107] Example 34 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 50°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 50 minutes. The temperature was then increased to 130°C and kept at this temperature for 2 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 50°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 50 minutes. The temperature was then decreased to -12°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 10 over a period of 2.5 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 1 hour. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.73 million and a bulk density of 0.40 g / cm³. 3 The notched impact strength of the simply supported beam is 92 kJ / m. 2 .

[0108] Example 35 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and azidocyclooctynyl succinate imine ester, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and 1,2-dimethoxyethane, an electron donor, was added at a molar ratio of 0.1 to the MgCl2 support and kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloroprene was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and ethyl benzoate, an electron donor, was added at a molar ratio of 0.2 to the MgCl2 support and kept at this temperature for 2 hours. The mixture was then decreased to 65°C and decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.58 million and a bulk density of 0.42 g / cm³. 3 The notched impact strength of the simply supported beam is 94 KJ / m. 2 .

[0109] Example 36 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and dodecanetetraacetic acid-succinimide ester electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and diisobutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the mixture was decanted and washed 8 times. The washed catalyst was dried in a nitrogen drying oven using nitrogen gas. Small-scale evaluation was conducted using the prepared catalyst; the polymer product had a molecular weight of 4.51 million and a bulk density of 0.39 g / cm³. 3 The notched impact strength of a simply supported beam is 90 kJ / m. 2 .

[0110] Example 37 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and dicyclopentyldimethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.53 million and a bulk density of 0.4 g / cm³. 3 The notched impact strength of the simply supported beam is 92 kJ / m. 2 .

[0111] Example 38 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then increased to 130°C and kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. Dibutyl phthalate electron donor was then added at a molar ratio of 0.1 to the MgCl2 support, and the mixture was kept at this temperature for 30 minutes. The temperature was then decreased to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support, and the mixture was kept at this temperature for 2 hours. The temperature was then decreased to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.48 million and a bulk density of 0.41 g / cm³. 3 The notched impact strength of the simply supported beam is 91 kJ / m. 2 .

[0112] Comparative Example 1 At 25℃, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 60℃, and dibutyl phthalate, 3-chloropropyltriethoxysilane, and SMCC electron donor were added at a molar ratio of 0.4 to the MgCl2 support. The mixture was held at this temperature for 60 minutes. The temperature was then increased to 130℃ and held for 4 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60℃ and held for 30 minutes. The temperature was then decreased to -10℃, and TiCl4 was added dropwise at a titanium-to-Mg ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The mixture was then heated to 110℃ and held at this temperature for 2 hours. The temperature was then decreased to 65℃, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was evaluated in a small-scale test. The polymer product had a molecular weight of 4.29 million and a bulk density of 0.36 g / cm³. 3 The notched impact strength of a simply supported beam is 82 kJ / m. 2 .

[0113] Comparative Example 2 At 25℃, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were added to a catalyst preparation vessel and mixed. The mixture was heated to 60℃ and held at that temperature for 30 minutes. The temperature was then increased to 130℃ and held at that temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was lowered to 60℃, and dibutyl phthalate, 3-chloropropyltriethoxysilane, and SMCC electron donors were added at a molar ratio of 0.4 to the MgCl2 support. The mixture was held at that temperature for 60 minutes. The temperature was then lowered to -10℃, and TiCl4 was added dropwise at a titanium-to-Mg ratio of 8 over a period of 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support, and the mixture was heated to 110℃ and held at that temperature for 2 hours. The temperature was then lowered to 65℃, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluations were conducted using the prepared catalyst. The polymer product had a molecular weight of 4.28 million and a bulk density of 0.36 g / cm³. 3 The notched impact strength of the simply supported beam is 83 KJ / m. 2 .

[0114] Comparative Example 3 At 25℃, 0.05 mol MgCl2, 0.14 mol isooctyl alcohol, and 0.513 mol decane were added to a catalyst preparation vessel and mixed. The mixture was heated to 60℃ and held at that temperature for 30 minutes. The temperature was then increased to 130℃ and held at that temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then decreased to 60℃ and held at that temperature for 60 minutes. The temperature was then decreased to -10℃, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over a period of 2 hours. After the titanium addition was complete, cyclohexane chloride was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then increased to 110℃, and dibutyl phthalate, 3-chloropropyltriethoxysilane, and SMCC electron donors were added at a molar ratio of 0.4 to the MgCl2 support, and the reaction was held at that temperature for 2 hours. The temperature was then decreased to 65℃, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. Small-scale evaluations were conducted using the prepared catalyst. The polymer product had a molecular weight of 4.29 million and a bulk density of 0.35 g / cm³. 3 The notched impact strength of the simply supported beam is 81 KJ / m. 2 .

[0115] Comparative Example 4 At 25°C, 0.05 mol MgCl2, 0.14 mol isooctol, and 0.513 mol decane were mixed in a catalyst preparation vessel. The mixture was heated to 130°C, and SMCC (methyl methacrylate) electron donor was added at a molar ratio of 0.1 to the MgCl2 support. The mixture was kept at this temperature for 3 hours until the solution became clear and free of insoluble matter. The temperature was then lowered to 60°C, and dibutyl phthalate electron donor was added at a molar ratio of 0.1 to the MgCl2 support. The mixture was kept at this temperature for 30 minutes. The temperature was then lowered to -10°C, and TiCl4 was added dropwise at a titanium-to-magnesium ratio of 8 over 2 hours. After the titanium addition was complete, chlorocyclohexane was added at a molar ratio of 3.3 to the MgCl2 support. The temperature was then raised to 110°C, and 3-chloropropyltriethoxysilane electron donor was added at a molar ratio of 0.2 to the MgCl2 support. The mixture was kept at this temperature for 2 hours. The temperature was then lowered to 65°C, and the catalyst was decanted and washed 8 times. The washed catalyst was then dried in a nitrogen oven using nitrogen gas. The prepared catalyst was used for small-scale evaluation, and the polymer product had a molecular weight of 4.28 million and a bulk density of 0.35 g / cm³. 3 The notched impact strength of a simply supported beam is 82 kJ / m. 2 .

[0116] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing a polyethylene catalyst, characterized in that, The method includes the following steps: (1) Under diluent conditions, the magnesium halide precursor, alcohol compound and first internal electron donor are subjected to a first contact reaction to obtain a first reaction solution; (2) Add a second internal electron donor to the first reaction solution to carry out a second contact reaction, and obtain a second reaction solution; (3) Add titanium precursor to the second reaction solution to carry out the third contact reaction to obtain the third reaction solution; (4) After adding a haloalkane to the third reaction solution, add a third internal electron donor to carry out the fourth contact reaction.

2. The method according to claim 1, characterized in that, The first, second, and third internal electron donors each independently include at most two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors; and / or The titanium precursor is titanium halide.

3. The method according to claim 2, characterized in that, The molar content of any one of the first, second, and third internal electron donors is 10-100%.

4. The method according to claim 1, characterized in that, When the first, second, and third internal electron donors each independently include at least two types of internal electron donors selected from ester-based internal electron donors, ether-based internal electron donors, and organosiloxane-based internal electron donors, one of these types is an ester-based internal electron donor.

5. The method according to claim 4, characterized in that, The molar content of any one of the first, second, and third internal electron donors is 20-50%.

6. The method according to claim 1, characterized in that, The first, second, and third internal electron donors are selected from at least two types of internal electron donors, including ester-based internal electron donors, ether-based internal electron donors, and organosiloxane-based internal electron donors.

7. The method according to claim 6, characterized in that, When the first, second, and third internal electron donors are two types of internal electron donors selected from ester-based, ether-based, and organosiloxane-based internal electron donors, the molar content of any one type of internal electron donor is 10-90%; and / or When the first, second, and third internal electron donors are selected from three types of internal electron donors: ester-based internal electron donors, ether-based internal electron donors, and organosiloxane-based internal electron donors, the molar content of any one type of internal electron donor is 10-80%.

8. The method according to any one of claims 2-7, characterized in that, The titanium precursor is titanium tetrachloride; and / or The first, second, and third internal electron donors are all different; and / or The electron donor within the ester is selected from at least one of 4-(N-maleiminomethyl)cyclohexane-1-carboxylic acid succinimide, azadibenzocyclooctyl succinate succinimide, dibutyl phthalate, ethyl benzoate, dimethyl 2-cyanobutylsuccinate, ethyl silicate, di(2-ethylhexyl) phthalate, dimethyl succinate, and diethyl terephthalate; and / or The electron donor within the ether is selected from at least one of 2,3-dimethoxybutane, 1-allyl-3,4-dimethoxybenzene, and fluorene diether; and / or The internal electron donor of the organosiloxane is selected from 3-chloropropyltriethoxysilane and / or cyclohexylphenyldimethoxysilane.

9. The method according to any one of claims 1-7, characterized in that, The temperature of the first contact reaction is 10–40°C higher than the temperature of the fourth contact reaction; The temperature of the fourth contact reaction is 20–80°C higher than the temperature of the second contact reaction.

10. The method according to any one of claims 1-7, characterized in that, The conditions for the first contact reaction include: The temperature is 130–140℃; and / or The time is 2 to 4 hours.

11. The method according to any one of claims 1-7, characterized in that, The conditions for the second contact reaction include: Temperature is 40–80℃; and / or The time is 30 to 60 minutes.

12. The method according to any one of claims 1-7, characterized in that, The conditions for the third contact reaction include: Temperature range: -5 to -15℃; and / or The time is 2 to 3 hours.

13. The method according to any one of claims 1-7, characterized in that, The conditions for the fourth contact reaction include: Temperature is 100–120℃; and / or The time is 1 to 3 hours.

14. The method according to any one of claims 1-7, characterized in that, The diluent is a C9-C11 alkane; and / or The magnesium halide precursor is selected from at least one of magnesium dihalides, alkoxy magnesium halides, and alkyl magnesium halides; and / or The alcohols are C5-C8 alcohols; and / or The haloalkane is a halocycloalkane.

15. The method according to any one of claims 1-7, characterized in that, The molar ratio of the alcohol compound to the magnesium halide precursor is 2.5–3; and / or The molar ratio of the diluent to the magnesium halide precursor is 9–11; and / or The molar ratio of the first internal electron donor to the magnesium halide precursor is 0.05–0.2; and / or The molar ratio of the second internal electron donor to the magnesium halide precursor is 0.05–0.2; and / or The molar ratio of the third internal electron donor to the magnesium halide precursor is 0.1–0.4; and / or The total molar amount of the first and second internal electron donors is not greater than the molar amount of the third internal electron donor; and / or The molar ratio of the titanium precursor to the magnesium halide precursor is 7–11; and / or The molar ratio of the halohydrocarbon to the magnesium halide precursor is 3 to 4.

16. The method according to any one of claims 1-7, characterized in that, The method further includes drying after the fourth contact reaction.

17. A polyethylene catalyst, characterized in that, The catalyst is prepared by the method described in any one of claims 1-16.

18. A method for preparing ultra-high molecular weight polyethylene, characterized in that, The method includes: polymerizing ethylene, alkylaluminum and a catalyst in contact under solvent conditions; The catalyst is the polyethylene catalyst according to claim 17.

19. The method according to claim 18, characterized in that, The conditions for the polymerization reaction include: The temperature is 70–75°C; and / or The time is 1 to 2 hours; and / or The pressure is 0.7–0.8 MPa.

20. The method according to claim 18 or 19, characterized in that, The mass ratio of the alkylaluminum to the catalyst is 1:10-20.

21. A type of ultra-high molecular weight polyethylene, characterized in that, The ultra-high molecular weight polyethylene is prepared by the method described in any one of claims 18-20.

22. The ultra-high molecular weight polyethylene according to claim 21, characterized in that, The ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 4.4 million to 5 million; and / or The bulk density of the ultra-high molecular weight polyethylene is 0.38–0.45 g / cm³. 3 ; and / or The notched impact strength of the ultra-high molecular weight polyethylene is 90-110 KJ / m. 2 .