Ultra-high molecular weight polyethylene and its manufacturing method

Abstract

The present invention relates to ultra-high molecular weight polyethylene and a method for producing the same. The ultra-high molecular weight polyethylene has a viscosity average molecular weight of 150 to 1000×10 4 g / mol, metal element content is 0-50 ppm, and bulk density is 0.30-0.55 g / cm 3 The polyethylene has a true density of 0.900 to 0.940 g / cm, a melting point of 140 to 152°C, and a crystallinity of 40 to 75%. The polyethylene also satisfies one or more of the following conditions (1) and (2). Condition (1): The tensile modulus is greater than 250 MPa, preferably greater than 280 MPa, and more preferably greater than 300 MPa. Condition (2): The Young's modulus is greater than 300 MPa, and preferably greater than 350 MPa. The ultra-high molecular weight polyethylene has high mechanical properties, a high melting point, and a low metal element content and ash content. The production method is simple, flexible, and adjustable. The ultra-high molecular weight ethylene copolymer has a high tensile modulus.

Description

[Technical Field]

[0001] The present invention relates to ultra-high molecular weight ethylene homopolymers and ethylene copolymers having low metal element contents and excellent mechanical properties. The present invention also relates to a process for producing ethylene homopolymers and ethylene copolymers in a slurry using an alkane or mixed alkanes as a polymerization solvent and a catalyst system containing a supported nonmetallocene catalyst as the main catalyst. [Background technology]

[0002] Generally, ultra-high molecular weight polyethylene (UHMWPE) is a material with a relative molecular weight of 150 x 10 4 Ultra-high molecular weight polyethylene (ULHMWPE) refers to polyethylene with a linear structure of 1000 g / mol or more. The advantages of UHMWPE include excellent abrasion resistance, very high impact strength, self-lubrication, chemical and low-temperature resistance, excellent adhesive resistance, hygienic properties, non-toxicity, non-polluting properties, and recyclability / reusability. These are characteristics not found in conventional polyethylene. For this reason, UHMWPE is widely used in a variety of fields, including textiles, paper, food, the chemical industry, packaging, agriculture, construction, medicine, water purification, sports, entertainment, and the military.

[0003] For high quality applications, the viscosity average molecular weight is very high (typically 400 x 10 4 Ultra-high molecular weight polyethylene (UMPE) with a low ash content (>100 g / mol) can be used in dry spinning or wet gel spinning to produce high-strength UHMWPE fibers. These fibers are used in bulletproof materials, stab-resistant fibers, parachutes, fishing boxes, fishing nets, etc. With its low metal element content and excellent mechanical properties, UHMWPE can also be used in medical materials such as artificial joints.

[0004] Currently, ultra-high molecular weight polyethylene is primarily polymerized by slurry polymerization using Ziegler-Natta catalysts. Patent ZL94116488.8 discloses a method for producing ultra-high molecular weight polyethylene with high bulk density. In this method, ethylene is catalytically polymerized using a mixed catalyst containing an organoaluminum compound and a titanium component. Patent CN200410054344.7 discloses an ultra-high molecular weight polyethylene catalyst and its production method and use. The catalyst consists of a magnesium compound supported on a titanium-containing component and a silicon-containing component.

[0005] Ultra-high molecular weight polyethylene is produced in the presence of an organoaluminum compound. CN200710042467.2 discloses an ultra-high molecular weight polyethylene catalyst and a method for producing the same. The main component of this catalyst is obtained by the following steps: (1) reacting a magnesium halide with an alcohol to produce a magnesium compound; (2) reacting a magnesium compound with a silicon compound to produce an intermediate product having one or more halogen groups; and (3) reacting the intermediate product with a titanium compound to produce the main component of the catalyst. A benzoate ester compound may be optionally added in each reaction step. This ultra-high molecular weight polyethylene catalyst is highly active, and the resulting ultra-high molecular weight polyethylene has a high bulk density.

[0006] CN200710042468.7 discloses an ultra-high molecular weight polyethylene catalyst and a method for producing the same. The main component of this catalyst is obtained by the following steps: (1) reacting a magnesium halide compound with an alcohol compound and a titanate ester compound to obtain a magnesium compound solution; (2) reacting the magnesium compound solution with an alkylaluminum chloride compound to obtain an intermediate product; and (3) reacting the intermediate product with a titanium compound and an electron donor. This ultra-high molecular weight polyethylene catalyst has high activity, and the resulting ultra-high molecular weight polyethylene has a high bulk density. US4962167A1 discloses a method for obtaining a polyethylene catalyst. This method involves reacting the reaction product of a magnesium halide compound and a titanium alkoxide with the reaction product of an aluminum halide and a silicon alkoxide. US5587440 discloses a method for producing ultra-high molecular weight polyethylene with a narrow particle size distribution and high bulk density. In this production method, titanium(IV) halide is reduced with an organoaluminum compound, followed by post-treatment. However, the activity of this catalyst is relatively low.

[0007] The main methods for producing polyethylene include high-pressure polymerization, gas-phase polymerization, slurry polymerization, and solution polymerization. Among these, slurry polymerization of ethylene is one of the main methods for producing polyethylene. This production method can be divided into polymerization processes in loop reactors and slurry polymerization processes in stirred tanks.

[0008] To obtain ultra-high molecular weight polyethylene, ethylene is usually polymerized in a hexane or heptane solvent at the lowest possible polymerization temperature and pressure. Higher polymerization temperatures promote chain transfer and inhibit the elongation of the polyethylene molecular chains, making it difficult to obtain polyethylene with a high viscosity average molecular weight.

[0009] It is also known that copolymerization of ethylene and a comonomer reduces the molecular weight of the resulting polyethylene. 4Even synthesizing ultra-high molecular weight ethylene copolymers in the g / mol range has been difficult.

[0010] Patent CN201480057309.2 discloses a method for producing granular ultra-high molecular weight polyethylene copolymer. In this production method, an organometallic compound (R 33 P=N-TiCpXn) on a magnesium support. However, the activity of this catalyst is relatively low and the ash content of the copolymer is relatively high.

[0011] Patent CN201780000391.9 discloses an ultra-high molecular weight ethylene copolymer powder and a molded article using the same. In this document, the total amount of α-olefin units is 0.01-0.10 mol%. However, referring to the examples, the titanium content in the copolymer is relatively high.

[0012] Patents CN201610892732.5, CN201610892836.6, CN201610892837.0, and CN201610892424.2 disclose ultra-high molecular weight polyethylene and its production and use. These documents describe the homopolymerization of ethylene and the copolymerization of ethylene and an α-olefin using a supported nonmetallocene catalyst. The resulting ultra-high molecular weight polyethylene molecular chain is composed of two or more segments (homopolymerized segment A and copolymerized segment B), resulting in a block copolymer with a broad molecular weight distribution.

[0013] A common approach to obtaining ultra-high molecular weight polyethylene with low metal element content is to select or prepare an appropriate catalyst system under ethylene polymerization conditions to maximize polymerization activity. This requires a catalyst with high intrinsic polymerization activity. Another approach is to increase polymerization activity by extending the polymerization time as much as possible under intermittent ethylene slurry polymerization conditions. This requires a catalyst with a long polymerization activity life. Furthermore, even if the instantaneous consumption of ethylene, the polymerization monomer, increases, remains constant, or decreases over time, it must not decrease rapidly or rapidly to a very low level (which would obviate the significance of extending the reaction time). Furthermore, the ultra-high molecular weight polyethylene obtained by polymerization must be post-treated. For example, Chinese Patent 200410024103.8 discloses post-treatment of ultra-high molecular weight polyethylene. This post-treatment includes filtration, washing with a solvent, drying, washing with water, and sieving. However, this process is complicated, and impurities are inevitably present in the washing solvent. Consequently, washing and drying are costly.

[0014] Chinese Patent No. 201610747653.5 discloses a continuous water washing apparatus and a method for producing ultra-high molecular weight polyethylene. The document notes that during the ultra-high molecular weight polyethylene polymerization process, catalysts and alkyl aluminums form active centers, which initiate the ethylene polymerization reaction, while also producing small amounts of metallic acid. If water washing is not performed, the metallic acid may corrode the processing equipment during subsequent powder processing. Furthermore, if excessive alkyl aluminums with high boiling points are present during the polymerization process, they will react with small amounts of oxygen and trace amounts of water in the solvent to produce aluminum hydroxide, resulting in a high aluminum content in the polyethylene. This results in reduced tensile strength, impact strength, and abrasion resistance.

[0015] Therefore, given the current state of the art, there remains a need for an ultra-high molecular weight polyethylene (UHMWPE) with a high and tunable viscosity average molecular weight, high bulk density, excellent mechanical properties, low metal element content, and low ash content. Similarly, there is a need for a method for producing UHMWPE under ethylene slurry polymerization conditions that provides a long-life, highly active catalyst, a flexible and tunable polymerization process, and is suitable for large-scale implementation. The resulting UHMWPE has a high bulk density, low branching for ethylene homopolymers, and a high tensile modulus for ethylene copolymers, which are beneficial for product packaging, storage, transportation, loading, and downstream processing. Summary of the Invention

[0016] The inventors have found, through extensive research based on existing technologies, that ultra-high molecular weight polyethylene with a low metal element content and excellent mechanical properties can be obtained by slurry polymerization of ethylene and one or more optional comonomers as raw materials. The polymerization solvent used is an alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa at 20°C. A supported nonmetallocene catalyst is used as the main catalyst. One or more of aluminoxane, alkylaluminum, and haloalkylaluminum are used as the cocatalyst. The slurry polymerization of ethylene is carried out in the absence of hydrogen gas. This has solved the above-mentioned problems, leading to the completion of the present invention.

[0017] Specifically, the ultra-high molecular weight polyethylene and its production method of the present invention can produce ultra-high molecular weight polyethylene with a low metal element content and excellent mechanical properties. This does not require harsh ethylene slurry polymerization reactors or polymerization conditions, nor does it require a post-treatment process for the complex. Specifically, the resulting polyethylene has excellent mechanical properties (high tensile modulus, Young's modulus, tensile yield strength, tensile fracture strength, impact strength, etc.). Therefore, it is highly suitable for industrial-scale production and the subsequent fabrication of high-strength ultra-high molecular weight polyethylene fibers and medical artificial joints.

[0018] Specifically, the present invention provides an ultra-high molecular weight polyethylene. The viscosity average molecular weight of this ultra-high molecular weight polyethylene is 150 to 1000 × 10 4 g / mol, preferably 200 to 850 × 10 4 g / mol, more preferably 300 to 700 × 10 4 g / mol. The metal element content is 0 to 50 ppm, preferably 0 to 30 ppm. The polyethylene satisfies one or more of the following conditions (1) and (2): Condition (1): The tensile modulus is greater than 250 MPa, preferably greater than 280 MPa, and more preferably greater than 300 MPa. Condition (2): Young's modulus is greater than 300 MPa, preferably greater than 350 MPa.

[0019] More specifically, when the ultra-high molecular weight polyethylene is an ethylene homopolymer, the viscosity average molecular weight is 150 to 1000 × 10 4 g / mol, preferably 200 to 850 × 10 4g / mol. The titanium content is 0 to 3 ppm, preferably 0 to 2 ppm, and more preferably 0 to 1 ppm. The calcium content is 0 to 5 ppm, preferably 0 to 3 ppm, and more preferably 0 to 2 ppm. The magnesium content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 2 ppm. The aluminum content is 0 to 30 ppm, preferably 0 to 20 ppm, and more preferably 0 to 15 ppm. The silicon content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 3 ppm. The chlorine content is 0 to 50 ppm, and preferably 0 to 30 ppm. The ash content is less than 200 ppm, preferably less than 150 ppm, and more preferably 80 ppm or less. The tensile yield strength is greater than 22 MPa, and preferably greater than 25 MPa. The tensile strength at break is greater than 32 MPa, and preferably greater than 35 MPa. The elongation at break is greater than 350%, preferably greater than 400%. The impact strength is greater than 70 kJ / m 2 more than 75 kJ / m 2 The Young's modulus is greater than 300 MPa, preferably greater than 350 MPa, and more preferably greater than 400 MPa.

[0020] More specifically, when the ultra-high molecular weight polyethylene is an ethylene copolymer, the viscosity average molecular weight is 150 to 800 × 10 4 g / mol, preferably 200 to 700 × 10 4g / mol. The titanium content is 0 to 3 ppm, preferably 0 to 2 ppm, and more preferably 0 to 1 ppm. The calcium content is 0 to 5 ppm, preferably 0 to 3 ppm, and more preferably 0 to 2 ppm. The magnesium content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 2 ppm. The aluminum content is 0 to 30 ppm, preferably 0 to 20 ppm, and more preferably 0 to 15 ppm. The silicon content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 3 ppm. The chlorine content is 0 to 50 ppm, and preferably 0 to 30 ppm. The ash content is less than 200 ppm, preferably less than 150 ppm, and more preferably 80 ppm or less. The tensile modulus is greater than 250 MPa, preferably greater than 280 MPa, and more preferably greater than 300 MPa.

[0021] The present invention also provides a method for producing ultra-high molecular weight polyethylene. The ultra-high molecular weight polyethylene has a viscosity average molecular weight of 150 to 1000×10 4 g / mol, preferably 200 to 850 × 10 4 g / mol, more preferably 300 to 700 × 10 4 g / mol. In this production method, raw materials containing ethylene and one or more optional comonomers are slurry polymerized in the absence of hydrogen gas. A supported nonmetallocene catalyst is used as the main catalyst. One or more of aluminoxane, alkylaluminum, and haloalkylaluminum are used as the co-catalyst. An alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa (preferably 40 to 110 kPa) at 20°C is used as the polymerization solvent. This produces ultra-high molecular weight polyethylene with a low metal element content. [Effects of the Invention]

[0022] The ultra-high molecular weight polyethylene of the present invention has a high viscosity average molecular weight, a low metal element content, a low ash content, and excellent mechanical properties. Specifically, this polyethylene has high tensile modulus, tensile yield strength, tensile strength at break, impact strength, Young's modulus, and elongation at break. This is extremely beneficial in improving the tensile strength, impact strength, and abrasion resistance of products made from this polyethylene.

[0023] The production method of the present invention requires a small amount of cocatalyst, provides a stable polymerization process, stabilizes the real-time consumption of ethylene, extends the active life of the polymerization system, and produces a high polymerization activity of the ethylene slurry. Furthermore, polyethylene (ethylene homopolymer or ethylene copolymer) having a very high viscosity average molecular weight can be obtained at a relatively high polymerization temperature.

[0024] In the polymerization process of the present invention, an alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa at 20°C is used as the polymerization solvent. This allows for a wide range of polymerization solvents to be selected, enabling various methods of heat removal during the polymerization reaction and in post-processing of the resulting ultra-high molecular weight polyethylene powder. Furthermore, post-processing of the resulting ultra-high molecular weight polyethylene is also easy. Furthermore, when a nonmetallocene catalyst is used, the amount of solvent remaining in the resulting ultra-high molecular weight polyethylene is reduced. This significantly reduces the drying time of the polyethylene material and reduces the cost of post-processing of the polyethylene. This promotes the subsequent industrial use of ethylene polymers. Additionally, polyethylene with low metal element and ash contents and excellent mechanical properties can be achieved.

[0025] In the polymerization process of the present invention, only an alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure of 20 to 150 kPa at 20°C is used as the polymerization solvent, and no other solvents (dispersants, diluents, etc.) are required. Therefore, the reaction system is simple, and post-treatment is simple and easy. DETAILED DESCRIPTION OF THE INVENTION

[0026] Reference will now be made in detail to the embodiments of the invention, however it will be understood that the scope of the invention is not limited to these embodiments but is defined by the appended claims.

[0027] In the context of the present invention, unless expressly defined otherwise or contrary to the understanding of one skilled in the art, hydrocarbon or hydrocarbon-derived groups having three or more carbon atoms without the prefix "n-" (e.g., propyl, propyloxy, butyl, butane, butene, butenyl, hexane, etc.) have the same meaning as those with the prefix "n-". For example, "propyl" generally refers to "n-propyl". "Butyl" generally refers to "n-butyl" unless otherwise specified.

[0028] In order to avoid complicating the description, the present specification does not specify whether the valence of the substituents or groups contained in the compound is monovalent, divalent, trivalent, or tetravalent. A person skilled in the art should be able to make a specific judgment based on the position or substitution of the substituents or groups (such as the G group, D group, B group, A group, and F group described herein) in the structural formula of the compound. Furthermore, a person skilled in the art should be able to select a valence appropriate for the position or substitution state based on the definition of the substituents or groups described herein.

[0029] All publications, patent applications, patents, and other references mentioned herein are incorporated by reference. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

[0030] In this specification, materials, substances, processes, steps, apparatus, devices, and the like may be referred to by expressions such as "well-known to those skilled in the art" or "prior art." The intended meaning of such expressions is that the structures are conventionally used in the art at the time of filing of this application. Additionally, the intended meaning includes structures that are not currently common but may become known in the art in the future as suitable for a similar purpose.

[0031] In connection with this specification, unless expressly stated otherwise, those known in the art may be applied to any article or substance not directly mentioned without any modifications. Furthermore, any embodiment described herein may be freely combined with one or more other embodiments described herein. Any technical solutions or technical ideas derived therefrom are also considered to be the original disclosure or part of the present invention. Unless a person skilled in the art believes that a combination is clearly unreasonable, such a combination should not be construed as a new matter not disclosed or anticipated herein.

[0032] Unless expressly stated otherwise, all percentages, parts, ratios, etc. in the specification are by weight, except where using a weight basis would be inconsistent with the prior knowledge of a person skilled in the art.

[0033] Reference will now be made in detail to the embodiments of the invention, however it will be understood that the scope of the invention is not limited to these embodiments but is defined by the appended claims.

[0034] In connection with the present invention, unless otherwise specified, the physical properties of substances (such as boiling point) are values ​​measured at room temperature (25°C) and atmospheric pressure (101,325 Pa).

[0035] The inventors have found through extensive research that the polymerization process of the present invention uses an alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa at 20°C as the polymerization solvent. This results in a reaction product of the specific polymerization solvent of the present invention, ethylene, and one or more optional copolymerizable olefins (e.g., propylene, 1-butene, 1-hexene, 1-octene), with a significantly different boiling point from conventional polymerization solvents. This facilitates and streamlines post-processing of the resulting ultra-high molecular weight polyethylene powder. Furthermore, the amount of solvent remaining in the resulting ultra-high molecular weight polyethylene powder is reduced, shortening the drying time of the polyethylene powder and reducing post-processing costs for the polyethylene powder. Furthermore, the present invention uses only an alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa at 20°C as the polymerization solvent, eliminating the need for other solvents (e.g., dispersants, diluents, etc.). Therefore, the reaction system is simple and post-treatment is simple and easy.

[0036] In the present invention, the catalytic activity of a slurry polymerization system can be further improved. To achieve this, a catalyst system consisting of a nonmetallocene catalyst and a co-catalyst is used in an alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure at 20°C of 20 to 150 kPa (preferably 40 to 110 kPa). This stabilizes the polymerization process and real-time ethylene consumption. Therefore, polyethylene with a very high viscosity-average molecular weight can be obtained at a relatively high polymerization temperature. Furthermore, when the slurry polymerization system of the present invention is used in copolymerization, the insertion rate of the copolymerized olefin can be improved.

[0037] Therefore, the ultra-high molecular weight polyethylene obtained in the present invention has a high viscosity average molecular weight, a low metal element content, and a low ash content. The obtained polyethylene has excellent mechanical properties. Specifically, the polyethylene has high tensile modulus, tensile yield strength, tensile strength at break, impact strength, Young's modulus, and elongation at break. Therefore, products obtained using the ultra-high molecular weight polyethylene of the present invention have excellent mechanical strength and a low impurity content. Therefore, products obtained using the ultra-high molecular weight polyethylene of the present invention are suitable for applications in aerospace, medical materials, and other fields where strict quality is required.

[0038] In the polymerization process of the present invention, no complicated purification process is required after the production of the crude ultra-high molecular weight polyethylene product (washing with high-purity solvents, washing with high-purity water, high-temperature steaming, polymer melting and filtration, etc.). In other words, nothing is required other than removing the solvent (filtration, decantation, flash evaporation, evaporation to dryness, etc.). This allows for the production of high-purity ultra-high molecular weight polyethylene with low metal element content, low ash content, and excellent mechanical properties.

[0039] In the present invention, ethylene homopolymer and ethylene copolymer are collectively referred to as “ethylene polymer” or “polyethylene.” When copolymerized units are present, the ultra-high molecular weight polyethylene of the present invention has a random copolymer structure rather than a block copolymer structure.

[0040] The ultra-high molecular weight polyethylene provided by the present invention has a viscosity average molecular weight of 150 to 1000 × 10 4 g / mol, preferably 200 to 850 × 10 4 g / mol, more preferably 300 to 700 × 10 4 g / mol. The metal element content is 0 to 50 ppm, preferably 0 to 30 ppm. This polyethylene satisfies one or more of the following conditions (1) and (2): Condition (1): The tensile modulus is greater than 250 MPa, preferably greater than 280 MPa, and more preferably greater than 300 MPa. Condition (2): Young's modulus is greater than 300 MPa, preferably greater than 350 MPa.

[0041] In one embodiment of the present invention, the bulk density of the polyethylene is 0.30 to 0.55 g / cm 3 and preferably 0.33 to 0.52 g / cm 3 and more preferably 0.40 to 0.50 g / cm 3 In one embodiment of the present invention, the true density of the polyethylene is 0.900 to 0.940 g / cm 3 and preferably 0.905 to 0.935 g / cm 3 and more preferably 0.915 to 0.930 g / cm 3 In one embodiment of the present invention, the melting point of the polyethylene is 140 to 152° C., and preferably 142 to 150° C. In one embodiment of the present invention, the crystallinity of the polyethylene is 40 to 75%, and preferably 45 to 70%.

[0042] In one embodiment of the present invention, the titanium content of the polyethylene is 0 to 3 ppm, preferably 0 to 2 ppm, and more preferably 0 to 1 ppm. In one embodiment of the present invention, the calcium content of the polyethylene is 0 to 5 ppm, preferably 0 to 3 ppm, and more preferably 0 to 2 ppm. In one embodiment of the present invention, the magnesium content of the polyethylene is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 2 ppm. In one embodiment of the present invention, the aluminum content of the polyethylene is 0 to 30 ppm, preferably 0 to 20 ppm, and more preferably 0 to 15 ppm. In one embodiment of the present invention, the silicon content of the polyethylene is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 3 ppm. In one embodiment of the present invention, the chlorine content of the polyethylene is 0 to 50 ppm, and preferably 0 to 30 ppm.

[0043] In one embodiment of the present invention, the polyethylene has a comonomer unit. This polyethylene is a random copolymer. The molar insertion rate of the comonomer is 0.05 to 4.0%, preferably 0.10 to 2.0%.

[0044] In one embodiment of the present invention, the polyethylene satisfies one or more of the following conditions (3) to (6): Condition (3): The tensile yield strength is greater than 22 MPa, and preferably greater than 25 MPa. Condition (4): The tensile strength at break is greater than 32 MPa, and preferably greater than 35 MPa. Condition (5): The breaking elongation is greater than 350%, and preferably greater than 400%. Condition (6): Impact strength is 70kJ / m 2 more than 75 kJ / m 2 It's super.

[0045] In one embodiment of the present invention, the ash content of the polyethylene is less than 200 ppm, preferably less than 150 ppm, and more preferably 80 ppm or less.

[0046] In one embodiment of the present invention, when the polyethylene is an ethylene homopolymer, the viscosity average molecular weight is 150 to 1000 × 10 4 g / mol, preferably 200 to 850 × 10 4 g / mol.

[0047] In one embodiment of the present invention, when the polyethylene is an ethylene homopolymer, the titanium content is 0 to 3 ppm, preferably 0 to 2 ppm, and more preferably 0 to 1 ppm. The calcium content is 0 to 5 ppm, preferably 0 to 3 ppm, and more preferably 0 to 2 ppm. The magnesium content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 2 ppm. The aluminum content is 0 to 30 ppm, preferably 0 to 20 ppm, and more preferably 0 to 15 ppm. The silicon content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 3 ppm. The chlorine content is 0 to 50 ppm, and preferably 0 to 30 ppm.

[0048] In one embodiment of the present invention, when the polyethylene is an ethylene homopolymer, the bulk density is 0.30 to 0.55 g / cm 3 and preferably 0.33 to 0.52 g / cm 3 and more preferably 0.40 to 0.45 g / cm 3 The true density is 0.910 to 0.940 g / cm 3 and preferably 0.915 to 0.935 g / cm 3 and more preferably 0.920 to 0.930 g / cm 3 The melting point is 140 to 152° C., preferably 142 to 150° C. The crystallinity is 40 to 75%, preferably 45 to 70%.

[0049] In one embodiment of the present invention, when the polyethylene is an ethylene homopolymer, the tensile yield strength is greater than 22 MPa, preferably greater than 25 MPa. The tensile strength at break is greater than 32 MPa, preferably greater than 35 MPa. The elongation at break is greater than 350%, preferably greater than 400%. The impact strength is greater than 70 kJ / m 2 more than 75 kJ / m 2 The Young's modulus is greater than 300 MPa, preferably greater than 350 MPa.

[0050] In one embodiment of the present invention, when the polyethylene is an ethylene homopolymer, the ash content is less than 200 ppm, preferably less than 150 ppm, and more preferably 80 ppm or less.

[0051] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the viscosity average molecular weight is 150 to 800 × 10 4 g / mol, preferably 200 to 700 × 10 4 g / mol.

[0052] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the titanium content is 0 to 3 ppm, preferably 0 to 2 ppm, and more preferably 0 to 1 ppm. The calcium content is 0 to 5 ppm, preferably 0 to 3 ppm, and more preferably 0 to 2 ppm. The magnesium content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 2 ppm. The aluminum content is 0 to 30 ppm, preferably 0 to 20 ppm, and more preferably 0 to 15 ppm. The silicon content is 0 to 10 ppm, preferably 0 to 5 ppm, and more preferably 0 to 3 ppm. The chlorine content is 0 to 50 ppm, and preferably 0 to 30 ppm.

[0053] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the bulk density is 0.30 to 0.55 g / cm 3 and preferably 0.33 to 0.52 g / cm 3 and more preferably 0.41 to 0.50 g / cm 3 The true density is 0.900 to 0.940 g / cm 3 and preferably 0.905 to 0.935 g / cm 3 and more preferably 0.910 to 0.930 g / cm 3 The melting point is 140 to 152° C., preferably 142 to 150° C. The crystallinity is 40 to 75%, preferably 45 to 70%.

[0054] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the copolymer has a random copolymer structure, and the molar insertion rate of the comonomer is 0.05 to 4.0%, preferably 0.10 to 2.0%.

[0055] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the tensile modulus is greater than 250 MPa, preferably greater than 280 MPa, more preferably greater than 300 MPa.

[0056] In one embodiment of the present invention, when the polyethylene is an ethylene copolymer, the ash content is less than 200 ppm, preferably less than 150 ppm, and more preferably 80 ppm or less.

[0057] The metal element content of the ultra-high molecular weight polyethylene provided by the present invention is 0 to 50 ppm, preferably 0 to 30 ppm.

[0058] The ultra-high molecular weight polyethylene of the present invention can be obtained by the ethylene slurry production method of the present invention described below.

[0059] The present invention provides a method for producing ultra-high molecular weight polyethylene. In this method, raw materials containing ethylene and, as an optional ingredient, one or more comonomers are subjected to slurry polymerization in the absence of hydrogen gas. In this process, a supported nonmetallocene catalyst is used as the main catalyst. One or more of aluminoxane, alkylaluminum, and haloalkylaluminum are used as the co-catalyst. As the polymerization solvent, an alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure at 20°C of 20 to 150 kPa (preferably 40 to 110 kPa) is used.

[0060] In one embodiment of the present invention, in the method for producing ultra-high molecular weight polyethylene, the polymerization temperature is 50 to 100° C., and preferably 60 to 90° C. The polymerization pressure is 0.4 to 4.0 MPa, preferably 1.0 to 3.0 MPa, and most preferably 1.5 to 3.0 MPa.

[0061] In one embodiment of the present invention, in a method for producing ultra-high molecular weight polyethylene, the slurry polymerization activity of ethylene is 2×10 polyethylene per 1 g of main catalyst. 4 g, preferably 3×10 polyethylene per gram of main catalyst 4 g of polyethylene per gram of main catalyst, and most preferably 4×10 4 It is over g.

[0062] In one embodiment of the present invention, in the method for producing ultra-high molecular weight polyethylene, when a comonomer is present, the molar ratio of the comonomer to the active metal in the catalyst is (10 to 500): 1, and preferably (20 to 400): 1. Ethylene and the comonomer are both charged into a polymerization system and polymerized in one step.

[0063] In one embodiment of the present invention, no hydrogen gas is used in the process for producing ultra-high molecular weight polyethylene.

[0064] In the present invention, the term "ethylene homopolymer" refers to a homopolymer formed by homopolymerization using ethylene as the only polymerization monomer, and the term "ethylene copolymer" refers to a copolymer formed by polymerization of ethylene with one or more comonomers other than ethylene.

[0065] Specifically, for ethylene copolymers, the comonomers are selected from α-olefins, diolefins, cyclic olefins, and other olefinically unsaturated compounds. α-olefins are C3 to C 10It may be an α-olefin. Examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 4-methyl-1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and styrene. Examples of cyclic olefins include 1-cyclopentene, ethylidene, norbornene, and norbornene. Examples of diolefins include 1,4-butadiene, 2,5-pentadiene, 1,5-hexadiene, vinylnorbornene, norbornadiene, and 1,7-octadiene. Examples of other olefinically unsaturated compounds include vinyl acetate and (meth)acrylic acid esters. Among these, the comonomer is preferably a C3-C 10 The α-olefin is more preferably selected from 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and mixtures thereof, and even more preferably selected from 1-butene, 1-hexene, 1-octene, and mixtures thereof.

[0066] The α-olefin comonomer may be used alone or in combination of two or more. In one embodiment of the present invention, when a comonomer is used in the polymerization reaction, the molar ratio of the comonomer to the active metal in the catalyst is (10 to 500):1, preferably 20 to (400:1), and more preferably (50 to 300):1. In one embodiment of the present invention, when a comonomer is used in the polymerization reaction, the proportion of the comonomer to the total number of moles of ethylene and comonomer is 0.01 to 3 mol%, and preferably 0.01 to 2 mol%.

[0067] In the polymerization reaction, ethylene and a comonomer are charged together into a polymerization tank. In the present invention, "charging ethylene and a comonomer together into a polymerization tank" means that raw materials containing ethylene and a comonomer are charged together into a reaction tank and the polymerization reaction is allowed to proceed. In this case, there is no separate polymerization step. That is, there is no separate step in which ethylene is first polymerized and then a comonomer is added for polymerization, nor is there a separate step in which the comonomer is homogenized and then ethylene is added for polymerization.

[0068] In the present invention, the supported nonmetallocene catalyst, which is the main catalyst, can be produced by a method well known in the art, for example, by the following steps. Dissolving a magnesium compound in a first solvent in the presence of an alcohol to obtain a magnesium compound solution. A step of mixing the porous carrier with the magnesium compound solution to obtain a first mixed slurry. Optionally, the porous carrier may be subjected to a thermal activation treatment and / or a chemical activation treatment. A step of adding a precipitant to the first mixed slurry or drying the first mixed slurry to obtain a composite carrier. contacting the composite support with a chemical treating agent selected from Group IVB metal compounds to obtain a modified composite support; contacting the nonmetallocene complex with the modified composite support in the presence of a second solvent to obtain a second mixed slurry, which is optionally further dried to obtain a supported nonmetallocene catalyst;

[0069] The magnesium compound is described below.

[0070] In the present invention, the term "magnesium compound" includes the common concept in the art. This term refers to organic or inorganic anhydrous solid magnesium-containing compounds, which are commonly used as supports in supported olefin polymerization catalysts.

[0071] Specific examples of magnesium halides include magnesium chloride (MgCl2), magnesium bromide (MgBr2), magnesium iodide (MgI2), and magnesium fluoride (MgF2). Among these, magnesium chloride is preferred.

[0072] Examples of alkoxy magnesium halides include methyloxy(chloro)magnesium (Mg(OCH3)Cl), ethyloxy(chloro)magnesium (Mg(OC2H5)Cl), propyloxy(chloro)magnesium (Mg(OC3H7)Cl), n-butyloxy(chloro)magnesium (Mg(OC4H9)Cl), isobutyloxy(chloro)magnesium (Mg(i-OC4H9)Cl), methyloxy(bromo)magnesium (Mg(OCH3)Br), ethyloxy(bromo)magnesium (Mg(OC2H5)Br), propyloxy( Examples of magnesium iodides include magnesium iodides (bromo) (Mg(OC3H7)Br), n-butyloxy(bromo) (Mg(OC4H9)Br), isobutyloxy(bromo) (Mg(i-OC4H9)Br), methyloxy(iodo) magnesium (Mg(OCH3)I), ethyloxy(iodo) magnesium (Mg(OC2H5)I), propyloxy(iodo) magnesium (Mg(OC3H7)I), n-butyloxy(iodo) magnesium (Mg(OC4H9)I), and isobutyloxy(iodo) magnesium (Mg(i-OC4H9)I). Among these, methyloxy(chloro) magnesium, ethyloxy(chloro) magnesium, and isobutyloxy(chloro) magnesium are preferred.

[0073] Examples of alkoxymagnesium include methyloxymagnesium (Mg(OCH3)2), ethyloxymagnesium (Mg(OC2H5)2), propyloxymagnesium (Mg(OC3H7)2), butyloxymagnesium (Mg(OC4H9)2), isobutyloxymagnesium (Mg(i-OC4H9)2), and 2-ethylhexyloxymagnesium (Mg(OCH2CH(C2H5)C4H8)2). Of these, ethyloxymagnesium and isobutyloxymagnesium are preferred.

[0074] Examples of alkyl magnesium include methyl magnesium (Mg(CH3)2), ethyl magnesium (Mg(C2H5)2), propyl magnesium (Mg(C3H7)2), n-butyl magnesium (Mg(C4H9)2), and isobutyl magnesium (Mg(i-C4H9)2). Of these, ethyl magnesium and n-butyl magnesium are preferred.

[0075] Examples of alkyl magnesium halides include methyl(chloro)magnesium (Mg(CH3)Cl), ethyl(chloro)magnesium (Mg(C2H5)Cl), propyl(chloro)magnesium (Mg(C3H7)Cl), n-butyl(chloro)magnesium (Mg(C4H9)Cl), isobutyl(chloro)magnesium (Mg(i-C4H9)Cl), methyl(bromo)magnesium (Mg(CH3)Br), ethyl(bromo)magnesium (Mg(C2H5)Br), propyl(bromo)magnesium (Mg(CH3)Br), and propyl(bromo)magnesium (Mg(CH3)Br). Examples of magnesium iodides include magnesium iodides (Mg(CH)Br), n-butyl(bromo)magnesium (Mg(CH)Br), isobutyl(bromo)magnesium (Mg(i-CH)Br), methyl(iodo)magnesium (Mg(CH)I), ethyl(iodo)magnesium (Mg(CH)I), propyl(iodo)magnesium (Mg(CH)I), n-butyl(iodo)magnesium (Mg(CH)I), and isobutyl(iodo)magnesium (Mg(i-CH)I). Among these, methyl(chloro)magnesium, ethyl(chloro)magnesium, and isobutyl(chloro)magnesium are preferred.

[0076] Examples of alkylalkoxymagnesium include methylmethyloxymagnesium (Mg(OCH3)(CH3)), methylethyloxymagnesium (Mg(OC2H5)(CH3)), methylpropyloxymagnesium (Mg(OC3H7)(CH3)), methyln-butyloxymagnesium (Mg(OC4H9)(CH3)), methylisobutyloxymagnesium (Mg(i-OC4H9)(CH3)), ethylmethyloxymagnesium (Mg(OCH3)(C2H5)), ethylethyloxymagnesium (Mg(OCH3)(CH3)), methylisobutyloxymagnesium (Mg(i-OC4H9)(CH3)), methylisobutyloxymagnesium (Mg(OCH3 ... Magnesium chloride (Mg(OC2H5)(C2H5)), ethyl propyl oxymagnesium (Mg(OC3H7)(C2H5)), ethyl n-butyl oxymagnesium (Mg(OC4H9)(C2H5)), ethyl isobutyl oxymagnesium (Mg(i-OC4H9)(C2H5)), propyl methyl oxymagnesium (Mg(OCH3)(C3H7)), propyl ethyl oxymagnesium (Mg(OC2H5)(C3H7)), propyl propyl oxymagnesium (Mg(OC3H7)(C3 H7)), propyl n-butyloxymagnesium (Mg(OC4H9)(C3H7)), propyl isobutyloxymagnesium (Mg(i-OC4H9)(C3H7)), n-butylmethyloxymagnesium (Mg(OCH3)(C4H9)), n-butylethyloxymagnesium (Mg(OC2H5)(C4H9)), n-butylpropyloxymagnesium (Mg(OC3H7)(C4H9)), n-butyl n-butyloxymagnesium (Mg(OC4H9)(C4H9)), n-butyliso Examples include butyloxymagnesium (Mg(i-OC4H9)(C4H9)), isobutylmethyloxymagnesium (Mg(OCH3)(i-C4H9)), isobutylethyloxymagnesium (Mg(OC2H5)(i-C4H9)), isobutylpropyloxymagnesium (Mg(OC3H7)(i-C4H9)), isobutyl n-butyloxymagnesium (Mg(OC4H9)(i-C4H9)), and isobutylisobutyloxymagnesium (Mg(i-OC4H9)(i-C4H9)). Of these, butylethyloxymagnesium is preferred.

[0077] These magnesium compounds may be used alone or in combination of two or more without particular limitation.

[0078] When a combination is used, the molar ratio of the two types of magnesium compounds in the mixture of magnesium compounds is, for example, (0.25 to 4):1, preferably (0.5 to 3):1, and more preferably (1 to 2):1.

[0079] The method for obtaining a solution of magnesium compounds is described below.

[0080] In this method, a magnesium compound is dissolved in a first solvent in the presence of an alcohol to obtain a solution of the magnesium compound. Hereinafter, the first solvent will also be referred to as a solvent for dissolving the magnesium compound.

[0081] Examples of first solvents include C 6-12 Aromatic hydrocarbons, halogenated C 6-12 Aromatic hydrocarbons, C 5-12 Examples of the solvent include alkanes, esters, and ethers.

[0082] C 6-12 Examples of aromatic hydrocarbons include toluene, xylene, trimethylbenzene, ethylbenzene, and diethylbenzene.

[0083] Halogenated C 6-12 Examples of aromatic hydrocarbons include chlorotoluene, chloroethylbenzene, bromotoluene, and bromoethylbenzene.

[0084] C 5-12 Examples of alkanes include pentane, hexane, heptane, octane, nonane, and decane, of which hexane, heptane, and decane are preferred, with hexane being most preferred.

[0085] Examples of esters include methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and butyl butyrate.

[0086] Examples of ethers include diethyl ether, methyl ethyl ether, and tetrahydrofuran.

[0087] Among these, C 6-12 Aromatic hydrocarbons, C 5-12 Alkanes and tetrahydrofuran are preferred, with tetrahydrofuran being most preferred.

[0088] These solvents may be used alone or in combination of two or more in any proportion.

[0089] In the present invention, the term "alcohol" refers to a hydrocarbon chain (C 1-30 It refers to a compound in which one or more hydrogen atoms of an alcohol (such as a hydrocarbon) have been replaced with a hydroxyl group. The alcohol may be selected from aliphatic alcohols, aromatic alcohols, alicyclic alcohols, and mixtures thereof.

[0090] Examples of alcohols include C 1-30 Fatty alcohol (preferably C 1-30 Aliphatic monohydric alcohol), C 6-30 Aromatic alcohol (preferably C 6-30 Aromatic monohydric alcohol), C 4-30 Alicyclic alcohol (preferably C 4-30 Alicyclic monohydric alcohols). Among these, C 1-30 Aliphatic monohydric alcohol or C 2-8 Aliphatic monohydric alcohols are preferred, with ethanol and butanol being more preferred. Optionally, the alcohol may contain a halogen atom or a C 1-6 It may be substituted with one or more substituents selected from alkoxy groups.

[0091] C 1-30Examples of aliphatic alcohols include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, 2-methylpentanol, 2-ethylpentanol, 2-hexylbutanol, hexanol, and 2-ethylhexanol, of which ethanol, butanol, and 2-ethylhexanol are preferred.

[0092] C 6-30 Examples of aromatic alcohols include benzyl alcohol, phenylethyl alcohol, and methylbenzyl alcohol, of which phenylethyl alcohol is preferred.

[0093] C 4-30 Examples of alicyclic alcohols include cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, and propylcyclooctanol. Among these, cyclohexanol and methylcyclohexanol are preferred.

[0094] Examples of halogen-substituted alcohols include trichloromethanol, trichloroethanol, and trichlorohexanol, with trichloromethanol being preferred.

[0095] Examples of alkoxy-substituted alcohols include ethylene ethyl ether, ethylene n-butyl ether, and 1-butoxy-2-propanol, of which ethylene ethyl ether is preferred.

[0096] These alcohols may be used alone or in combination of two or more. When used in combination, the ratio of the two alcohols in the alcohol mixture may be determined arbitrarily without any particular limitation.

[0097] When preparing a solution of the magnesium compound, the magnesium compound may be added to a mixed solvent containing the first solvent and alcohol and dissolved therein. Alternatively, the magnesium compound may be added to the first solvent, and then simultaneously or subsequently, alcohol may be added to dissolve the magnesium compound. However, these orders are not limited to these. The preparation time for the magnesium compound solution (the dissolution time for the magnesium compound) is not particularly limited. It is generally 0.5 to 24 hours, preferably 4 to 24 hours. During the preparation process, stirring may be performed to promote dissolution of the magnesium compound. Stirring can be performed by any means. For example, a stirring blade may be used (the rotation speed is usually 10 to 1,000 rpm). If necessary, dissolution may be promoted by appropriate heating (however, the maximum temperature must be below the boiling points of the first solvent and alcohol).

[0098] In the present invention, the porous support is mixed with a solution of a magnesium compound to obtain a first mixed slurry. Optionally, the porous support has been subjected to a thermal activation treatment and / or a chemical activation treatment.

[0099] The porous carrier is described below.

[0100] In the present invention, examples of porous supports include organic or inorganic porous solids, which are supports conventionally used in the preparation of supported olefin polymerization catalysts.

[0101] Specific examples of organic porous solids include olefin homopolymers or copolymers, polyvinyl alcohol or copolymers thereof, cyclodextrin, (co)polyesters, (co)polyamides, vinyl chloride homopolymers or copolymers, acrylate homopolymers or copolymers, methacrylate homopolymers or copolymers, styrene homopolymers or copolymers, and partially crosslinked versions of these homopolymers or copolymers. Among these, partially crosslinked styrene polymers are preferred (for example, the degree of crosslinking is 2% or more but less than 100%).

[0102] In a preferred embodiment of the present invention, the surface of the organic porous solid preferably has one or more active functional groups. For example, the active functional groups are selected from hydroxy, primary amino, secondary amino, sulfonic acid, carboxyl, amide, N-monosubstituted amide, sulfamide, N-monosubstituted sulfamide, mercapto, imide, and hydrazide. Preferably, the active functional groups are one or more of carboxyl and hydroxy.

[0103] In one embodiment of the present invention, the organic porous solid is subjected to a thermal and / or chemical activation treatment before use.

[0104] In the present invention, before use, the organic porous solid may be subjected to only a thermal activation treatment, only a chemical activation treatment, or a combination of a thermal activation treatment and a chemical activation treatment in any order, without any particular limitation.

[0105] Thermal activation treatment can be performed according to conventional methods. For example, the organic porous solid is heated under reduced pressure or in an inert atmosphere. As used herein, "inert atmosphere" means that the gas contains only small amounts of components that can react with the organic porous solid, or none of these components at all. Examples of inert atmospheres include a nitrogen gas atmosphere and a rare gas atmosphere. Of these, a nitrogen gas atmosphere is preferred. Because organic porous solids have poor heat resistance, the thermal activation process should be carried out so as not to damage the structure and basic composition of the organic porous solid. Generally, the thermal activation temperature is 50 to 400°C, preferably 100 to 250°C. The thermal activation time is 1 to 24 hours, preferably 2 to 12 hours.

[0106] After the thermal / chemical activation process, the organic porous solid needs to be kept under positive pressure in an inert atmosphere for further use.

[0107] Examples of inorganic porous solids include refractory oxides of metals from Group IIA, IIIA, IVA, or IVB of the periodic table (such as silica (also known as silicon oxide or silica gel), alumina, magnesia, titania, zirconia, and thoria); any refractory composite oxides of these metals (such as silica-alumina, magnesia-alumina, titania-silica, titania-magnesia, and titania-alumina); clay; molecular sieves (such as ZSM-5 and MCM-41); mica; montmorillonite; bentonite; and diatomaceous earth. Further examples of inorganic porous solids include oxides obtained by the pyrohydrolysis of gaseous metal halides or gaseous silicon compounds (such as silica gel obtained by the pyrohydrolysis of silicon tetrachloride and alumina obtained by the pyrohydrolysis of aluminum trichloride).

[0108] As the inorganic porous solid, silica, alumina, magnesia, silica-alumina, magnesia-alumina, titania-silica, titania, molecular sieve, montmorillonite, etc. are preferred, with silica being particularly preferred.

[0109] In the present invention, more suitable silica can be produced. Alternatively, commercially available products may be used. Examples of commercially available products include Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Grace 2480D, Grace 2212D, Grace 2485, Davsion Syloid 245, and Aerosil 812 (all from Grace); ES70, ES70X, ES70Y, ES70W, ES757, EP10X, and EP11 (all from Ineos); and CS-2133 and MS-3040 (all from PQ).

[0110] In a preferred embodiment of the present invention, it is preferred that an active functional group such as hydroxyl is present on the surface of the inorganic porous solid.

[0111] In one embodiment of the present invention, the inorganic porous solid is subjected to a thermal and / or chemical activation treatment before use.

[0112] In the present invention, before use, the inorganic porous solid may be subjected to only a thermal activation treatment, only a chemical activation treatment, or a combination of a thermal activation treatment and a chemical activation treatment in any order, without any particular limitation.

[0113] Thermal activation treatment can be performed according to conventional methods. For example, the inorganic porous solid is heated under reduced pressure or in an inert atmosphere. As used herein, "inert atmosphere" means that the gas contains only small amounts of components that can react with the inorganic porous solid, or that the gas does not contain any of these components at all. Examples of inert atmospheres include a nitrogen gas atmosphere and a rare gas atmosphere. Of these, a nitrogen gas atmosphere is preferred. Generally, the thermal activation temperature is 200 to 800°C, preferably 400 to 700°C, and most preferably 400 to 650°C. The thermal activation time is, for example, 0.5 to 24 hours, preferably 2 to 12 hours, and most preferably 4 to 8 hours.

[0114] After the thermal / chemical activation process, the inorganic porous solid needs to be kept under positive pressure in an inert atmosphere for further use.

[0115] In the present invention, the organic or inorganic porous solid can be subjected to a chemical activation treatment according to a conventional method, for example, a process in which the organic or inorganic porous solid is chemically activated using a chemical activator.

[0116] In the present invention, a Group IVB metal compound is used as a chemical activator.

[0117] Examples of Group IVB metal compounds include one or more of Group IVB metal halides, Group IVB metal alkyl compounds, Group IVB metal alkoxy compounds, Group IVB metal halide alkyl compounds, and Group IVB metal halide alkoxy compounds.

[0118] As the Group IVB metal compound, a Group IVB metal halide is preferred, with TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4 and HfBr4 being more preferred, and TiCl4 and ZrCl4 being most preferred.

[0119] These Group IVB metal compounds may be used alone or in combination of two or more in any proportion.

[0120] If the chemical activator is liquid at room temperature, it may be used directly, i.e., a predetermined amount of the chemical activator is added dropwise to the organic or inorganic porous solid to be activated.

[0121] When the chemical activator is a solid at room temperature, it is preferable to use the chemical activator in a solution state for the convenience of measurement and operation. Of course, when the chemical activator is a liquid at room temperature, it may also be used in a solution state. There are no particular limitations on these.

[0122] The solvent used to prepare the solution of the chemical activator is not particularly limited as long as it can dissolve the chemical activator.

[0123] Specifically, C 5-12 Alkane, C 5-12 Cycloalkanes, halogenated C 5-12 Alkanes, halogenated C 5-12 Cycloalkane, C 6-12 Aromatic hydrocarbons, halogenated C 6-12Examples of aromatic hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, toluene, ethylbenzene, xylene, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, chlorotoluene, chloroethylbenzene, and chloroxylene. Among these, pentane, hexane, decane, cyclohexane, and toluene are preferred, and hexane and toluene are most preferred.

[0124] These solvents may be used alone or in combination of two or more in any proportion.

[0125] The concentration of the chemical activator in the solution is not particularly limited as long as the chemical activation is achieved with a predetermined amount of the chemical activator, and can be appropriately selected as needed. As described above, if the chemical activator is a liquid, it may be directly used for activation, or a solution of the chemical activator may be prepared and used.

[0126] Preferably, the molar concentration of the chemical activator in the solution is generally, but not limited to, 0.01 to 1.0 mol / L.

[0127] Examples of chemical activation processes include: ◆ When the chemical activator is a solid (e.g., zirconium tetrachloride) First, a solution of the chemical activator is prepared, and then the solution containing a predetermined amount of the chemical activator is added (preferably dropwise) to an organic or inorganic porous solid to allow the chemical activation reaction to occur. ◆ When the chemical activator is a liquid (e.g. titanium tetrachloride) A predetermined amount of chemical activator is added directly (preferably dropwise) to the organic or inorganic porous solid to cause the chemical activation reaction to occur. Alternatively, a solution of the chemical activator is prepared. The solution containing the predetermined amount of chemical activator is then added (preferably dropwise) to the organic or inorganic porous solid to be activated to cause the chemical activation reaction to occur.

[0128] Generally, the time for the chemical activation reaction is 0.5 to 24 hours, preferably 1 to 8 hours, and more preferably 2 to 6 hours. The reaction temperature is -30 to 60°C, and preferably -20 to 30°C. The chemical activation reaction is carried out with stirring, if necessary.

[0129] After the chemical activation reaction is completed, the chemically activated organic or inorganic porous solid is obtained through filtration, washing and drying.

[0130] In the present invention, filtration, washing, and drying may be carried out according to conventional methods. The solvent used for washing may be the same as the solvent used to dissolve the chemical activator. If necessary, the number of washings is generally 1 to 8 times, preferably 2 to 6 times, and most preferably 2 to 4 times.

[0131] Drying may be carried out according to a conventional method. Examples include drying with an inert gas, drying in a vacuum, and drying by heating in a vacuum. Drying with an inert gas or drying by heating in a vacuum is preferred. Drying by heating in a vacuum is most preferred. The drying temperature is generally from room temperature to 140°C. The drying time is generally from 2 to 20 hours, but is not limited to these ranges.

[0132] In the present invention, the amount of chemical activator used is an amount such that the amount of chemical activator (Group IVB metal element) per gram of porous carrier is 1 to 100 mmol, preferably 2 to 5 mmol, and more preferably 10 to 25 mmol.

[0133] In the present invention, the surface area of ​​the porous carrier is not particularly limited. Generally, it is 10 to 1000 m 2 / g, preferably 100 to 600m 2 / g (measured by the BET method). The pore volume of the porous carrier is generally 0.1 to 4 cm 3 / g, preferably 0.2 to 2 cm 3 / g (measured by nitrogen adsorption method). The average particle size is preferably 1 to 500 mm, more preferably 1 to 100 mm (measured by a laser particle size distribution analyzer).

[0134] In the present invention, the porous carrier may be in any shape (fine powder, granules, spheres, aggregates, etc.).

[0135] The porous support and the magnesium compound solution are mixed to obtain a first mixed slurry. Optionally, the porous support may be subjected to a thermal activation treatment and / or a chemical activation treatment.

[0136] In the present invention, the process of mixing the porous carrier with the magnesium compound solution may be carried out according to a conventional method without any particular limitations. For example, the following process may be mentioned. First, a weighed amount of the porous carrier is added to the magnesium compound solution, or a weighed amount of the magnesium compound solution is added to the porous carrier. The temperature at this time is the temperature at which the magnesium compound solution is prepared from room temperature. Next, the resulting substance is mixed for 0.1 to 8 hours, preferably 0.5 to 4 hours, and preferably 1 to 2 hours. Mixing is carried out while stirring as necessary.

[0137] In the present invention, the amount of the porous carrier used is an amount such that the mass ratio of the magnesium compound to the porous carrier is 1:(0.1 to 20), preferably 1:(0.5 to 10), and more preferably 1:(1 to 5). Here, the mass of the magnesium compound refers to the mass of the magnesium compound as a solid contained in the solution of the magnesium compound.

[0138] At this stage, the first mixed slurry is a slurry-like system. Although not essential, to ensure the uniformity of the system, it is preferable to allow the prepared first mixed slurry to stand in a sealed state for a predetermined period of time. This period is 2 to 48 hours, preferably 4 to 24 hours, and most preferably 6 to 18 hours.

[0139] In the present invention, the first mixed slurry is directly dried to obtain a solid product with good fluidity, which is the composite carrier of the present invention.

[0140] In this case, direct drying may be carried out according to a conventional method. Examples include drying in an inert gas atmosphere, drying in a vacuum, and drying by heating in a vacuum. Among these, drying by heating in a vacuum is preferred.

[0141] The drying temperature is generally 30 to 160° C., and preferably 60 to 130° C. The drying time is generally 2 to 24 hours, although it is not limited to these ranges.

[0142] Alternatively, in the present invention, a measured amount of precipitant may be added to the first mixed slurry to precipitate solids, thereby obtaining a composite support.

[0143] Precipitants are described below.

[0144] In the present invention, the term "precipitant" includes the common concept in the art, and refers to a chemically inert liquid that can reduce the solubility of a solid solute (such as a magnesium compound, a porous support, a nonmetallocene ligand, or a nonmetallocene complex) in a solution, thereby causing the solid to precipitate.

[0145] In the present invention, examples of the precipitant include a solvent that is a poor solvent for the solid solute to be precipitated (magnesium compound, porous support, nonmetallocene ligand, nonmetallocene complex, etc.) and a good solvent for the solvent in which the solid solute (magnesium compound, etc.) is dissolved. 5-12 Alkane, C5-12 Cycloalkanes, halogenated C 1-10 Alkanes, halogenated C 5-12 Examples include cycloalkanes.

[0146] C 5-12 Examples of alkanes include pentane, hexane, heptane, octane, nonane, and decane, of which hexane, heptane, and decane are preferred, with hexane being most preferred.

[0147] C 5-12 Examples of cycloalkanes include cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, of which cyclohexane is most preferred.

[0148] Halogenated C 1-10 Examples of alkanes include dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane.

[0149] Halogenated C 5-12 Examples of cycloalkanes include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.

[0150] These precipitants may be used alone or in combination of two or more in any proportion.

[0151] The precipitant may be added all at once or dropwise. Preferably, it is added all at once. In the precipitation process, stirring may be used to promote dispersion of the precipitant and to facilitate the final precipitation of the solid product. Stirring may be in any form (e.g., stirring with a stirring blade). The rotation speed is usually about 10 to 1000 rpm.

[0152] The amount of the precipitant used is not particularly limited. Generally, the volume ratio of the precipitant to the solvent dissolving the magnesium compound is 1:(0.2 to 5), preferably 1:(0.5 to 2), and more preferably 1:(0.8 to 1.5).

[0153] The temperature of the precipitating agent is not particularly limited. Generally, a temperature between room temperature and below the boiling point of any of the solvents and precipitating agents used is preferred. It is preferably 20 to 80°C, more preferably 40 to 60°C. However, it is not limited to these ranges. Generally, the temperature of the precipitation process is between room temperature and below the boiling point of any of the solvents and precipitating agents used. It is preferably 20 to 80°C, more preferably 40 to 60°C. The time of the precipitation process is 0.3 to 12 hours. This allows the solid product to be substantially completely precipitated. However, it is not limited to these ranges.

[0154] After complete precipitation, the obtained solid product is filtered, washed and dried. The processes of filtering, washing and drying are not particularly limited. Methods commonly used in the art may be used as needed.

[0155] If necessary, the number of washing steps is generally 1 to 6, and preferably 3 to 4. The solvent used for washing is preferably the same as the solvent used as the precipitant, but may be different.

[0156] Drying may be carried out according to a conventional method. Examples include drying with an inert gas, drying in a vacuum, and drying by heating in a vacuum. Drying with an inert gas or drying by heating in a vacuum is preferred. Drying by heating in a vacuum is most preferred.

[0157] The drying temperature is generally room temperature to 140°C. The drying time is generally 2 to 20 hours. However, this may vary depending on the solvent in which the magnesium compound is dissolved. For example, when the solvent for dissolving the magnesium compound is tetrahydrofuran, the drying temperature is generally about 80°C, and drying in a vacuum is required for 2 to 12 hours. When the solvent for dissolving the magnesium compound is toluene, the drying temperature is generally about 100°C, and drying in a vacuum is required for 4 to 24 hours.

[0158] In the present invention, the above-mentioned composite support thus obtained is brought into contact with a chemical treating agent selected from Group IVB metal compounds to obtain a modified composite support.

[0159] The chemical treatment is described below.

[0160] In the present invention, a Group IVB metal compound is used as the chemical treating agent.

[0161] Examples of Group IVB metal compounds include one or more of Group IVB metal halides, Group IVB metal alkyl compounds, Group IVB metal alkoxy compounds, Group IVB metal halide alkyl compounds, and Group IVB metal halide alkoxy compounds.

[0162] Examples of Group IVB metal halides, Group IVB metal alkyl compounds, Group IVB metal alkoxy compounds, halogenated Group IVB metal alkyl compounds, and halogenated Group IVB metal alkoxy compounds include compounds having a structure represented by the following general formula: M(OR 1 ) m X n R 2 4-m-n

[0163] During the ceremony, m is 0, 1, 2, 3 or 4. n is 0, 1, 2, 3 or 4. M is a Group IVB metal of the periodic table. Examples include titanium, zirconium, and hafnium. X is a halogen. Examples include F, Cl, Br and I. R 1 and R 2 are each independently, C 1-10 The alkyl group is selected from the group consisting of methyl, ethyl, propyl, n-butyl, and isobutyl. R 1 and R 2 may be the same or different.

[0164] Specific examples of halides of Group IVB metals include titanium tetrafluoride (TiF4), titanium tetrachloride (TiCl4), titanium tetrabromide (TiBr4), titanium tetraiodide (TiI4); zirconium tetrafluoride (ZrF4), zirconium tetrachloride (ZrCl4), zirconium tetrabromide (ZrBr4), zirconium tetraiodide (ZrI4); hafnium tetrafluoride (HfF4), hafnium tetrachloride (HfCl4), hafnium tetrabromide (HfBr4), and hafnium tetraiodide (HfI4).

[0165] Examples of alkyl compounds of Group IVB metals include tetramethyltitanium (Ti(CH3)4), tetraethyltitanium (Ti(CH3CH2)4), tetraisobutyltitanium (Ti(i-C4H9)4), tetra-n-butyltitanium (Ti(C4H9)4), triethylmethyltitanium (Ti(CH3)(CH3CH2)3), diethyldimethyltitanium (Ti(CH3)2(CH3CH2)2), trimethylethyltitanium (Ti(CH3)3(CH3CH2)), triisobutylmethyltitanium (Ti(CH3)(i-C4H9)3), bisisobutyldimethyltitanium (Ti(CH3)2(i-C4H9)2), and trimethylisobutyltitanium (Ti(CH3)3(i-C4H9)). , triisobutylethyltitanium (Ti(CH3CH2)(i-C4H9)3), bisisobutyldiethyltitanium (Ti(CH3CH2)2(i-C4H9)2), triethylisobutyltitanium (Ti(CH3CH2)3(i-C4H9)), tri-n-butylmethyltitanium (Ti(CH3)(C4H9)3), bis-n-butyldimethyltitanium (Ti(CH3)2(C4H9)2), trimethyl-n-butyltitanium (Ti(CH3)3(C4H9)), tri-n-butylethyltitanium (Ti(CH3CH2)(C4H9)3), bis-n-butyldiethyltitanium (Ti(CH3CH2)2(C4H9)2), triethyl-n-butyltitanium (Ti(CH3CH2)3(C4H9));Tetramethylzirconium (Zr(CH3)4), tetraethylzirconium (Zr(CH3CH2)4), tetraisobutylzirconium (Zr(i-C4H9)4), tetra-n-butylzirconium (Zr(C4H9)4), triethylmethylzirconium (Zr(CH3)(CH3CH2)3), diethyldimethylzirconium (Zr(CH3)2(CH3CH2)2), trimethylethylzirconium (Zr(CH3)3(CH3CH2)), triisobutylmethylzirconium (Zr(CH3)(i-C4H9)3), bisisobutyldimethylzirconium (Zr(CH3)2(i-C4H9)2), trimethylisobutylzirconium (Zr(CH3)3(i-C4H9)), triisobutylethyl ethyl zirconium (Zr(CH3CH2)(i-C4H9)3), bisisobutyldiethylzirconium (Zr(CH3CH2)2(i-C4H9)2), triethylisobutylzirconium (Zr(CH3CH2)3(i-C4H9)), tri-n-butylmethylzirconium (Zr(CH3)(C4H9)3), bis-n-butyldimethylzirconium (Zr(CH3)2(C4H9)2), trimethyl-n-butylzirconium (Zr(CH3)3(C4H9)), tri-n-butylethylzirconium (Zr(CH3CH2)(C4H9)3), bis-n-butyldiethylzirconium (Zr(CH3CH2)2(C4H9)2), triethyl-n-butylzirconium (Zr(CH3CH2)3(C4H9));Tetramethylhafnium (Hf(CH3)4), tetraethylhafnium (Hf(CH3CH2)4), tetraisobutylhafnium (Hf(i-C4H9)4), tetra-n-butylhafnium (Hf(C4H9)4), triethylmethylhafnium (Hf(CH3)(CH3CH2)3), diethyldimethylhafnium (Hf(CH3)2(CH3CH2)2), trimethylethylhafnium (Hf(CH3)3(CH3CH2)), triisobutylmethylhafnium (Hf(CH3)(i-C4H9)3), bisisobutyldimethylhafnium (Hf(CH3)2(i-C4H9)2), trimethylisobutylhafnium (Hf(CH3)3(i-C4H9)), triisobutylethylhafnium hafnium (Hf(CH3CH2)(i-C4H9)3), bisisobutyldiethylhafnium (Hf(CH3CH2)2(i-C4H9)2), triethylisobutylhafnium (Hf(CH3CH2)3(i-C4H9)), tri-n-butylmethylhafnium (Hf(CH3)(C4H9)3), bis-n-butyldimethylhafnium (Hf(CH3)2(C4H9)2), trimethyl-n-butylhafnium (Hf(CH3)3(C4H9)), tri-n-butylethylhafnium (Hf(CH3CH2)(C4H9)3), bis-n-butyldiethylhafnium (Hf(CH3CH2)2(C4H9)2), triethyl-n-butylhafnium (Hf(CH3CH2)3(C4H9));

[0166] Examples of alkoxy compounds of Group IVB metals include tetramethyloxytitanium (Ti(OCH3)4), tetraethyloxytitanium (Ti(OCH3CH2)4), tetraisobutyloxytitanium (Ti(i-OC4H9)4), tetra-n-butyloxytitanium (Ti(OC4H9)4), triethyloxymethyloxytitanium (Ti(OCH3)(OCH3CH2)3), diethyloxydimethyloxytitanium (Ti(OCH3)2(OCH3CH2)2), trimethyloxyethyloxytitanium (Ti(OCH3)3(OCH3CH2)), triisobutyloxymethyloxytitanium (Ti(OCH3)(i-OC4H9)3), bisisobutyloxydimethyloxytitanium (Ti(OCH3)2(i-OC4H9)2), trimethyloxyisobutyloxytitanium (Ti(OCH3)3(i-OC4H9)), triisobutyloxymethyloxytitanium (Ti(OCH3)(i-OC4H9)), Isobutyloxyethyloxytitanium (Ti(OCH3CH2)(i-OC4H9)3), bisisobutyloxydiethyloxytitanium (Ti(OCH3CH2)2(i-OC4H9)2), triethyloxyisobutyloxytitanium (Ti(OCH3CH2)3(i-OC4H9)), tri-n-butyloxymethyloxytitanium (Ti(OCH3)(OC4H9)3), bis-n-butyloxydimethyloxytitanium (Ti(OCH3)2(OC4H9)2), trimethyloxy-n-butyloxytitanium (Ti(OCH3)3(OC4H9)), tri-n-butyloxyethyloxytitanium (Ti(OCH3CH2)(OC4H9)3), bis-n-butyloxydiethyloxytitanium (Ti(OCH3CH2)2(OC4H9)2), triethyloxy-n-butyloxytitanium (Ti(OCH3CH2)3(OC4H9));Tetramethyloxyzirconium (Zr(OCH3)4), tetraethyloxyzirconium (Zr(OCH3CH2)4), tetraisobutyloxyzirconium (Zr(i-OC4H9)4), tetra-n-butyloxyzirconium (Zr(OC4H9)4), triethyloxymethyloxyzirconium (Zr(OCH3)(OCH3CH2)3), diethyloxydimethyloxyzirconium (Zr(OCH3)2(OC H3CH2)2), trimethyloxyethyloxyzirconium (Zr(OCH3)3(OCH3CH2)), triisobutyloxymethyloxyzirconium (Zr(OCH3)(i-OC4H9)3), bisisobutyloxydimethyloxyzirconium (Zr(OCH3)2(i-OC4H9)2), trimethyloxyisobutyloxyzirconium (Zr(OCH3)3(i-C4H9)), triisobutyloxyethyl Oxyzirconium (Zr(OCH3CH2)(i-OC4H9)3), bisisobutyloxydiethyloxyzirconium (Zr(OCH3CH2)2(i-OC4H9)2), triethyloxyisobutyloxyzirconium (Zr(OCH3CH2)3(i-OC4H9)), tri-n-butyloxymethyloxyzirconium (Zr(OCH3)(OC4H9)3), bis-n-butyloxydimethyloxyzirconium (Z r(OCH3)2(OC4H9)2), trimethyloxy n-butyloxy zirconium (Zr(OCH3)3(OC4H9)), tri n-butyloxyethyloxy zirconium (Zr(OCH3CH2)(OC4H9)3), bis n-butyloxydiethyloxy zirconium (Zr(OCH3CH2)2(OC4H9)2), triethyloxy n-butyloxy zirconium (Zr(OCH3CH2)3(OC4H9));Tetramethyloxyhafnium (Hf(OCH3)4), tetraethyloxyhafnium (Hf(OCH3CH2)4), tetraisobutyloxyhafnium (Hf(i-OC4H9)4), tetra-n-butyloxyhafnium (Hf(OC4H9)4), triethyloxymethyloxyhafnium (Hf(OCH3)(OCH3CH2)3), diethyloxydimethyloxyhafnium (Hf(OCH3)2(OCH3 CH2)2), trimethyloxyethyloxyhafnium (Hf(OCH3)3(OCH3CH2)), triisobutyloxymethyloxyhafnium (Hf(OCH3)(i-OC4H9)3), bisisobutyloxydimethyloxyhafnium (Hf(OCH3)2(i-OC4H9)2), trimethyloxyisobutyloxyhafnium (Hf(OCH3)3(i-OC4H9)), triisobutyloxyethyloxy Hafnium (Hf(OCH3CH2)(i-OC4H9)3), bisisobutyloxydiethyloxyhafnium (Hf(OCH3CH2)2(i-OC4H9)2), triethyloxyisobutyloxyhafnium (Hf(OCH3CH2)3(i-C4H9)), tri-n-butyloxymethyloxyhafnium (Hf(OCH3)(OC4H9)3), bis-n-butyloxydimethyloxyhafnium (Hf(OCH 3)2(OC4H9)2), trimethyloxy-n-butyloxyhafnium (Hf(OCH3)3(OC4H9)), tri-n-butyloxyethyloxyhafnium (Hf(OCH3CH2)(OC4H9)3), bis-n-butyloxydiethyloxyhafnium (Hf(OCH3CH2)2(OC4H9)2), triethyloxy-n-butyloxyhafnium (Hf(OCH3CH2)3(OC4H9));

[0167] Examples of alkyl compounds of Group IVB metal halides include trimethyl(chloro)titanium (TiCl(CH3)3), triethyl(chloro)titanium (TiCl(CH3CH2)3), triisobutyl(chloro)titanium (TiCl(i-C4H9)3), tri-n-butyl(chloro)titanium (TiCl(C4H9)3), dimethyl(dichloro)titanium (TiCl2(CH3)2), diethyl(dichloro)titanium (TiCl2(CH3CH2)2), bisisobutyl(dichloro)titanium (TiCl2(i-C4H9)2), tri-n-butyl(chloro)titanium (TiCl(C4H9)3), methyl(trichloro)titanium (Ti(CH3)Cl3), ethyl(trichloro)titanium (Ti(CH3CH2)Cl3), isobutyl(trichloro)titanium (Ti(i-C4H9)Cl3), n-butyl(trichloro)titanium ( Ti(C4H9)Cl3; trimethyl(bromo)titanium (TiBr(CH3)3), triethyl(bromo)titanium (TiBr(CH3CH2)3), triisobutyl(bromo)titanium (TiBr(i-C4H9)3), tri-n-butyl(bromo)titanium (TiBr(C4H9)3), dimethyl(dibromo)titanium (TiBr2(CH3)2), diethyl(dibromo)titanium (TiBr2(CH3CH2 )2), bisisobutyl(dibromo)titanium (TiBr2(i-C4H9)2), tri-n-butyl(bromo)titanium (TiBr(C4H9)3), methyl(tribromo)titanium (Ti(CH3)Br3), ethyl(tribromo)titanium (Ti(CH3CH2)Br3), isobutyl(tribromo)titanium (Ti(i-C4H9)Br3), n-butyl(tribromo)titanium (Ti(C4H9)Br3);Trimethyl(chloro)zirconium (ZrCl(CH3)3), triethyl(chloro)zirconium (ZrCl(CH3CH2)3), triisobutyl(chloro)zirconium (ZrCl(i-C4H9)3), tri-n-butyl(chloro)zirconium (ZrCl(C4H9)3), dimethyl(dichloro)zirconium (ZrCl2(CH3)2), diethyl(dichloro)zirconium (ZrCl2(CH3CH2)2), bis Isobutyl(dichloro)zirconium (ZrCl2(i-C4H9)2), tri-n-butyl(chloro)zirconium (ZrCl(C4H9)3), methyl(trichloro)zirconium (Zr(CH3)Cl3), ethyl(trichloro)zirconium (Zr(CH3CH2)Cl3), isobutyl(trichloro)zirconium (Zr(i-C4H9)Cl3), n-butyl(trichloro)zirconium (Zr(C4H9)Cl3); Trimethyl(bromo)zirconium (ZrBr(CH3)3), triethyl(bromo)zirconium (ZrBr(CH3CH2)3), triisobutyl(bromo)zirconium (ZrBr(i-C4H9)3), tri-n-butyl(bromo)zirconium (ZrBr(C4H9)3), dimethyl(dibromo)zirconium (ZrBr2(CH3)2), diethyl(dibromo)zirconium (ZrBr2(CH3CH2)2), bis Isobutyl(dibromo)zirconium (ZrBr2(i-C4H9)2), tri-n-butyl(bromo)zirconium (ZrBr(C4H9)3), methyl(tribromo)zirconium (Zr(CH3)Br3), ethyl(tribromo)zirconium (Zr(CH3CH2)Br3), isobutyl(tribromo)zirconium (Zr(i-C4H9)Br3), n-butyl(tribromo)zirconium (Zr(C4H9)Br3);Trimethyl(chloro)hafnium (HfCl(CH3)3), triethyl(chloro)hafnium (HfCl(CH3CH2)3), triisobutyl(chloro)hafnium (HfCl(i-C4H9)3), tri-n-butyl(chloro)hafnium (HfCl(C4H9)3), dimethyl(dichloro)hafnium (HfCl2(CH3)2), diethyl(dichloro)hafnium (HfCl2(CH3CH2)2), bisiso Butyl(dichloro)hafnium (HfCl2(i-C4H9)2), tri-n-butyl(chloro)hafnium (HfCl(C4H9)3), methyl(trichloro)hafnium (Hf(CH3)Cl3), ethyl(trichloro)hafnium (Hf(CH3CH2)Cl3), isobutyl(trichloro)hafnium (Hf(i-C4H9)Cl3), n-butyl(trichloro)hafnium (Hf(C4H9)Cl3); trime Thil(bromo)hafnium (HfBr(CH3)3), triethyl(bromo)hafnium (HfBr(CH3CH2)3), triisobutyl(bromo)hafnium (HfBr(i-C4H9)3), tri-n-butyl(bromo)hafnium (HfBr(C4H9)3), dimethyl(dibromo)hafnium (HfBr2(CH3)2), diethyl(dibromo)hafnium (HfBr2(CH3CH2)2), bisisobutyl (Dibromo)hafnium (HfBr2(i-C4H9)2), tri-n-butyl(bromo)hafnium (HfBr(C4H9)3), methyl(tribromo)hafnium (Hf(CH3)Br3), ethyl(tribromo)hafnium (Hf(CH3CH2)Br3), isobutyl(tribromo)hafnium (Hf(i-C4H9)Br3), n-butyl(tribromo)hafnium (Hf(C4H9)Br3);

[0168] Examples of alkoxy compounds of Group IVB metal halides include trimethyloxy(chloro)titanium (TiCl(OCH3)3), triethyloxy(chloro)titanium (TiCl(OCH3CH2)3), triisobutyloxy(chloro)titanium (TiCl(i-OC4H9)3), tri-n-butyloxy(chloro)titanium (TiCl(OC4H9)3), dimethyloxy(dichloro)titanium (TiCl2(OCH3)2), diethyloxy(dichloro)titanium Titanium dioxide (TiCl2(OCH3CH2)2), bisisobutyloxy(dichloro)titanium (TiCl2(i-OC4H9)2), tri-n-butyloxy(chloro)titanium (TiCl(OC4H9)3), methyloxy(trichloro)titanium (Ti(OCH3)Cl3), ethyloxy(trichloro)titanium (Ti(OCH3CH2)Cl3), isobutyloxy(trichloro)titanium (Ti(i-C4H9)Cl3), n-butyloxy(trichloro)titanium ( Ti(OC4H9)Cl3; trimethyloxy(bromo)titanium (TiBr(OCH3)3), triethyloxy(bromo)titanium (TiBr(OCH3CH2)3), triisobutyloxy(bromo)titanium (TiBr(i-OC4H9)3), tri-n-butyloxy(bromo)titanium (TiBr(OC4H9)3), dimethyloxy(dibromo)titanium (TiBr2(OCH3)2), diethyloxy(dibromo)titanium (TiBr2(OCH3CH 2)2), bisisobutyloxy(dibromo)titanium (TiBr2(i-OC4H9)2), tri-n-butyloxy(bromo)titanium (TiBr(OC4H9)3), methyloxy(tribromo)titanium (Ti(OCH3)Br3), ethyloxy(tribromo)titanium (Ti(OCH3CH2)Br3), isobutyloxy(tribromo)titanium (Ti(i-C4H9)Br3), n-butyloxy(tribromo)titanium (Ti(OC4H9)Br3);Trimethyloxy(chloro)zirconium (ZrCl(OCH3)3), triethyloxy(chloro)zirconium (ZrCl(OCH3CH2)3), triisobutyloxy(chloro)zirconium (ZrCl(i-OC4H9)3), tri-n-butyloxy(chloro)zirconium (ZrCl(OC4H9)3), dimethyloxy(dichloro)zirconium (ZrCl2(OCH3)2), diethyloxy(dichloro)zirconium (ZrCl2(OCH3CH2)2), bis isobutyloxy(dichloro)zirconium (ZrCl2(i-OC4H9)2), tri-n-butyloxy(chloro)zirconium (ZrCl(OC4H9)3), methyloxy(trichloro)zirconium (Zr(OCH3)Cl3), ethyloxy(trichloro)zirconium (Zr(OCH3CH2)Cl3), isobutyloxy(trichloro)zirconium (Zr(i-C4H9)Cl3), n-butyloxy(trichloro)zirconium (Zr(OC4H9)Cl3); Trimethyloxy(bromo)zirconium (ZrBr(OCH3)3), triethyloxy(bromo)zirconium (ZrBr(OCH3CH2)3), triisobutyloxy(bromo)zirconium (ZrBr(i-OC4H9)3), tri-n-butyloxy(bromo)zirconium (ZrBr(OC4H9)3), dimethyloxy(dibromo)zirconium (ZrBr2(OCH3)2), diethyloxy(dibromo)zirconium (ZrBr2(OCH3CH2)2), bis isobutyloxy(dibromo)zirconium (ZrBr2(i-OC4H9)2), tri-n-butyloxy(bromo)zirconium (ZrBr(OC4H9)3), methyloxy(tribromo)zirconium (Zr(OCH3)Br3), ethyloxy(tribromo)zirconium (Zr(OCH3CH2)Br3), isobutyloxy(tribromo)zirconium (Zr(i-C4H9)Br3), n-butyloxy(tribromo)zirconium (Zr(OC4H9)Br3);Trimethyloxy(chloro)hafnium (HfCl(OCH3)3), triethyloxy(chloro)hafnium (HfCl(OCH3CH2)3), triisobutyloxy(chloro)hafnium (HfCl(i-OC4H9)3), tri-n-butyloxy(chloro)hafnium (HfCl(OC4H9)3), dimethyloxy(dichloro)hafnium (HfCl2(OCH3)2), diethyloxy(dichloro)hafnium (HfCl2(OCH3CH2)2), bis(isobutyloxy)hafnium Isobutyloxy(dichloro)hafnium (HfCl2(i-OC4H9)2), tri-n-butyloxy(chloro)hafnium (HfCl(OC4H9)3), methyloxy(trichloro)hafnium (Hf(OCH3)Cl3), ethyloxy(trichloro)hafnium (Hf(OCH3CH2)Cl3), isobutyloxy(trichloro)hafnium (Hf(i-C4H9)Cl3), n-butyloxy(trichloro)hafnium (Hf(OC4H9)Cl3); trime Triethyloxy(bromo)hafnium (HfBr(OCH3)3), triethyloxy(bromo)hafnium (HfBr(OCH3CH2)3), triisobutyloxy(bromo)hafnium (HfBr(i-OC4H9)3), tri-n-butyloxy(bromo)hafnium (HfBr(OC4H9)3), dimethyloxy(dibromo)hafnium (HfBr2(OCH3)2), diethyloxy(dibromo)hafnium (HfBr2(OCH3CH2)2), bisisobutyloxy Examples include dibromooxyhafnium (HfBr2(i-OC4H9)2), tri-n-butyloxy(bromo)hafnium (HfBr(OC4H9)3), methylbromooxyhafnium (Hf(OCH3)Br3), ethylbromooxyhafnium (Hf(OCH3CH2)Br3), isobutyloxy(tribromo)hafnium (Hf(i-C4H9)Br3), and n-butyloxy(tribromo)hafnium (Hf(OC4H9)Br3);

[0169] Among the Group IVB metal compounds, the halides of Group IVB metals are preferred, with TiCl4, TiBr4, ZrCl4, ZrBr4, HfCl4 and HfBr4 being more preferred, and TiCl4 and ZrCl4 being most preferred.

[0170] These Group IVB metal compounds may be used alone or in combination of two or more in any proportion.

[0171] When the chemical treating agent is a liquid at room temperature, the chemical treating agent may be used directly for chemical treatment. When the chemical treating agent is a solid at room temperature, it is preferable to make the chemical treating agent in a solution state for ease of measurement and operation. Of course, even when the chemical treating agent is a liquid at room temperature, the chemical treating agent may be used in a solution state as needed. There are no particular limitations on these.

[0172] The solvent used when preparing the solution of the chemical treating agent is not particularly limited as long as it can dissolve the chemical treating agent and does not damage (e.g., does not dissolve) the carrier structure present in the composite carrier.

[0173] Specifically, C 5-12 Alkane, C 5-12 Cycloalkanes, halogenated C 5-12 Alkanes, halogenated C 5-12 Examples include cycloalkanes. Examples include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane < cycloheptane, cyclooctane, chloropentane, chlorohexane < chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane. Among these, pentane, hexane, decane, and cyclohexane are preferred, and hexane is most preferred.

[0174] These solvents may be used alone or in combination of two or more in any proportion.

[0175] The concentration of the chemical treating agent in the solution is not particularly limited as long as the chemical treatment is carried out with a predetermined amount of the chemical treating agent, and can be appropriately selected as needed. As mentioned above, if the chemical treating agent is a liquid, it may be used directly for treatment, or a solution of the chemical treating agent may be prepared and used.

[0176] Generally speaking, the molar concentration of the chemical treating agent in the solution is generally 0.01 to 1.0 mol / L (however, it is not limited to this range).

[0177] In the present invention, an example of a method for carrying out the chemical treatment is to bring the composite carrier into contact with a chemical treating agent in the presence of a solvent (also referred to as a chemical treatment solvent).

[0178] In the present invention, the chemical treatment solvent is not particularly limited as long as it can dissolve the chemical treatment agent and does not damage (does not dissolve) the carrier structure present in the composite carrier.

[0179] Specifically, the chemical treatment solvent is C 5-12 Alkane, C 5-12 Cycloalkanes, halogenated C 5-12 Alkanes, halogenated C 5-12 Examples of cycloalkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane. Among these, pentane, hexane, decane, and cyclohexane are preferred, and hexane is most preferred.

[0180] These solvents may be used alone or in combination of two or more in any proportion.

[0181] In the present invention, the amount of chemical treatment solvent used is 1 to 100 mL, preferably 2 to 40 mL per gram of composite carrier (however, it is not limited to these ranges). When using a chemical treatment agent in a solution state as described above, the amount of chemical treatment solvent used may be appropriately reduced without any particular limitation depending on the actual situation.

[0182] In the present invention, the amount of the chemical treating agent used is an amount such that the molar ratio of the composite carrier (as magnesium element) to the chemical treating agent (as Group IVB metal element) is 1:(0.01 to 1), preferably 1:(0.01 to 0.50), and more preferably 1:(0.10 to 0.30).

[0183] In one embodiment of the present invention, the chemical treatment is carried out by contacting the composite carrier with a chemical treating agent in the presence of a chemical treating solvent.

[0184] Examples of contact methods include the following: First, the composite carrier is added to the chemical treatment solvent while stirring. Next, the chemical treatment agent or a solution thereof is added simultaneously or continuously (preferably dropwise). After the addition is complete, the reaction is carried out while stirring. The temperature at this time is 0 to 100°C, preferably 20 to 80°C. The reaction time is not particularly limited, but is, for example, 0.5 to 8 hours, preferably 1 to 4 hours.

[0185] After the chemical treatment reaction is completed, the chemically treated product (modified composite carrier) is obtained through filtration, washing and drying.

[0186] In the present invention, filtration, washing, and drying may be carried out according to conventional methods. The solvent used for washing may be the same as the solvent used for the chemical treatment. If necessary, the number of washings is generally 1 to 8 times, preferably 2 to 6 times, and most preferably 2 to 4 times.

[0187] Drying may be carried out according to a conventional method. Examples include drying with an inert gas, drying in a vacuum, and drying by heating in a vacuum. Drying with an inert gas or drying by heating in a vacuum is preferred. Drying by heating in a vacuum is most preferred. The drying temperature is generally from room temperature to 140°C. The drying time is generally from 2 to 20 hours, but is not limited to these ranges.

[0188] In the present invention, the nonmetallocene complex is contacted with the modified composite support in the presence of a second solvent to obtain a supported nonmetallocene catalyst.

[0189] In the present invention, the term "nonmetallocene complex" refers to a single-center olefin polymerization catalyst. Unlike metallocene catalysts, this complex does not have a cyclopentadienyl group or its derivatives (such as a cyclopentadiene ring, a fluorene ring, or an indene ring) in its structure. When combined with a cocatalyst (such as those described below), this metal organic compound exhibits olefin polymerization catalytic activity. For this reason, the nonmetallocene complex is sometimes referred to as a nonmetallocene olefin polymerizable composite. This compound contains a central metal atom and one or more multidentate ligands (preferably tridentate or higher ligands) coordinately bonded to the central metal atom. The term "nonmetallocene ligand" refers to this multidentate ligand.

[0190] In the present invention, the nonmetallocene complex is selected from compounds represented by the following chemical structural formulas: [ka]

[0191] In the chemical structural formula, the ligands forming coordinate bonds with the central metal atom M include n X groups and m multidentate ligands (structural formula in parentheses). In the chemical structural formula of the multidentate ligand, the A, D, and E groups (coordinating groups) form coordinate bonds with the central metal atom M via the coordinating atoms (heteroatoms such as N, O, S, Se, and P) contained in these groups. In the present invention, the central metal atom M is also referred to as the active metal. The amount of catalyst is usually expressed as the amount of the central metal atom M contained in the nonmetallocene complex.

[0192] In the present invention, the sum of the negative charges carried by all the ligands (including the X group and the multidentate ligand) and the sum of the positive charges carried by the central metal atom M are balanced.

[0193] In a more specific embodiment, the nonmetallocene complex is selected from Compound (A) and Compound (B) represented by the following chemical structural formula: [ka]

[0194] In a more specific embodiment, the nonmetallocene complex is selected from compounds (A-1) to (A-4) and compounds (B-1) to (B-4) represented by the following chemical structural formulas. [ka]

[0195] In all of the above chemical structural formulas, q is 0m or 1. d is 0 or 1. m is 1, 2, or 3. M is a central metal atom and is a metal atom selected from Groups III to XI of the periodic table. Preferably, M is a metal atom of Group IVB. Examples include Ti(IV), Zr(IV), Hf(IV), Cr(III), Fe(III), Ni(II), Pd(II), and Co(II). n is 1, 2, 3, or 4, depending on the valence of the central metal atom M. X is a halogen atom, a hydrogen atom, a C1 to C2 30 Hydrocarbon groups, C1-C 30 A is selected from a substituted hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, and a tin-containing group. Multiple Xs may be the same or different. Multiple Xs may bond to each other or form a ring. A is an oxygen atom, a sulfur atom, a selenium atom, [ka] -NR 23 R 24 , -N(O)R 25 R 26 , [ka] -PR 28 R 29 , -P(O)R 30 OR 31 , sulfonyl, sulfinyl or -Se(O)R 39 (wherein N, O, S, Se and P are each a coordinating atom). B is a nitrogen atom, a nitrogen-containing group, a phosphorus-containing group or a C1-C 30 D is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a nitrogen-containing group, a phosphorus-containing group, a C1-C 30 E is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or cyano (-CN) (wherein N, O, S, Se, and P are each a coordinating atom). F is selected from a nitrogen atom, a nitrogen-containing group, an oxygen atom, a sulfur atom, a selenium atom, or a phosphorus-containing group (wherein N, O, S, Se, and P are each a coordinating atom). G is C1-C 30 Hydrocarbon groups, C1-C 30 Y is selected from an oxygen atom, a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, or a phosphorus-containing group (where N, O, S, Se, and P are each a coordinating atom). Z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or cyano (-CN) (where N, O, S, Se, and P are each a coordinating atom). An example of Z is -NR 23 R 24 , -N(O)R 25 R 26 , -PR 28 R 29 , -P(O)R 30 R 31 , -OR 34 , -SR 35 , -S(O)R 36 , -SeR 38 , -Se(O)R 39The symbol → represents a single bond or a double bond. The symbol -- represents a covalent bond or an ionic bond. The symbol - - - - represents a coordinate bond, a covalent bond, or an ionic bond.

[0196] R 1 ~R 4 and R 6 ~R 21 are each independently hydrogen, C1 to C 30 Hydrocarbon groups, C1-C 30 R is selected from substituted hydrocarbon groups (preferably halogenated hydrocarbon groups such as -CH2Cl, -CH2CH2Cl, etc.) or inert functional groups. 22 ~R 36 , R 38 and R 39 are each independently hydrogen, C1 to C 30 Hydrocarbon group or C1-C 30 Substituted hydrocarbon groups (preferably halogenated hydrocarbon groups such as -CH2Cl, -CH2CH2Cl, etc.) are selected from the group consisting of: a substituted hydrocarbon group; a halogenated hydrocarbon group; a substituted ... 1 and R 2 , R 6 and R 7 , R 7 and R 8 , R 8 and R 9 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 18 and R 19 , R 19 and R 20 , R 20 and R 21 , R 23 and R 24 , R 25 and R 26 Preferably, these adjacent groups form an aromatic ring. Examples of aromatic rings include an unsubstituted benzene ring and a benzene ring substituted with 1 to 4 substituents. The substituents are C1 to C630 Hydrocarbon group or C1-C 30 R is selected from substituted hydrocarbon groups (preferably halogenated hydrocarbon groups such as -CH2Cl, -CH2CH2Cl, etc.). 5 is the lone pair of nitrogen, hydrogen atom, C1-C 30 Hydrocarbon groups, C1-C 30 R is selected from a substituted hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group. 5 is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group, R 5 The N, O, S, P, and Se contained in are coordination atoms (coordinated to the central metal atom M).

[0197] In the context of the present invention, examples of inert functional groups include halogens, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C1-C 10 ester group, and nitro (-NO2). However, usually, C1 to C 30 Hydrocarbon groups and C1-C 30 Substituted hydrocarbon groups are excluded.

[0198] In the context of the present invention, according to the chemical structure of the polydentate ligand, the inert functional group has the following characteristics: (1) It does not inhibit the formation of a coordination bond between the A group, D group, E group, F group, Y group, or Z group and the central metal atom M. (2) The coordination ability with the central metal atom M is lower than that of the groups A, D, E, F, Y, and Z. Therefore, they do not replace the coordination existing between these groups and the central metal atom M.

[0199] In the present invention, in all the above-mentioned chemical structural formulas, depending on the specific situation, two or more adjacent groups may be bonded to each other to form a ring (R 21 group and Z group, R 13 Preferably, the ring has a heteroatom contained in the Z group or the Y group. 30Optionally, the aromatic heterocycle is a C1-C 30 Hydrocarbon groups and C1-C 30 It is substituted by one or more substituents selected from substituted hydrocarbon groups.

[0200] In the context of the present invention, halogen is selected from F, Cl, Br or I. The nitrogen-containing group is [ka] -NR 23 R 24 , -T-NR 23 R 24 or -N(O)R 25 R 26 The phosphorus-containing group is selected from [ka] -PR 28 R 29 , -P(O)R 30 R 31 or -P(O)R 32 (OR 33 The oxygen-containing group is selected from hydroxy, -OR 34 and -T-OR 34 The sulfur-containing group is selected from: 35 , -T-SR 35 , -S(O)R 36 or -T-SO2R 37 The selenium-containing group is selected from: -SeR 38 , -T-SeR 38 , -Se(O)R 39 or -T-Se(O)R 39 In these groups, T is selected from C1 to C 30 Hydrocarbon group or C1-C 30 R is selected from substituted hydrocarbon groups. 37 is hydrogen, C1 to C 30 Hydrocarbon group or C1-C 30 The alkyl group is selected from substituted hydrocarbon groups.

[0201] In relation to the present invention, C1 to C 30 The hydrocarbon group is C1 to C 30 Alkyl groups (preferably C1-C6 alkyl groups such as isobutyl), C7-C 30 Alkylaryl group (tolyl, dimethylphenyl, diisobutylphenyl, etc.) C7-C 30 Arylalkyl groups (benzyl, etc.) C3-C 30 Cycloalkyl groups, C2-C 30 Alkenyl groups, C2-C 30 Alkynyl groups, C6-C 30 Aryl groups (phenyl, naphthyl, anthracyl, etc.), C8-C 30 Fused ring group or C4-C 30 The heterocyclic group has 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms (pyridyl, pyrrolyl, furyl, thienyl, etc.).

[0202] In the present invention, C1 to C 30 The hydrocarbon group is usually C1 to C 30 Hydrocarbon diyl (divalent group, C1-C 30 Also called hydrocarbylene group) or C1-C 30 It represents a hydrocarbon triyl (trivalent group). These will depend on the specific conditions of the group to which the hydrocarbon group is combined, and this will be clear to those skilled in the art.

[0203] In relation to the present invention, C1 to C 30 A substituted hydrocarbon group is a C1-C group having one or more inert substituents. 30 The so-called inert substituents are the above-mentioned coordinating groups (A group, D group, E group, F group, Y group, and Z group). 5 The substituents represent substituents that do not substantially inhibit the formation of a coordination bond between the central metal atom M and a halogen atom (which may contain a C1-C1 group). In other words, due to the limitations imposed by the chemical structure of the polydentate ligands described herein, these substituents have no ability or possibility of forming a coordination bond with the central metal atom M through a coordination reaction (due to the influence of steric hindrance, etc.). Generally speaking, inert substituents are halogens or C1-C1 30It is selected from alkyl (preferably C1-C6 alkyl such as isobutyl).

[0204] In the context of the present invention, the boron-containing group is BF4 - , (C6F5)4B - or (R 40 BAr3) - The aluminum-containing group is selected from alkyl aluminum, AlPh4 - , AlF4 - , AlCl4 - , AlBr4 - ,AlI4 - or R 41 AlAr3 - The silicon-containing group is selected from: 42 R 43 R 44 or -T-SiR 45 The germanium-containing group is selected from: -GeR 46 R 47 R 48 or -T-GeR 49 The tin-containing group is selected from: -SnR 50 R 51 R 52 , -T-SnR 53 or -T-Sn(O)R 54 In the formula, Ar is selected from C6 to C 30 R represents aryl. 40 ~R 54 are each independently hydrogen, the above-mentioned C1 to C 30 Hydrocarbon groups or the above C1-C 30 substituted hydrocarbon groups. The above groups may be the same or different. Adjacent groups may be bonded to each other to form a bond or a ring. T is as defined above.

[0205] Examples of nonmetallocene complexes include the following compounds: [ka] JPEG0007775318000009.jpg201169JPEG0007775318000010.jpg195169

[0206] Preferably, the nonmetallocene complex is selected from the following compounds: [ka]

[0207] More preferably, the nonmetallocene complex is selected from the following compounds: [ka]

[0208] More preferably, the nonmetallocene complex is selected from the following compounds: [ka]

[0209] These nonmetallocene complexes may be used alone or in combination of two or more in any ratio.

[0210] In the present invention, the polydentate ligand contained in the nonmetallocene complex is not a diethyl compound, which is a compound that has been conventionally used as an electron donor compound in the technical field.

[0211] The nonmetallocene complex or the polydentate ligand can be prepared by any preparation method known to those skilled in the art. For specific descriptions of the preparation method, see WO03 / 010207, Chinese Patent No. ZL01126323.7, Chinese Patent No. ZL02110844.7, etc. (these documents are incorporated herein by reference in their entirety).

[0212] In the present invention, for the convenience of measurement and operation, the nonmetallocene complex is used in the form of a solution, if necessary.

[0213] The solvent used to prepare the solution of the nonmetallocene complex is not particularly limited as long as it can dissolve the nonmetallocene complex. 6-12 Aromatic hydrocarbons, halogenated C 6-12 Aromatic hydrocarbons, halogenated C 1-10 Examples of suitable alkane, ester, and ether compounds include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, dichloromethane, dichloroethane, ethyl acetate, and tetrahydrofuran. 6-12 The aromatic hydrocarbons, dichloromethane and tetrahydrofuran are preferred.

[0214] These solvents may be used alone or in combination of two or more in any proportion.

[0215] When dissolving the nonmetallocene complex, stirring may be performed as necessary. The stirring speed is generally 10 to 500 rpm.

[0216] In the present invention, the ratio of the nonmetallocene complex to the solvent is generally conveniently set to 0.02 to 0.30 g / mL, preferably 0.05 to 0.15 g / mL (however, it is not limited to these ranges).

[0217] An example of a method for contacting the nonmetallocene complex with the modified composite support in the presence of the second solvent is as follows.

[0218] First, the modified composite support and the nonmetallocene complex are contacted (reacted through contact) in the presence of a second solvent to obtain a second mixed slurry.

[0219] When preparing the second mixed slurry, the method and order of contacting the modified composite support and the nonmetallocene complex (and the second solvent) are not particularly limited. For example, the modified composite support and the nonmetallocene complex may be first mixed, and then the second solvent may be added to the resulting mixture. Alternatively, the nonmetallocene complex may be dissolved in the second solvent to prepare a nonmetallocene complex solution, and then the modified composite support and the nonmetallocene complex solution may be mixed. Of these, the latter method is preferred.

[0220] Furthermore, when preparing the second mixed slurry, the temperature at which the modified composite support and the nonmetallocene complex are contacted and reacted in the presence of the second solvent may be from room temperature to a temperature lower than the boiling point of either of the solvents used. The time for contact and reaction may be 0.5 to 24 hours, preferably 1 to 8 hours, and more preferably 2 to 6 hours. If necessary, the contact may be carried out with stirring.

[0221] The second mixed slurry obtained at this time is a slurry-like system. Although not essential, in order to ensure the uniformity of the system, it is preferable to leave the second mixed slurry in a sealed state after preparation. The time for leaving it is 2 to 48 hours, preferably 4 to 24 hours, and most preferably 6 to 18 hours.

[0222] In the present invention, the second solvent (hereinafter also referred to as a solvent for dissolving the nonmetallocene complex) used when preparing the second mixed slurry or when contacting the modified composite support with the nonmetallocene complex is not particularly limited as long as it can dissolve the nonmetallocene complex.

[0223] Examples of second solvents include C 6-12 Aromatic hydrocarbons, halogenated C 6-12 Aromatic hydrocarbons, C 5-12 Alkanes, halogenated C 1-10Examples of the alkane and ether include one or more of toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, hexane, dichloromethane, dichloroethane, and tetrahydrofuran. 6-12 The aromatic hydrocarbons, dichloromethane and tetrahydrofuran are preferred, with dichloromethane being most preferred.

[0224] These solvents may be used alone or in combination of two or more in any proportion.

[0225] When preparing the second mixed slurry or the nonmetallocene complex solution, stirring may be performed as necessary. The stirring speed is generally 10 to 500 rpm.

[0226] In the present invention, the amount of the second solvent used is not particularly limited as long as it is an amount sufficient to bring the modified composite carrier and the nonmetallocene complex into contact with each other. For example, the ratio of the nonmetallocene complex to the second solvent is generally 0.01 to 0.25 g / mL, preferably 0.05 to 0.16 g / mL (however, it is not limited to these ranges).

[0227] In one embodiment of the present invention, the second mixed slurry is directly dried to obtain a solid product with good flowability, which is the supported nonmetallocene catalyst of the present invention.

[0228] In one embodiment of the present invention, the second mixed slurry does not need to be dried, and the undried second mixed slurry may be used directly as a supported nonmetallocene catalyst.

[0229] In this case, direct drying is carried out according to a conventional method. Examples include drying in an inert gas atmosphere, drying in a vacuum, and heat drying in a vacuum. Of these, heat drying in a vacuum is preferred. The drying temperature is generally 5 to 15°C lower than the boiling point of any of the solvents contained in the mixed slurry (generally 30 to 160°C, preferably 60 to 130°C). The drying time is generally 2 to 24 hours, although it is not limited to these ranges.

[0230] In the present invention, the amount of the first solvent used per 1 mol of the magnesium compound is 75 to 400 mL, preferably 150 to 300 mL, and more preferably 200 to 250 mL.

[0231] In the present invention, the amount of alcohol used is such that the molar ratio of the magnesium compound (as elemental magnesium) to the alcohol is 1:(0.02 to 4.00), preferably 1:(0.05 to 3.00), and more preferably 1:(0.10 to 2.50).

[0232] In the present invention, the amount of the porous carrier used is an amount such that the mass ratio of the magnesium compound (solid magnesium compound) to the porous carrier is 1:(0.1 to 20), preferably 1:(0.5 to 10), and more preferably 1:(1 to 5).

[0233] In the present invention, the amount of precipitant used is such that the volume ratio of the precipitant to the first solvent is 1:(0.2 to 5), preferably 1:(0.5 to 2), and more preferably 1:(0.8 to 1.5).

[0234] In the present invention, the amount of chemical treating agent used is an amount such that the molar ratio of the composite carrier (as magnesium element) to the chemical treating agent (as Group IVB metal element) is 1:(0.01 to 1), preferably 1:(0.01 to 0.50), and more preferably 1:(0.10 to 0.30).

[0235] In the present invention, the amount of the nonmetallocene complex used is such that the molar ratio of the composite support (as magnesium element) to the nonmetallocene complex is 1:(0.01 to 1), preferably 1:(0.04 to 0.4), and more preferably 1:(0.08 to 0.2).

[0236] As will be understood by those skilled in the art, the above-mentioned production process is preferably carried out under substantially anhydrous and oxygen-free conditions. As used herein, "substantially anhydrous and oxygen-free" means that the water and oxygen contents in the system are always less than 100 ppm. After production of the supported nonmetallocene catalyst of the present invention, it is usually necessary to temporarily store the catalyst in a sealed condition under a slightly positive pressure of an inert gas (such as nitrogen gas, argon gas, or helium gas).

[0237] In the present invention, unless otherwise specified, the amount of supported nonmetallocene catalyst is expressed in terms of the amount of active Group IVB metal element.

[0238] In the present invention, the cocatalyst is selected from aluminoxanes, alkylaluminums, haloalkylaluminums, and mixtures thereof.

[0239] Examples of aluminoxanes include linear aluminoxanes represented by the following general formula (III-1) and cyclic aluminoxanes represented by the following general formula (III-2). [ka]

[0240] In the above general formula, the R groups are the same or different, preferably the same. Each R group is independently selected from C1 to C8 alkyl, preferably methyl, ethyl, propyl, butyl, and isobutyl, and most preferably methyl. n is an integer from 1 to 50, preferably 10 to 30.

[0241] As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, methylaluminoxane and isobutylaluminoxane are more preferred, and methylaluminoxane is most preferred.

[0242] These aluminoxanes may be used alone or in combination of two or more in any proportion.

[0243] Examples of alkylaluminum include compounds represented by the following general formula (III). Al(R)3(III)

[0244] wherein the R groups are the same or different, preferably the same, and each R group is independently selected from C1 to C8 alkyl, preferably methyl, ethyl, propyl, butyl, and isobutyl, and most preferably methyl.

[0245] Specific examples of alkyl aluminum include trimethyl aluminum (Al(CH3)3), triethyl aluminum (Al(CH3CH2)3), tri-n-propyl aluminum (Al(C3H7)3), triisopropyl aluminum (Al(i-C3H7)3), triisobutyl aluminum (Al(i-C4H9)3), tri-n-butyl aluminum (Al(C4H9)3), and triisopentyl aluminum (Al(i-C5H 11 )3), tri-n-pentyl aluminum (Al(CH 11 )3), tri-n-hexylaluminum (Al(CH 13 )3), triisohexylaluminum (Al(i-CH 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2), and dimethylethylaluminum (Al(CH3CH2)(CH3)2). Among these, trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum are preferred, and triethylaluminum and triisobutylaluminum are most preferred.

[0246] These alkylaluminums may be used alone or in combination of two or more in any proportion.

[0247] Examples of haloalkylaluminum include compounds represented by the following general formula (III'). Al(R) n X 3-n (III')

[0248] In the formula, R groups are the same or different, and preferably the same. Each R group is independently selected from C1 to C8 alkyl, preferably methyl, ethyl, propyl, butyl, and isobutyl, and most preferably methyl. X represents F, Cl, Br, or I. n represents 1 or 2.

[0249] Specific examples of haloalkylaluminum include dimethyl(chloro)aluminum (Al(CH3)2Cl), methyl(dichloro)aluminum (Al(CH3)Cl2), diethyl(chloro)aluminum (Al(CH3CH2)2Cl), ethyl(dichloro)aluminum (Al(CH3CH2)Cl2), dipropyl(chloro)aluminum (Al(C3H7)2Cl), propyl(dichloro)aluminum (Al(C3H7)Cl2)), di-n-butyl(chloro)aluminum (Al(C4H9)2Cl), n-butyl(dichloro)aluminum (Al(C4H9)Cl2), diisobutyl(chloro)aluminum (Al(i-C4H9)2Cl), isobutyl(dichloro)aluminum (Al(i-C4H9)Cl2), and di-n-pentyl(chloro)aluminum (Al(C5H 11 )2Cl), n-pentyl(dichloro)aluminum (Al(CH 11 )Cl2), diisopentyl(chloro)aluminum (Al(i-CH 11 )2Cl), isopentyl(dichloro)aluminum (Al(i-CH 11 )Cl2), di-n-hexyl(chloro)aluminum (Al(CH 13)2Cl), n-hexyl(dichloro)aluminum (Al(CH 13 )Cl2), diisohexyl(chloro)aluminum (Al(i-CH 13 )2Cl), isohexyl(dichloro)aluminum (Al(i-CH 13 )Cl2), methylethyl(chloro)aluminum (Al(CH3)(CH3CH2)Cl), methylpropyl(chloro)aluminum (Al(CH3)(C3H7)Cl), methyl n-butyl(chloro)aluminum (Al(CH3)(C4H9)Cl), methyl isobutyl(chloro)aluminum (Al(CH3)(i-C4H9)Cl), ethylpropyl(chloro)aluminum (Al(CH2CH3)(C3H7)Cl), ethyl n-butyl(chloro)aluminum (AlCH2CH3)(C4H9)Cl), and methyl isobutyl(chloro)aluminum (Al(CH2CH3)(i-C4H9)Cl). Among these, diethyl(chloro)aluminum, ethyl(dichloro)aluminum, di-n-butyl(chloro)aluminum, n-butyl(dichloro)aluminum, diisobutyl(chloro)aluminum, isobutyl(dichloro)aluminum, di-n-hexyl(chloro)aluminum, and n-hexyl(dichloro)aluminum are preferred, diethyl(chloro)aluminum, ethyl(dichloro)aluminum, and di-n-hexyl(chloro)aluminum are more preferred, and diethyl(chloro)aluminum is most preferred.

[0250] These haloalkylaluminums may be used alone or in combination of two or more in any proportion.

[0251] In the present invention, the promoter may be used alone or in combination of two or more kinds in any ratio, without any particular limitation.

[0252] In the present invention, unless otherwise specified, the amount of promoter is expressed in terms of the content of aluminum element.

[0253] In the present invention, the polymerization solvent for the production of ultra-high molecular weight polyethylene is selected from an alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure at 20°C of 20 to 150 kPa (preferably 40 to 110 kPa).

[0254] In the present invention, examples of alkane solvents having a boiling point of 5 to 55°C include 2,2-dimethylpropane (also known as neopentane; boiling point: 9.5°C, saturated vapor pressure at 20°C: 146.63 kPa), 2-methylbutane (also known as isopentane; boiling point: 27.83°C, saturated vapor pressure at 20°C: 76.7 kPa), n-pentane (boiling point: 36.1°C, saturated vapor pressure at 20°C: 56.5 kPa), and cyclopentane (boiling point: 49.26°C, saturated vapor pressure at 20°C: 34.6 kPa). Preferably, the boiling point of the alkane solvent is 25 to 52°C.

[0255] A mixed alkane solvent having a saturated vapor pressure of 20 to 150 kPa (preferably 40 to 110 kPa) at 20°C is a mixed solvent obtained by mixing different types of alkane solvents in a specific ratio. Examples include a mixed solvent obtained by mixing hexane and its isomers with pentane and its isomers, and an alkane mixture obtained by removing a certain distillation range from a solvent distillation unit. A mixed solvent composed of hexane and its isomers is preferred. Specific examples include a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of n-pentane and neopentane, a combination of isopentane and cyclopentane, a combination of neopentane and cyclopentane, a combination of n-hexane and cyclopentane, a combination of n-hexane and n-pentane, a combination of n-pentane, isopentane and cyclopentane, and a combination of n-pentane, n-hexane and isopentane. However, there are no limitations as long as the saturated vapor pressure of the mixed alkane at 20° C. is 20 to 150 kPa (preferably 40 to 110 kPa).

[0256] In one embodiment of the present invention, the mixed alkane solvent, which has a saturated vapor pressure of 20 to 150 kPa (preferably 40 to 110 kPa) at 20°C, is preferably a solvent obtained by mixing two or more alkanes selected from n-pentane, isopentane, neopentane, and cyclopentane. More preferably, the mixed alkane solvent is a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of isopentane and cyclopentane, a combination of neopentane and cyclopentane, a combination of neopentane and n-pentane, a combination of n-pentane, isopentane and cyclopentane, or a combination of neopentane, isopentane and n-pentane. Regarding the ratio of each alkane in the mixed alkane, for example, when two types of alkane solvents are mixed, the molar ratio thereof may be (0.01 to 100):1, and preferably (0.1 to 10):1. When three types of alkane solvents are mixed, the molar ratio thereof may be (0.01-100):(0.01-100):1, and preferably (0.1-10):(0.1-10):1. However, the saturated vapor pressure of the resulting mixed alkane solvent at 20°C is 20-150 kPa (preferably 40-110 kPa). In one embodiment of the present invention, only an alkane solvent having a boiling point of 5-55°C or a mixed alkane solvent having a saturated vapor pressure of 20-150 kPa at 20°C is used as the polymerization solvent.

[0257] In the method for producing ultra-high molecular weight polyethylene of the present invention, the polymerization temperature for the slurry polymerization of ethylene is 50 to 100°C, preferably 60 to 90°C. If ethylene is slurry polymerized at a high polymerization temperature, a solvent with a high boiling point can be used. Conversely, if ethylene is slurry polymerized at a low polymerization temperature, a solvent with a low boiling point can be used. It is known that in the slurry polymerization of ethylene, provided that the polymerization pressure, main catalyst, cocatalyst, solvent, and other conditions are similar or equivalent, as the polymerization temperature increases within the polymerization temperature range described herein, the viscosity-average molecular weight of the resulting ultra-high molecular weight polyethylene initially increases and then decreases. Therefore, in the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene obtained by the slurry polymerization of ethylene can be adjusted and controlled by the polymerization temperature.

[0258] In the method for producing ultra-high molecular weight polyethylene of the present invention, the polymerization pressure is 0.4 to 4.0 MPa, preferably 1.0 to 3.0 MPa, and more preferably 1.5 to 3.0 MPa. If ethylene is slurry polymerized at a high polymerization temperature, the polymerization pressure may be lowered. Conversely, if ethylene is slurry polymerized at a low polymerization temperature, the polymerization pressure may be higher. In the slurry polymerization of ethylene, provided that the polymerization temperature, main catalyst, cocatalyst, solvent, and other conditions are similar or equivalent, within the polymerization pressure range described herein, as the polymerization pressure increases, the viscosity-average molecular weight of the resulting ultra-high molecular weight polyethylene initially increases and then decreases. Therefore, in the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene obtained by the slurry polymerization of ethylene can also be adjusted and controlled by the polymerization pressure.

[0259] In the present invention, an alkane solvent with a boiling point of 5 to 55°C or a mixed alkane solvent with a saturated vapor pressure of 20 to 150 kPa at 20°C is used as the polymerization solvent. This allows for the production of ultra-high molecular weight polyethylenes with different viscosity-average molecular weights by ethylene slurry polymerization, and also provides greater flexibility in selecting the viscosity-average molecular weight. For example, the use of an alkane solvent with a low boiling point (e.g., n-pentane, isopentane, cyclopentane) or a mixed alkane solvent with a high saturated vapor pressure at 20°C (e.g., a combination of n-pentane and neopentane, or a combination of isopentane and neopentane) facilitates heat removal in the ethylene slurry polymerization reaction, allowing for a higher polymerization pressure and a lower polymerization temperature. On the other hand, the use of an alkane solvent with a high boiling point or a mixed alkane solvent with a low saturated vapor pressure at 20°C allows for a lower polymerization pressure and a higher polymerization temperature, thereby effectively removing the heat of the polymerization reaction.

[0260] In one embodiment of the present invention, polyethylene having a very high viscosity average molecular weight is provided. The viscosity average molecular weight of the polyethylene having a very high viscosity average molecular weight is 150 to 1000 × 10 4 g / mol. The bulk density is 0.30-0.55 g / cm 3 The true density is 0.910 to 0.950 g / cm 3 The titanium content is 0-3 ppm. The calcium content is 0-5 ppm. The magnesium content is 0-10 ppm. The aluminum content is 0-30 ppm. The chlorine content is 0-50 ppm. The total ash content is less than 200 ppm. The melting point is 140-152°C. The crystallinity is 40-70%. The tensile yield strength is greater than 22 MPa. The tensile strength at break is greater than 32 MPa. The elongation at break is greater than 350%. The impact strength is 70 kJ / m 2 The Young's modulus is greater than 300 MPa.

[0261] In one embodiment of the present invention, polyethylene having a very high viscosity average molecular weight is provided. The viscosity average molecular weight is 300 to 800 × 10 4 g / mol. The bulk density is 0.33 to 0.52 g / cm3 The true density is 0.915 to 0.945 g / cm 3 The titanium content is 0-2 ppm. The calcium content is 0-3 ppm. The magnesium content is 0-5 ppm. The aluminum content is 0-20 ppm. The chlorine content is 0-30 ppm. The total ash content is less than 150 ppm. The melting point is 142-150°C. The crystallinity is 45-65%. The tensile yield strength is greater than 25 MPa. The tensile strength at break is greater than 35 MPa. The elongation at break is greater than 400%. The impact strength is 75 kJ / m 2 The Young's modulus is greater than 350 MPa.

[0262] In one embodiment of the present invention, an ethylene copolymer having a very high viscosity average molecular weight is provided. The viscosity average molecular weight of the ultra-high molecular weight ethylene copolymer is 150 to 800 × 10 4 g / mol. The bulk density is 0.30-0.55 g / cm 3 The true density is 0.900 to 0.950 g / cm 3 The molar insertion ratio of the comonomer is 0.05-4.0%. The titanium content is 0-3 ppm. The calcium content is 0-5 ppm. The magnesium content is 0-10 ppm. The aluminum content is 0-30 ppm. The chlorine content is 0-50 ppm. The total ash content is less than 200 ppm. The melting point is 140-152°C. The crystallinity is 40-70%. The tensile modulus is greater than 250 MPa.

[0263] In one embodiment of the present invention, an ethylene copolymer having a very high viscosity average molecular weight is provided. The viscosity average molecular weight of the ethylene copolymer is 300 to 700 × 10 4 g / mol. The bulk density is 0.33 to 0.52 g / cm 3 The true density is 0.905 to 0.945 g / cm 3The molar insertion ratio of the comonomer is 0.10-2.0%. The titanium content is 0-2 ppm. The calcium content is 0-3 ppm. The magnesium content is 0-5 ppm. The aluminum content is 0-20 ppm. The chlorine content is 0-30 ppm. The total ash content is less than 150 ppm. The melting point is 142-150°C. The crystallinity is 45-65%. The tensile modulus is greater than 280 MPa.

[0264] One embodiment of the present invention provides a method for producing polyethylene with a very high viscosity average molecular weight by polymerization. In this production method, ethylene and an optional comonomer are slurry polymerized. A supported nonmetallocene catalyst is used as the main catalyst. One or more of aluminoxane, alkylaluminum, and haloalkylaluminum are used as the cocatalyst. An alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure at 20°C of 20 to 150 kPa is used as the polymerization solvent. The conditions for the slurry polymerization of ethylene are a polymerization temperature of 50 to 100°C and a polymerization pressure of 0.4 to 4.0 MPa. The polymerization activity of the ethylene slurry is 2 x 10 polyethylene per 1 g of main catalyst. 4 It is over g.

[0265] In one embodiment of the present invention, there is provided a method for producing polyethylene having a very high viscosity average molecular weight by polymerization. In this production method, ethylene is slurry polymerized. The conditions for the slurry polymerization of ethylene are a polymerization temperature of 60 to 90°C and a polymerization pressure of 1.0 to 3.0 MPa. The polymerization activity of the ethylene slurry is 3 x 10 polyethylene per 1 g of main catalyst. 4 When a comonomer is present, the molar ratio of the comonomer to the active metal catalyst is (20-400):1.

[0266] In the method for producing ultra-high molecular weight polyethylene of the present invention, the reactor used for the slurry polymerization of ethylene is not particularly limited. However, the reactor must be one that allows ethylene and optional comonomers to come into contact with the main catalyst and cocatalyst in a solvent at the polymerization pressure and polymerization temperature described above. To effectively avoid adhesion and aggregation of materials, a tank-type ethylene slurry stirred reactor may be used. The stirring speed in the stirred tank is not particularly limited. As long as the slurry in the reactor can be dispersed normally, the stirring rotation speed varies depending on the volume of the reactor. Generally, the smaller the reactor volume, the faster the stirring rotation speed is required. The stirring rotation speed is 10 to 1,000 rpm, preferably 20 to 500 rpm.

[0267] In the method for producing ultra-high molecular weight polyethylene of the present invention, the polymerization time is not particularly limited, provided that the polymerization time is set so that the polymerization activity of the main catalyst of the present invention in the slurry polymerization of ethylene is 2×10 polyethylene per 1 g of the main catalyst. 4 g (preferably 3 × 10 4 g, most preferably greater than 4 × 10 4 g).

[0268] In the present invention, the main catalyst (supported nonmetallocene catalyst) and the co-catalyst (one or more of aluminoxane, alkylaluminum, and haloalkylaluminum) can be added to the polymerization reaction system in the following manner. ◆ Add the main catalyst first, then the promoter. ◆Add the promoter first, then the main catalyst. * The main catalyst and the co-catalyst are first mixed and contacted, and then added together. ◆ The main catalyst and the co-catalyst are added simultaneously and separately.

[0269] When the main catalyst and the co-catalyst are added separately, they may be introduced successively into the same introduction pipe or into different introduction pipes. When the main catalyst and the co-catalyst are added separately, they should be introduced into different introduction pipes.

[0270] In the production of the ultra-high molecular weight polyethylene of the present invention having a low metal element content, it is necessary to fully release and exert the catalytic activity of the main catalyst for ethylene polymerization in order to reduce the metal element content of the polymer. By using the supported nonmetallocene catalyst described herein, ultra-high molecular weight polyethylene having a low metal element content and ash content can be obtained under the above-mentioned polymerization conditions (polymerization pressure, polymerization temperature, polymerization solvent, optional comonomer, etc.).

[0271] In the present invention, the polymerization pressure and polymerization solvent are useful for increasing the catalytic activity and obtaining ultra-high molecular weight polyethylene with a low metal element content. In the present invention, the polymerization temperature is useful for increasing the catalytic activity, but affects the viscosity average molecular weight of the resulting polyethylene. In addition, extending the polymerization time is also useful for increasing the catalytic activity.

[0272] The ultra-high molecular weight polyethylene of the present invention is an ultra-high molecular weight polyethylene having low metal element and ash contents and excellent mechanical properties (high tensile yield strength, tensile breaking strength, impact strength, etc.), and is therefore suitable for producing high-quality materials (high-strength ultra-high molecular weight polyethylene fibers, medical artificial joints, etc.). [Example]

[0273] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0274] The bulk density of the ultra-high molecular weight polyethylene was measured according to standard GB1636-79. The true density of the ultra-high molecular weight polyethylene was measured by the density gradient column method according to standard GB / T1033-86.

[0275] The polymerization activity of the main catalyst was calculated using the following procedure. First, after the polymerization reaction was completed, the polymerization product in the reaction tank was filtered and dried. Next, the polymerization product was weighed. The polymerization activity of the catalyst (amount of polymer (kg) per gram of catalyst or kgPE / gCat) represents the ratio of the mass of the polymerization product divided by the mass of the polyethylene main catalyst (supported nonmetallocene catalyst).

[0276] The contents of active metal elements in the supported nonmetallocene catalyst and the contents of elements (titanium, magnesium, calcium, aluminum, silicon, chlorine, etc.) in the ultra-high molecular weight polyethylene were measured by ICP-AES.

[0277] The ash content of ultra-high molecular weight polyethylene was measured by the direct calcination method in accordance with the national standard GBT9345.1-2008. The polymer was burned in a muffle furnace, and the residue was treated at high temperature until it reached a constant weight. The ash content was calculated by dividing the mass of the residue by the initial mass of the polymer.

[0278] The comonomer insertion ratio in ultra-high molecular weight ethylene copolymers was measured as follows: First, the copolymers with known comonomer contents were calibrated by nuclear magnetic resonance spectroscopy, and then the insertion ratio was measured using a 66 / S Fourier transform infrared spectrometer (Bruck Corporation, Germany).

[0279] The viscosity-average molecular weight of the ultra-high molecular weight ethylene was calculated using the following procedure. First, the intrinsic viscosity of the polymer was measured according to the standard ASTM D4020-00. For the measurement, a high-temperature dilution type Ubbelohde viscometer method was used. The measurement conditions were as follows: capillary inner diameter: 0.44 mm, thermostatic bath medium: silicone oil 300#, dilution solvent: decalin, and measurement temperature: 135°C. The viscosity-average molecular weight Mv of the polymer was calculated based on the following equation: Mv=5.37×10 4 ×[η] 1.37 (η is the intrinsic viscosity)

[0280] The residual solvent amount contained in the wet material after the polymerization reaction was measured by the following procedure. First, the ethylene slurry polymer powder obtained after the completion of the polymerization reaction was directly filtered through a 100 filter. Next, the wet polymer was weighed, and its mass was designated m1. Next, the wet polymer was completely dried at 80°C under a vacuum of 20 mBar. Next, the dried polymer powder was weighed, and its mass was designated m2. The residual solvent amount was calculated using the following formula.

number

[0281] The melting point and crystallinity of the ultra-high molecular weight polyethylene were measured by differential scanning calorimetry. A Q1000 differential scanning calorimeter (TA Corporation, USA) was used. Measurements were performed in accordance with standard YYT0815-2010. The tensile yield strength, fracture strength, and elongation at break of the polymer were measured in accordance with standard GB / T1040.2-2006. The impact strength of the polymer was measured in accordance with GB / T1043-1993. Young's modulus was measured using a universal testing machine. The compression conditions were pre-pressed at 80°C and 7.0 MPa, followed by hot pressing at 190°C and 7.0 MPa, followed by cold pressing at room temperature and 15.0 MPa. The tensile modulus was measured using a universal testing machine in accordance with GB / T1040.2-2006. The compression conditions were pre-pressing at 80°C and 7.0 MPa, hot pressing at 190°C and 7.0 MPa, and cold pressing at room temperature and 15.0 MPa.

[0282] Example 1: Preparation of the main catalyst [Example 1-1] Anhydrous magnesium chloride was used as the magnesium compound. Tetrahydrofuran was used as the first solvent. Ethanol was used as the alcohol. Silica (silica gel, ES757, Ineos Company) was used as the porous support. First, the silica gel was activated by heat. Specifically, it was baked continuously at 600°C for 4 hours under a nitrogen atmosphere. Titanium tetrachloride (TiCl4) was used as the Group IVB chemical treating agent. Dichloromethane was used as the second solvent. A compound with the following structure was used as the nonmetallocene complex. [ka]

[0283] 5 g of magnesium compound was added to the first solvent, followed by the addition of alcohol. The mixture was completely dissolved at room temperature to obtain a solution of the magnesium compound. Next, the porous carrier was added. The resulting mixture was stirred for 2 hours to obtain a first mixed slurry. Next, the slurry was uniformly heated at 90°C. Next, it was directly vacuum dried to obtain a composite carrier.

[0284] The resulting composite support was added to a hexane solvent. Within 30 minutes at room temperature, a Group IVB chemical treatment agent was added dropwise. The resulting mixture was then uniformly heated to 60°C and reacted at a constant temperature for 2 hours. It was then filtered and washed three times with hexane solvent. The same amount of solvent was used for each wash. Finally, the modified composite support was obtained by vacuum drying at 60°C.

[0285] At room temperature, the nonmetallocene complex was added to the second solvent, followed by the modified composite support. The resulting mixture was stirred for 4 hours. After storing in a sealed state for 12 hours, it was directly vacuum dried at room temperature. In this way, a supported nonmetallocene catalyst was obtained.

[0286] The mass ratio of the magnesium compound to the porous support was 1:2. The molar ratio of the magnesium compound (as elemental Mg) to the alcohol was 1:2. The amount of the first solvent per mole of the magnesium compound was 210 mL. The molar ratio of the composite support (as elemental Mg) to the chemical treating agent (as Group IVB metal element) was 1:0.20. The molar ratio of the composite support (as elemental Mg) to the nonmetallocene complex was 1:0.08. The proportion of the nonmetallocene complex to the second solvent was 0.1 g / mL.

[0287] This supported nonmetallocene catalyst is referred to as CAT-1.

[0288] [Example 1-2] Example 1-1 was changed as follows, but otherwise the same as Example 1-1. The magnesium compound was changed to ethyloxymagnesium (Mg(OC2H5)2). The alcohol was changed to n-butanol. The first solvent was changed to toluene. The porous carrier was changed to partially cross-linked polystyrene (degree of cross-linking: 30%). The polystyrene was dried continuously for 12 hours at 85°C under a nitrogen gas atmosphere. The chemical treating agent was changed to zirconium tetrachloride (ZrCl4). The nonmetallocene complex used was changed as follows: [ka] The second solvent was changed to toluene. The treatment procedure for the first mixed slurry was changed to adding a precipitant (hexane) to the first mixed slurry to completely precipitate it, filtering it, washing it three times with the precipitant, and drying it in a vacuum at 60°C.

[0289] The mass ratio of the magnesium compound to the porous support was 1:1. The molar ratio of the magnesium compound (as elemental Mg) to the alcohol was 1:1. The amount of the first solvent per mole of the magnesium compound was 150 mL. The molar ratio of the composite support (as elemental Mg) to the chemical treating agent (as Group IVB metal element) was 1:0.30. The molar ratio of the composite support (as elemental Mg) to the nonmetallocene complex was 1:0.10. The volume ratio of the precipitating agent to the first solvent was 1:1. The ratio of the nonmetallocene complex to the second solvent was 0.06 g / mL.

[0290] This supported nonmetallocene catalyst is referred to as CAT-2.

[0291] [Examples 1-3] The following changes were made in Example 1-1, and the rest was the same as Example 1-1. The magnesium compound was changed to anhydrous magnesium bromide (MgBr2). The alcohol was changed to 2-ethylhexanol. The first solvent and the second solvent were changed to hexane. The porous carrier used was changed to montmorillonite. The montmorillonite was calcined at 300°C for 6 hours under a nitrogen gas atmosphere. The chemical treating agent was changed to titanium tetrabromide (TiBr4). The nonmetallocene complex used was changed as follows: [ka] The treatment of the first mixed slurry was changed to a procedure of directly drying it under vacuum at 105°C.

[0292] The mass ratio of the magnesium compound to the porous support was 1:5. The molar ratio of the magnesium compound (as elemental Mg) to the alcohol was 1:0.7. The amount of the first solvent per mole of the magnesium compound was 280 mL. The molar ratio of the composite support (as elemental Mg) to the chemical treating agent (as a Group IVB metal element) was 1:0.10. The molar ratio of the composite support (as elemental Mg) to the nonmetallocene complex was 1:0.05. The proportion of the nonmetallocene complex to the second solvent was 0.05 g / mL.

[0293] This supported nonmetallocene catalyst is referred to as CAT-3.

[0294] Example 2: Production of ultra-high molecular weight ethylene homopolymer A 5-L polymerization autoclave was purged with high-purity nitrogen at 100°C for 2 hours. The autoclave was then evacuated to return the internal pressure to normal pressure. 2.5 L of solvent was added. Next, while stirring at 300 rpm, the main catalysts (supported nonmetallocene catalysts CAT1 to CAT-3) and cocatalysts prepared in Example 1 of the present invention were added. The autoclave was heated to a predetermined temperature, and ethylene was continuously introduced while maintaining constant temperature and pressure. This condition was maintained for a predetermined polymerization time. The introduction of ethylene was stopped, the autoclave was evacuated, and the internal pressure was returned to normal pressure. The autoclave was then cooled to room temperature. The polymer was removed from the autoclave together with the solvent. The supernatant solvent was removed, and the remaining material was dried and weighed to determine the final mass. The specific conditions for the homopolymerization reaction of the ethylene slurry are shown in Table 1. The basic properties of the resulting ultra-high molecular weight polyethylene are shown in Table 2. Table 3 shows the metal element contents, ash contents and mechanical properties of the ultra-high molecular weight polyethylene produced by slurry polymerization of ethylene.

[0295] [Comparative Example 2-1] The procedure was essentially the same as in Example 2, except that the polymerization solvent was changed to n-hexane. The polymer number of the obtained polymer was UHMWPE15. Specific conditions for the slurry polymerization reaction of ethylene are shown in Table 1. The results of performance evaluation of the ultra-high molecular weight polyethylene produced by the slurry polymerization of ethylene are shown in Table 2. The metal element contents, ash contents, and crystallinity of the ultra-high molecular weight polyethylene produced by the slurry polymerization of ethylene are shown in Table 3.

[0296] [Comparative Example 2-2] The procedure was essentially the same as in Example 2, except that the polymerization solvent was changed to n-heptane. The polymer number of the obtained polymer was UHMWPE16. Specific conditions for the slurry polymerization reaction of ethylene are shown in Table 1. The results of performance evaluation of the ultra-high molecular weight polyethylene produced by the slurry polymerization of ethylene are shown in Table 2. The metal element contents, ash contents, and crystallinity of the ultra-high molecular weight polyethylene produced by the slurry polymerization of ethylene are shown in Table 3.

[0297] [Comparative Example 2-3] The following changes were made in Example 2, and the rest was essentially the same as Example 2. The catalyst used was changed to a metallocene catalyst (dichlorozirconocene supported on silica gel). The co-catalyst used was changed to methylaluminoxane. The polymerization time was changed to 6 hours. In Comparative Example 2-3, the polymerization activity was extremely low (less than 2 kgPE / gCat), and the viscosity average molecular weight of the polymer was 60 × 10 4 It was less than g / mol.

[0298] [Comparative Example 2-4] The catalyst used in Example 2 was changed to a CM-type Ziegler-Natta catalyst (Beijing Auda Division of Sinopec Catalyst Co, Ltd.), but the rest was essentially the same as in Example 2. The support for this catalyst was a silicon-free magnesium compound, also known as a CMU catalyst. The polymer number of the obtained polymer was UHMWPE17. Specific conditions for the ethylene slurry polymerization reaction are shown in Table 1. The results of performance evaluation of the ultra-high molecular weight polyethylene produced by ethylene slurry polymerization are shown in Table 2. The metal element content, ash content, and crystallinity of the ultra-high molecular weight polyethylene produced by ethylene slurry polymerization are shown in Table 3.

[0299] [Table 1] JPEG0007775318000020.jpg67169

[0300] [Table 2]

[0301] [Table 3]

[0302] Comparing the effects of No. 1 and No. 2 in Table 1, it can be seen that although the molar ratio of cocatalyst to active metal of catalyst in the polymerization process was different, 40 and 100, the polymerization activity of both was similar. This result shows that when the catalyst provided by the present invention is used in olefin polymerization, the amount of cocatalyst required is relatively small. Therefore, according to the present invention, the amount of cocatalyst used can be reduced.

[0303] As can be seen from a comparison of No. 1 and No. 2 in Table 2, under the same polymerization conditions, the viscosity-average molecular weight of the polymer decreases as the amount of cocatalyst increases. Therefore, in the method for producing ultra-high molecular weight polyethylene according to the present invention, the viscosity-average molecular weight and properties of the ultra-high molecular weight polyethylene can be adjusted by changing the type, ratio, and amount of cocatalyst used.

[0304] As can be seen from a comparison of the results in Tables 1 and 2, the polymerization activity of the ethylene slurry increases as the polymerization pressure, polymerization temperature, and polymerization time increase, thereby reducing the metal element content of the resulting ultra-high molecular weight polyethylene.

[0305] As can be seen from a comparison of the effects in Tables 1 and 2, the present invention makes it possible to adjust the performance of the ultra-high molecular weight polyethylene obtained by selecting catalysts with various properties under appropriate ethylene slurry polymerization conditions. Examples of polymerization conditions include polymerization pressure, polymerization temperature, polymerization solvent, polymerization time, type of cocatalyst, and molar ratio of the cocatalyst.

[0306] As can be seen from a comparison of the results for Nos. 1, 15, 16, and 17 in Tables 1 to 3, the method for producing ultra-high molecular weight polyethylene of the present invention makes it very easy to dry the ethylene slurry polymer powder after polymerization is complete. Simply filtering the product directly after the polymerization reaction is complete resulted in less than 20% by weight of solvent remaining in the wet polymer. In contrast, in systems using n-hexane or n-heptane as the polymerization solvent, the amount of solvent remaining in the resulting wet polymer was greater than 25% by weight. This feature is extremely useful for shortening the drying time of polyethylene materials and reducing the post-processing costs of polyethylene.

[0307] As can be seen from Tables 2 and 3, when ultra-high molecular weight polyethylene is produced by the slurry polymerization of ethylene according to the present invention, the ultra-high molecular weight polyethylene produced has a higher bulk density, a higher viscosity average molecular weight, a lower element content (titanium, calcium, magnesium, aluminum, silicon, chlorine, etc.), and a lower ash content than when n-hexane or n-heptane is used as the polymerization solvent. Furthermore, the tensile yield strength, tensile strength at break, elongation at break, impact strength, and Young's modulus of the resulting ultra-high molecular weight ethylene homopolymer are relatively high.

[0308] As can be seen from the effects of Nos. 10 to 14 in Tables 1 to 3, when a mixed alkane solvent is used in the method for producing ultra-high molecular weight polyethylene of the present invention, the resulting polyethylene has a high bulk density, a high viscosity average molecular weight, a low element content (titanium, calcium, magnesium, aluminum, silicon, chlorine, etc.), and a low ash content. Furthermore, the resulting ultra-high molecular weight ethylene homopolymer all has high tensile yield strength, tensile strength at break, elongation at break, impact strength, and Young's modulus.

[0309] Example 3: Production of ultra-high molecular weight ethylene copolymer A 5-L polymerization autoclave was purged with high-purity nitrogen at 100°C for 2 hours. The autoclave was then evacuated to return the internal pressure to normal pressure. 2.5 L of solvent was then added. Next, while stirring at 300 rpm, the main catalysts (supported nonmetallocene catalysts CAT1 to CAT-3) prepared in Example 1 of the present invention, the cocatalyst, and the comonomer were added. The autoclave was heated to a predetermined temperature, and ethylene was continuously introduced while maintaining constant temperature and pressure. This condition was maintained for a predetermined polymerization time. The introduction of ethylene was stopped, the autoclave was evacuated, and the internal pressure was returned to normal pressure. The autoclave was then cooled to room temperature. The polymer was removed from the autoclave together with the solvent. The supernatant solvent was removed, and the remaining material was dried and weighed to determine the final mass. The specific conditions for the ethylene slurry copolymerization reaction are shown in Table 4. The basic performance and tensile properties of the ultra-high molecular weight ethylene copolymer obtained by ethylene slurry polymerization are shown in Table 5. Table 6 shows the metal element content, ash content, melting point and crystallinity of the ultra-high molecular weight ethylene copolymer produced by slurry polymerization of ethylene.

[0310] [Comparative Example 3-1] The procedure was essentially the same as in Example 3, except that the polymerization solvent was changed to n-hexane. The polymer number of the obtained polymer was UHMWPE35. Specific conditions for the slurry polymerization of ethylene are shown in Table 4. The basic performance and tensile properties of the ultra-high molecular weight ethylene copolymer produced by the slurry polymerization of ethylene are shown in Table 5. The metal element content, ash content, melting point, and crystallinity of the ultra-high molecular weight ethylene copolymer produced by the slurry polymerization of ethylene are shown in Table 6.

[0311] [Comparative Example 3-2] The procedure was essentially the same as in Example 3, except that the polymerization solvent was changed to n-heptane. The polymer number of the obtained polymer was UHMWPE36. Specific conditions for the slurry polymerization of ethylene are shown in Table 4. The basic performance and tensile properties of the ultra-high molecular weight ethylene copolymer produced by the slurry polymerization of ethylene are shown in Table 5. The metal element content, ash content, melting point, and crystallinity of the ultra-high molecular weight ethylene copolymer produced by the slurry polymerization of ethylene are shown in Table 6.

[0312] [Comparative Example 3-3] The following changes were made in Example 3, and the rest was essentially the same as Example 3. The catalyst used was changed to a metallocene catalyst (dichlorozirconocene supported on silica gel). The co-catalyst used was changed to methylaluminoxane. The polymerization time was changed to 6 hours. Under these conditions, a reaction slurry was not obtained and the reaction did not proceed.

[0313] [Comparative Example 3-4] The catalyst used in Example 3 was changed to a CM-type Ziegler-Natta catalyst (Beijing Auda Division of Sinopec Catalyst Co., Ltd.), but the rest was essentially the same as in Example 2. The support for this catalyst was a silicon-free magnesium compound, also known as a CMU catalyst. The polymer number of the obtained polymer was UHMWPE37. Specific conditions for the ethylene slurry polymerization reaction are shown in Table 4. The basic performance and tensile properties of the ultra-high molecular weight ethylene copolymer produced by ethylene slurry polymerization are shown in Table 5. The metal element content, ash content, melting point, and crystallinity of the ultra-high molecular weight ethylene copolymer produced by ethylene slurry polymerization are shown in Table 6.

[0314] [Table 4] JPEG0007775318000024.jpg71169

[0315] [Table 5]

[0316] [Table 6]

[0317] Comparing the effects of No. 1 and No. 2 in Table 4, it can be seen that although the molar ratio of cocatalyst to active metal of catalyst in the polymerization process was different, 40 and 100, the polymerization activity of both was similar. This result shows that when the catalyst provided by the present invention is used in olefin polymerization, the amount of cocatalyst required is relatively small. Therefore, according to the present invention, the amount of cocatalyst used can be reduced.

[0318] As can be seen from a comparison of No. 1 and No. 2 in Table 5, under the same polymerization conditions, the viscosity average molecular weight of the polymer decreases as the amount of cocatalyst increases. Therefore, in the method for producing an ethylene copolymer having a very high viscosity average molecular weight according to the present invention, the viscosity average molecular weight and performance of the polyethylene having a very high viscosity average molecular weight can be adjusted by changing the type, ratio and amount of cocatalyst used.

[0319] As can be seen from a comparison of the results in Tables 4 and 5, the polymerization activity of the ethylene slurry increases as the polymerization pressure, polymerization temperature, and polymerization time increase, thereby enabling the metal element content of the resulting polyethylene with a very high viscosity average molecular weight to be reduced.

[0320] As can be seen from a comparison of the effects in Tables 4 and 5, the present invention makes it possible to adjust the performance of polyethylene with a very high viscosity average molecular weight by selecting catalysts with various properties under appropriate ethylene slurry polymerization conditions. Examples of polymerization conditions include polymerization pressure, polymerization temperature, polymerization solvent, polymerization time, type of cocatalyst, and cocatalyst molar ratio.

[0321] As can be seen from a comparison of the results for Nos. 1, 15, 16, and 17 in Tables 4 to 6, the method for producing an ethylene copolymer with a very high viscosity average molecular weight according to the present invention makes it very easy to dry the ethylene slurry polymer powder after polymerization is complete. Simply filtering the product directly after the polymerization reaction is complete results in less than 20% by weight of the solvent remaining in the wet polymer. In contrast, in systems using n-hexane or n-heptane as the polymerization solvent, the amount of solvent remaining in the resulting wet polymer was greater than 25% by weight. This feature is extremely useful for shortening the drying time of polyethylene materials and reducing the post-processing costs of polyethylene.

[0322] As can be seen from Table 5, when ultra-high molecular weight polyethylene is produced by the slurry polymerization of ethylene according to the present invention, the ultra-high molecular weight polyethylene produced has a higher bulk density, a higher viscosity average molecular weight, a lower element content (titanium, calcium, magnesium, aluminum, silicon, chlorine, etc.), and a lower ash content than when n-hexane or n-heptane is used as the polymerization solvent. In addition, the tensile modulus of the resulting ultra-high molecular weight ethylene copolymer is relatively high.

[0323] As can be seen from the effects of Nos. 10 to 14 in Tables 4 to 6, when a mixed alkane solvent is used in the method of the present invention for producing an ethylene copolymer having a very high viscosity average molecular weight, the resulting polyethylene has a high bulk density, a high viscosity average molecular weight, a low element content (titanium, calcium, magnesium, aluminum, silicon, chlorine, etc.), and a low ash content. In addition, the tensile modulus of the resulting ultra-high molecular weight ethylene copolymer is also high.

[0324] The embodiments of the present invention have been described in detail above with reference to examples. However, it should be noted that the scope of the present invention is not limited to the above-described embodiments, but is defined by the appended claims. Those skilled in the art can make appropriate modifications to the embodiments without departing from the technical spirit and scope of the present invention. It is obvious that such modified embodiments also fall within the scope of the present invention.

Claims

1. A method for producing ultra-high molecular weight polyethylene, comprising: The viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150 to 1000×10 ４ g / mol, It is characterized by satisfying the following (i) to (iv): (i) slurry polymerizing a feedstock containing ethylene and, optionally, one or more comonomers in the absence of hydrogen gas; (ii) A supported nonmetallocene catalyst is used as the main catalyst; (iii) cocatalysts including one or more of aluminoxane, alkylaluminum, and haloalkylaluminum; (iv) An alkane solvent having a boiling point of 5 to 55°C or a mixed alkane solvent having a saturated vapor pressure at 20°C of 20 to 150 kPa is used as the polymerization solvent; A production method characterized by carrying out tank-type slurry polymerization under conditions that satisfy the following (v) to (ix): (v) the polymerization temperature is 50 to 100°C; (vi) the polymerization pressure is 0.4 to 4.0 MPa; (vii) The polymerization activity is 2 x 10 of polyethylene per 1 g of main catalyst. ４ is greater than g; (viii) when a comonomer is present, the ratio of the comonomer to the total number of moles of ethylene and the comonomer is 0.01 to 3 mol %; (ix) charging ethylene and the comonomer, if present, together into a polymerization tank; The supported nonmetallocene catalyst is selected from compounds having the formula shown below, and mixtures thereof: 【Chemistry 1】

2. A method for manufacturing a semiconductor device characterized by satisfying the following (i) or (ii): A method for producing the ultra-high molecular weight polyethylene according to claim 1: (i) the polymerization solvent is one of n-pentane, isopentane, neopentane, and cyclopentane; (ii) The polymerization solvent is a mixed alkane solvent containing two or more of n-pentane, isopentane, neopentane, and cyclopentane.

3. The method for producing ultra-high molecular weight polyethylene according to claim 1, which satisfies one or more of the following (i) to (iv): (i) The viscosity average molecular weight of the ultra-high molecular weight polyethylene is 300 to 700 × 10 ４ g / mol; (ii) Polymerization temperature is 60 to 90°C, polymerization pressure is 1.0 to 3.0 MPa, and polymerization activity is 3 x 10 polyethylene per 1 g of main catalyst ４ is greater than g; (iii) when a comonomer is present, the ratio of the comonomer to the total number of moles of ethylene and the comonomer is 0.01 to 2 mol %; (iv) The polymerization solvent is one of a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of n-pentane and neopentane, a combination of isopentane and cyclopentane, a combination of neopentane and cyclopentane, a combination of n-pentane, isopentane and cyclopentane, and a combination of neopentane, isopentane and n-pentane.

4. The comonomer is C ３ ~C １０ α-olefins, A method for producing the ultra-high molecular weight polyethylene according to claim 1.

5. the aluminoxane co-catalyst is selected from methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, n-butylaluminoxane, and mixtures thereof; the alkylaluminum co-catalyst is selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum, dimethylethylaluminum, and mixtures thereof; the haloalkylaluminum co-catalyst is selected from dimethyl(chloro)aluminum, methyl(dichloro)aluminum, diethyl(chloro)aluminum, ethyl(dichloro)aluminum, dipropyl(chloro)aluminum, propyl(dichloro)aluminum, di-n-butyl(chloro)aluminum, n-butyl(dichloro)aluminum, diisobutyl(chloro)aluminum, isobutyl(dichloro)aluminum, di-n-hexyl(chloro)aluminum, n-hexyl(dichloro)aluminum, diisohexyl(chloro)aluminum, isohexyl(dichloro)aluminum, and mixtures thereof; A method for producing the ultra-high molecular weight polyethylene according to claim 1.

6. The aluminoxane co-catalyst is selected from methylaluminoxane, isobutylaluminoxane, and mixtures thereof; the alkyl aluminum is selected from trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, and mixtures thereof; the haloalkylaluminum is selected from diethyl(chloro)aluminum, ethyl(dichloro)aluminum, di-n-butyl(chloro)aluminum, n-butyl(dichloro)aluminum, diisobutyl(chloro)aluminum, isobutyl(dichloro)aluminum, di-n-hexyl(chloro)aluminum, n-hexyl(dichloro)aluminum, and mixtures thereof; A method for producing the ultra-high molecular weight polyethylene according to claim 1.

7. The comonomer is selected from propene, 1-butene, 1-pentene, 1-hexene and 1-octene. A method for producing the ultra-high molecular weight polyethylene according to claim 1.

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