CN114621372B

CN114621372B - Ultra-high molecular weight ethylene homopolymers and process for preparing the same

Info

Publication number: CN114621372B
Application number: CN202210092625.XA
Authority: CN
Inventors: 李传峰; 卞政; 汪文睿; 景昆; 邢跃军; 郭峰
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2021-02-01
Filing date: 2022-01-26
Publication date: 2024-04-09
Anticipated expiration: 2042-01-26
Also published as: CN114621372A

Abstract

The invention relates to an ultra-high molecular weight polyethylene and a preparation method thereof, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-1000 Wanke/mol, the content of metal elements is 0-50ppm, and the bulk density is 0.30-0.55g/cm ³ The true density is 0.900-0.940g/cm ³ The melting point is 140-152 ℃, the crystallinity is 40-75%, and the Young's modulus of the polyethylene is more than 300MPa, preferably more than 350MPa. The ultra-high molecular weight polyethylene has high mechanical property, high melting point, low metal element content and ash content, and the preparation method is simple, feasible, flexible and adjustable.

Description

Ultra-high molecular weight ethylene homopolymers and process for preparing the same

Technical Field

The present invention relates to ultra high molecular weight ethylene homopolymers and copolymers having low metal content and high mechanical properties, and to a process for the slurry preparation of said ethylene homopolymers using an alkane or mixed alkane as polymerization solvent and a catalyst system comprising a supported non-metallocene catalyst as main catalyst.

Background

Ultra-high molecular weight polyethylene (UHMWPE) generally refers to linear structure polyethylene having a relative molecular mass of 150 g/mol or more, has excellent abrasion resistance, extremely high impact strength, excellent self-lubricating properties, excellent chemical resistance and low temperature resistance, excellent anti-adhesion properties, sanitary, non-toxic and pollution-free properties, recyclability and the like, which are not available in general polyethylene, and has been widely used in textile, papermaking, food, chemical industry, packaging, agriculture, construction, medical treatment, water purification, sports, entertainment, military and other fields.

In the aspect of high-end application, the ultra-high viscosity average molecular weight (the viscosity average molecular weight is generally required to be more than 400 ten thousand grams/mole) and the low ash content ultra-high molecular weight polyethylene can be used for gel or gel spinning of a dry method or a wet method to obtain high-strength ultra-high molecular weight polyethylene fibers, and the high-strength ultra-high molecular weight polyethylene fibers are used for bulletproof materials, anti-cutting fabrics, parachutes, fishing nets of fishing boxes and the like. The ultra-high molecular weight polyethylene with lower metal element content and high mechanical property can be used as medical materials such as artificial joints.

The existing preparation method of the ultra-high molecular weight polyethylene is mainly carried out by adopting a Ziegler-Natta catalyst and polymerizing under the slurry polymerization condition. Patent ZL94116488.8 discloses a process for the preparation of ultra-high molecular weight polyethylene having a high bulk density, obtained by polymerization of ethylene catalyzed by a mixed catalyst comprising an organoaluminum compound and a titanium component. CN200410054344.7 discloses a catalyst for ultra-high molecular weight polyethylene, a preparation method and application thereof, the catalyst is composed of a magnesium compound loaded titanium-containing component and a silicon-containing component, and ultra-high molecular weight polyethylene is prepared in the presence of an organic aluminum compound. CN200710042467.2 discloses an ultra-high molecular weight polyethylene catalyst and a preparation method thereof, wherein the preparation of the main catalyst component is obtained by the following steps: (1) reacting magnesium halide with alcohol to form magnesium compound; (2) Reacting a magnesium compound with a silicon compound having at least one halogen group to form an intermediate; and (3) reacting the intermediate with a titanium compound to produce a catalyst body component; benzoate compounds may be optionally added in each reaction step. The catalyst has high activity, and the obtained ultra-high molecular weight polyethylene has the characteristic of high bulk density.

CN200710042468.7 discloses an ultra-high molecular weight polyethylene catalyst and a preparation method thereof, and the main component of the catalyst is prepared by the following steps: (1) Reacting a magnesium halide compound with an alcohol compound and a titanate compound to form a magnesium compound solution; (2) The magnesium compound solution reacts with aluminum alkyl chloride compound to obtain an intermediate product, (3) the intermediate product reacts with titanium compound and electron donor, the activity of the catalyst of the ultra-high molecular weight polyethylene is high, and the obtained ultra-high molecular weight polyethylene has the characteristic of high bulk density. US4962167A1 discloses a process for obtaining a polyethylene catalyst by means of a mutual reaction between a reaction product of a magnesium halide compound and a titanium alkoxide and a reaction product of an aluminum halide and a silicon alkoxide. US 5587440 discloses a process for the preparation of ultra high molecular weight polyethylene with narrow particle size distribution and high bulk density by reduction of titanium (IV) halide with an organoaluminium compound and by a post-treatment process, but with a low activity of the catalyst.

The production method of polyethylene mainly includes high-pressure polymerization, gas-phase polymerization, slurry polymerization, solution polymerization and other processes and methods. Among them, the ethylene slurry polymerization method is one of the main methods for producing polyethylene. The method is classified into loop reactor polymerization and stirred tank slurry polymerization.

In order to obtain ultra-high molecular weight polyethylene, it is common to polymerize ethylene in a hexane or heptane solvent at a polymerization temperature and a polymerization pressure as low as possible. The high polymerization temperature is prone to chain transfer, limits the growth of polyethylene molecular chains, and makes it difficult to obtain polyethylene with high viscosity average molecular weight.

Also, it is known that copolymerizing ethylene with a comonomer will significantly reduce the molecular weight of the polyethylene thus obtained, and in the prior art it is even difficult to produce ultra high molecular weight ethylene copolymers having a viscosity average molecular weight of more than 150 g/mol.

Patent CN201480057309.2 discloses the use of magnesium support to support organometallics (R ³ ₃ p=n-TiCpXn), the catalytic activity is lower and the ash content in the copolymer is higher.

Patent CN201780000391.9 discloses an ultra-high molecular weight ethylene copolymer powder and a molded article using the ultra-high molecular weight ethylene copolymer powder. Wherein the total amount of alpha-olefin units is from 0.01 to 0.10 mole%. However, it is apparent from the examples that the titanium element content in the copolymer is high.

The patents CN201610892732.5, CN201610892836.6, CN201610892837.0 and CN201610892424.2 respectively disclose ultra-high molecular weight polyethylene, a preparation method and application thereof, wherein a supported non-metallocene catalyst is adopted to carry out ethylene homopolymerization and ethylene and alpha-olefin copolymerization in sections, and the obtained ultra-high molecular weight polyethylene molecular chain has at least two chain segments (a homopolymerization chain segment A and a copolymerization chain segment B) and is a block copolymer with wider molecular weight distribution.

To obtain ultra-high molecular weight polyethylene with low metal element content, the common practice is: selecting or preparing a proper catalytic system, and obtaining high polymerization activity as much as possible under ethylene polymerization conditions, wherein the catalyst is required to have high polymerization activity intrinsically; or under the condition of ethylene slurry intermittent polymerization, the polymerization reaction time is prolonged as much as possible, and further high polymerization activity is realized, the catalyst is required to have long polymerization activity service life, the instantaneous consumption of the polymerization monomer ethylene is prolonged with time and is increased, unchanged or reduced, but the instantaneous consumption of the polymerization monomer ethylene cannot be reduced rapidly, even is reduced to an extremely low value rapidly, and the meaning of the extension reaction is lost; or post-treating the ultra-high molecular weight polyethylene obtained by polymerization. For example, chinese patent 200410024103.8 discloses a post-treatment process of ultra-high molecular weight polyethylene, which comprises filtration, solvent washing, drying, water washing, screening and the like, but the treatment process is complex, and the treatment process has high requirements on the impurity content of the washing solvent, and the washing and drying cost is high.

Chinese patent 201610747653.5 discloses a continuous water washing apparatus and method for ultra-high molecular weight polyethylene, in which it is pointed out that in the polymerization process of ultra-high molecular weight polyethylene, a catalyst forms an active center with aluminum alkyl to initiate polymerization of ethylene, and a small amount of metal acid is also generated, which causes corrosion to processing equipment if no water washing is performed, and in addition, excessive presence of high boiling point aluminum alkyl in the polymerization process reacts with a small amount of oxygen and a small amount of water in a solvent to generate aluminum hydroxide, which causes high content of aluminum element in polyethylene, thereby reducing tensile strength, impact strength, wear resistance and the like of the product.

Accordingly, it is currently in the art that it is still desirable to develop a high and controllable viscosity average molecular weight ultra-high molecular weight polyethylene having an adjustable viscosity average molecular weight, high bulk density and mechanical properties, low metal element content and ash content, high mechanical properties, and a process for preparing ultra-high molecular weight polyethylene satisfying the following characteristics: under the condition of ethylene slurry polymerization, the catalyst has long activity life, high polymerization activity, flexible and adjustable polymerization preparation process, and is suitable for large-scale implementation, and the prepared ultra-high molecular weight polyethylene has high bulk density, and the ethylene homopolymer has low branching degree, thereby being beneficial to product packaging, storage, transportation, filling and downstream processing application.

Disclosure of Invention

Based on the prior art, the present inventors have intensively studied and found that an ultra-high molecular weight polyethylene (ethylene homopolymer) having a low metal element content and high mechanical properties can be produced by slurry polymerizing ethylene in the absence of hydrogen using an alkane solvent having a boiling point of 5 to 55 ℃ or a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa at 20 ℃ as a polymerization solvent for slurry polymerization of ethylene, using a supported non-metallocene catalyst as a main catalyst, and one or more of aluminoxane, alkylaluminum and haloalkylaluminum as a cocatalyst, thereby solving the problems as described above, and thus have completed the present invention.

Namely, by the ultra-high molecular weight polyethylene with low metal element content and high mechanical property and the preparation method thereof, the ultra-high molecular weight polyethylene with low metal element content and high mechanical property can be provided without the need of a strict ethylene slurry polymerization reactor configuration, a strict polymerization reaction condition and a complicated post-treatment step. Specifically, the obtained polyethylene has high Young's modulus, tensile yield strength, tensile breaking strength, impact strength and other mechanical properties, is very suitable for industrial mass production, and can be used for the subsequent preparation of high-strength ultrahigh molecular weight polyethylene fibers, high-end materials such as artificial medical joints and the like.

Specifically, the present invention provides an ultra-high molecular weight polyethylene (ethylene homopolymer), wherein the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150 to 1000 g/mol, preferably 200 to 850 g/mol, more preferably 300 to 700 g/mol, the metal element content is 0 to 50ppm, preferably 0 to 30ppm, and the Young's modulus of the polyethylene is more than 300MPa, preferably more than 350MPa.

More specifically, the ultra-high molecular weight polyethylene has a titanium content of 0 to 3ppm, preferably 0 to 2ppm, more preferably 0 to 1ppm, a calcium content of 0 to 5ppm, preferably 0 to 3ppm, more preferably 0 to 2ppm, a magnesium content of 0 to 10ppm, preferably 0 to 5ppm, more preferably 0 to 2ppm, an aluminum content of 0 to 30ppm, preferably 0 to 20ppm, more preferably 0 to 15ppm, a silicon content of 0 to 10ppm, preferably 0 to 5ppm, more preferably 0 to 3ppm, a chlorine content of 0 to 50ppm, preferably 0 to 30ppm, an ash content of less than 200ppm, preferably less than 150ppm, more preferably 80ppm or less, a tensile yield strength of more than 22MPa, preferably more than 25MPa, a tensile strength at break of more than 32MPa, preferably more than 35MPa, an elongation at break of more than 350%, preferably more than 400%, an impact strength of more than 70KJ/m ² Preferably greater than 75 KJ/m ² Young's modulus greater than 300MPa, preferably greater than 350MPa, and more preferably greater than 400MPa.

The present invention also provides a process for producing an ultra-high molecular weight polyethylene having a viscosity average molecular weight of 150 to 1000 g/mol, preferably 200 to 850 g/mol, more preferably 300 to 700 g/mol, wherein ethylene is slurry polymerized in the absence of hydrogen gas using a supported non-metallocene catalyst as a main catalyst, one or more of aluminoxane, alkylaluminum, haloalkylaluminum as a cocatalyst, an alkane solvent having a boiling point of 5 to 55 ℃ or a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃ as a polymerization solvent, thereby obtaining an ultra-high molecular weight polyethylene having a low metal element content.

Technical effects

The ultra-high molecular weight polyethylene has high viscosity average molecular weight, low metal element content, low ash content and excellent mechanical properties, and particularly, the polyethylene has high tensile yield strength, tensile strength at break, impact strength, young's modulus and elongation at break, and is very beneficial to improving the tensile strength, impact strength, wear resistance and the like of products manufactured by the polyethylene.

The preparation method of the invention has the advantages of low consumption of the cocatalyst required in the preparation process, stable polymerization process, stable real-time consumption of ethylene, long activity life of a polymerization system, high polymerization activity of ethylene slurry, and capability of obtaining polyethylene (ethylene homopolymer) with ultrahigh viscosity average molecular weight at higher polymerization temperature.

In addition, the polymerization method of the invention uses the alkane solvent with the boiling point of 5-55 ℃ or the mixed alkane solvent with the saturated vapor pressure of 20-150KPa at 20 ℃ as the polymerization solvent, the selection range of the polymerization solvent is wide, and the heat removal mode in the polymerization reaction process and the post-treatment mode of the obtained ultra-high molecular weight polyethylene powder have wide choices. Further, the post-treatment of the obtained ultra-high molecular weight polyethylene is easy. In addition, the non-metallocene catalyst is matched for use, so that the obtained ultra-high molecular weight polyethylene has low solvent residue content, which is very beneficial to shortening the drying time of polyethylene materials and saving the post-treatment cost of polyethylene and is further beneficial to the subsequent industrial application of ethylene polymers. In addition, the polyethylene with low metal element content, low ash content and excellent mechanical property can be realized.

In the polymerization method of the present invention, only an alkane solvent having a boiling point of 5 to 55 ℃ or a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa at 20 ℃ is used as the polymerization solvent, and no other solvents such as a dispersant and a diluent are required, so that the reaction system is single, and the post-treatment is simple and easy.

Detailed Description

The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the appended claims.

In the context of the present invention, unless otherwise specifically defined or the meaning is beyond the understanding of the skilled artisan, hydrocarbon or hydrocarbon derivative groups of 3 carbon atoms or more (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) have the same meaning as when the prefix "positive" is uncrowded. For example, propyl is generally understood to be n-propyl, while butyl is generally understood to be n-butyl, unless explicitly stated otherwise.

In this specification, in order to avoid complexity of expression, it is not clear whether the valence condition thereof is monovalent, divalent, trivalent, tetravalent, or the like for each substituent or group of a compound, and those skilled in the art can specifically judge the position or the represented substitution condition of these substituents or groups (such as the groups G, D, B, A and F and the like described or defined in this specification) on the structural formula of the corresponding compound, and select a definition appropriate for the valence condition of the position or substitution condition from the definitions given for these substituents or groups in this specification.

All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.

When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.

In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.

Unless explicitly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise clear to the routine knowledge of a person skilled in the art.

In the context of the present invention, physical property values of a substance (such as boiling point) are measured at normal temperature (25 ℃) and normal pressure (101325 Pa), unless specified otherwise.

As a result of intensive studies, the inventors of the present invention have found that, in the polymerization method of the present invention, the use of an alkane solvent having a boiling point of 5 to 55℃or a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20℃as a polymerization solvent can facilitate and efficiently post-treatment of the obtained ultra-high molecular weight polyethylene powder as compared with conventional polymerization solvents, and that the obtained ultra-high molecular weight polyethylene powder has a low solvent residue content, which is advantageous in shortening the drying time of the polyethylene powder and saving the cost of post-treatment of the polyethylene powder. In the invention, only alkane solvent with the boiling point of 5-55 ℃ or mixed alkane solvent with the saturated vapor pressure of 20-150KPa at 20 ℃ is used as a polymerization solvent, other solvents such as dispersing agent, diluent and the like are not needed, the reaction system is single, and the post-treatment is simple and easy.

In addition, in the invention, the catalyst system of the non-metallocene catalyst and the cocatalyst is adopted in the alkane solvent with the boiling point of 5-55 ℃ or the polymerization solvent of the mixed alkane solvent with the saturated vapor pressure of 20-150KPa (preferably 40-110 KPa) at 20 ℃, so that the catalytic activity of the slurry polymerization system is further improved, the polymerization process is stable, the real-time consumption of ethylene is stable, and the polyethylene with the ultra-high viscosity average molecular weight can be obtained at a higher polymerization temperature.

Therefore, the ultra-high molecular weight polyethylene obtained by the method of the invention has high viscosity average molecular weight, low metal element content and ash content, and the obtained polyethylene has excellent mechanical properties, high tensile yield strength, tensile strength at break, impact strength and Young's modulus and large elongation at break. Therefore, the product obtained by using the ultra-high molecular weight polyethylene has excellent mechanical strength and low impurity content, and is suitable for being applied to the fields of aerospace, medical materials and the like with strict requirements on quality.

By the polymerization method, after the ultra-high molecular weight polyethylene crude product is prepared, the ultra-high molecular weight polyethylene with low metal element content, low ash content and excellent mechanical property can be obtained without complex subsequent purification treatment (such as high-purity solvent washing, high-purity water washing, high-temperature steaming, polymer melting and filtering and the like) and only by removing the reaction solvent (such as filtering, decanting, flash evaporation, steaming and the like).

In the present invention, ethylene homopolymer is also referred to as ethylene polymer or polyethylene. That is, it is shown that the polyethylene of the present invention contains no comonomer units other than ethylene, except for possible unavoidable impurities.

The ultra-high molecular weight polyethylene provided by the invention is characterized in that the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-1000 g/mol, preferably 200-850 g/mol, more preferably 300-700 g/mol, the metal element content is 0-50ppm, preferably 0-30ppm, and the Young modulus of the polyethylene is more than 300MPa, preferably more than 350MPa.

In one embodiment of the invention, the polyethylene has a bulk density of 0.30 to 0.55g/cm ³ Preferably 0.33-0.52g/cm ³ More preferably 0.40-0.50g/cm ³ . In one embodiment of the invention, the polyethylene has a true density of 0.900 to 0.940g/cm ³ Preferably 0.905 to 0.935g/cm ³ Further preferably 0.915 to 0.930g/cm ³ . In one embodiment of the invention, the polyethylene has a melting point of 140-152 ℃, preferably 142-150 ℃. In one embodiment of the invention, the crystallinity of the polyethylene is 40-75%, preferably 45-70%.

In one embodiment of the invention, the polyethylene has a titanium content of 0 to 3ppm, preferably 0 to 2ppm, more preferably 0 to 1ppm. In one embodiment of the invention, the polyethylene has a calcium content of 0 to 5ppm, preferably 0 to 3ppm, more preferably 0 to 2ppm. In one embodiment of the invention, the polyethylene has a magnesium content of 0 to 10ppm, preferably 0 to 5ppm, more preferably 0 to 2ppm. In one embodiment of the invention, the polyethylene has an aluminium content of 0 to 30ppm, preferably 0 to 20ppm, more preferably 0 to 15ppm. In one embodiment of the invention, the polyethylene has a silicon content of 0 to 10ppm, preferably 0 to 5ppm, more preferably 0 to 3ppm. In one embodiment of the invention, the polyethylene has a chlorine content of 0 to 50ppm, preferably 0 to 30ppm.

In one embodiment of the present invention, the polyethylene satisfies at least one of the following conditions (1) to (4):

the tensile yield strength of condition (1) is greater than 22MPa, preferably greater than 25MPa,

the tensile strength at break of condition (2) is greater than 32MPa, preferably greater than 35MPa,

the elongation at break of condition (3) is greater than 350%, preferably greater than 400%,

condition (4) impact strength of more than 70KJ/m ² Preferably greater than 75KJ/m ² 。

In one embodiment of the invention, the polyethylene has an ash content of less than 200ppm, preferably less than 150ppm, more preferably less than 80 ppm.

In one embodiment of the invention, the polyethylene has a viscosity average molecular weight of 150 to 1000 vang/mol, preferably 200 to 850 vang/mol, more preferably 300 to 700 vang/mol.

In one embodiment of the invention, the polyethylene has a titanium content of 0-3ppm, preferably 0-2ppm, more preferably 0-1ppm, a calcium content of 0-5ppm, preferably 0-3ppm, more preferably 0-2ppm, a magnesium content of 0-10ppm, preferably 0-5ppm, more preferably 0-2ppm, an aluminum content of 0-30ppm, preferably 0-20ppm, more preferably 0-15ppm, a silicon content of 0-10ppm, preferably 0-5ppm, more preferably 0-3ppm, and a chlorine content of 0-50ppm, preferably 0-30ppm.

In one embodiment of the invention, the polyethylene has a bulk density of 0.30 to 0.55g/cm ³ Preferably a bulk density of 0.33-0.52g/cm ³ More preferably 0.40 to 0.45g/cm ³ The true density is 0.910-0.940g/cm ³ Preferably, the true density is 0.915-0.935g/cm ³ More preferably, the true density is 0.920-0.930g/cm ³ Melting point 140-152 deg.C, preferably 142-150 deg.C, crystallinity 40-75%, preferably 45-70%.

In one embodiment of the invention, the polyethylene has a tensile yield strength of greater than 22MPa, preferably greater than 25MPa, a tensile strength at break of greater than 32MPa, preferably greater than 35MPa, an elongation at break of greater than 350%, preferably greater than 400%, and an impact strength of greater than 70KJ/m ² Preferably greater than 75 KJ/m ² Young's modulus greater than 300MPa, preferably greater than 350MPa.

The content of metal elements in the ultra-high molecular weight polyethylene provided by the invention is 0-50ppm, preferably 0-30ppm.

The ultra-high molecular weight polyethylene according to the present invention is obtained by the following ethylene slurry preparation method according to the present invention.

The invention provides a preparation method of ultra-high molecular weight polyethylene, wherein ethylene is subjected to slurry polymerization by taking a supported non-metallocene catalyst as a main catalyst, one or more of aluminoxane, alkyl aluminum and halogenated alkyl aluminum as a cocatalyst, and an alkane solvent with a boiling point of 5-55 ℃ or a mixed alkane solvent with a saturated vapor pressure of 20-150KPa (preferably 40-110 KPa) at 20 ℃ as a polymerization solvent in the absence of hydrogen.

In one embodiment of the present invention, the ultra-high molecular weight polyethylene is produced at a polymerization temperature of 50 to 100 ℃, preferably 60 to 90 ℃, and a polymerization pressure of 0.4 to 4.0MPa, preferably 1.0 to 3.0MPa, most preferably 1.5 to 3.0MPa.

In one embodiment of the invention, the slurry polymerization is a tank slurry polymerization.

In one embodiment of the present invention, in the process for the preparation of ultra high molecular weight polyethylene, the ethylene slurry polymerization activity is higher than 2 g polyethylene/g procatalyst, preferably the polymerization activity is higher than 3 g polyethylene/g procatalyst, most preferably the polymerization activity is higher than 4 g polyethylene/g procatalyst.

In one embodiment of the present invention, hydrogen is not used in the process for producing ultra-high molecular weight polyethylene.

In the present invention, the ethylene homopolymer means a homopolymer obtained by homopolymerization using only ethylene as the only polymerizable monomer.

According to the present invention, the supported non-metallocene catalyst as a main catalyst may be prepared using a method well known in the art, for example, the following method may be used.

A step of dissolving a magnesium compound in a first solvent in the presence of an alcohol to obtain a magnesium compound solution;

A step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a first mixed slurry;

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 treatment agent selected from group IVB metal compounds to obtain a modified composite support;

and (3) contacting the non-metallocene complex with the modified composite carrier in the presence of a second solvent to obtain a second mixed slurry, and optionally drying to obtain the supported non-metallocene catalyst.

The magnesium compound is specifically described below.

According to the present invention, the term "magnesium compound" refers to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a carrier for a supported olefin polymerization catalyst, using the concept generally in the art.

Specifically, examples of magnesium halide include magnesium chloride (MgCl) ₂ ) Magnesium bromide (MgBr) ₂ ) Magnesium iodide (MgI) ₂ ) And magnesium fluoride (MgF) ₂ ) Among them, magnesium chloride is preferable.

Examples of the alkoxymagnesium halide include methoxymagnesium chloride (Mg (OCH) ₃ ) Cl), ethoxymagnesium chloride (Mg (OC) ₂ H ₅ ) Cl), magnesium chloride propoxy (Mg (OC) ₃ H ₇ ) Cl), magnesium n-butoxide (Mg (OC) ₄ H ₉ ) Cl), magnesium isobutoxy chloride (Mg (i-OC) ₄ H ₉ ) Cl), methoxy magnesium bromide (Mg (OCH) ₃ ) Br), ethoxymagnesium bromide (Mg (OC) ₂ H ₅ ) Br), magnesium propoxybromide (Mg (OC) ₃ H ₇ ) Br), n-butoxymagnesium bromide (Mg (OC) ₄ H ₉ ) Br), magnesium isobutoxy bromide (Mg (i-OC) ₄ H ₉ ) Br), magnesium methoxyiodide (Mg (OCH) ₃ ) I), magnesium ethoxyiodide (Mg (OC) ₂ H ₅ ) I), magnesium propoxyiodide (Mg (OC) ₃ H ₇ ) I), magnesium n-butoxide iodide (Mg (OC) ₄ H ₉ ) I) and magnesium isobutoxy iodide (Mg (I-OC) ₄ H ₉ ) I), etc., of which methoxy magnesium chloride, ethoxy magnesium chloride and isobutoxy magnesium chloride are preferred.

Examples of the magnesium alkoxide include magnesium methoxide (Mg (OCH) ₃ ) ₂ ）、Magnesium ethoxide (Mg (OC) ₂ H ₅ ) ₂ ) Magnesium propoxy (Mg (OC) ₃ H ₇ ) ₂ ) Magnesium butoxide (Mg (OC) ₄ H ₉ ) ₂ ) Magnesium isobutoxide (Mg (i-OC) ₄ H ₉ ) ₂ ) And 2-ethylhexyloxy magnesium (Mg (OCH) ₂ CH(C ₂ H ₅ )C ₄ H ₈ ) ₂ ) And the like, of which ethoxymagnesium and isobutoxymagnesium are preferable.

Examples of the alkyl magnesium include methyl magnesium (Mg (CH) ₃ ) ₂ ) Ethyl magnesium (Mg (C) ₂ H ₅ ) ₂ ) Propyl magnesium (Mg (C) ₃ H ₇ ) ₂ ) N-butylmagnesium (Mg (C) ₄ H ₉ ) ₂ ) And isobutyl magnesium (Mg (i-C) ₄ H ₉ ) ₂ ) And the like, of which ethyl magnesium and n-butyl magnesium are preferable.

Examples of the alkyl magnesium halide include methyl magnesium chloride (Mg (CH) ₃ ) Cl), ethyl magnesium chloride (Mg (C) ₂ H ₅ ) Cl), propyl magnesium chloride (Mg (C) ₃ H ₇ ) Cl), n-butyl magnesium chloride (Mg (C) ₄ H ₉ ) Cl), isobutyl magnesium chloride (Mg (i-C) ₄ H ₉ ) Cl), methyl magnesium bromide (Mg (CH) ₃ ) Br), ethyl magnesium bromide (Mg (C) ₂ H ₅ ) Br), propyl magnesium bromide (Mg (C) ₃ H ₇ ) Br), n-butylmagnesium bromide (Mg (C) ₄ H ₉ ) Br), isobutyl magnesium bromide (Mg (i-C) ₄ H ₉ ) Br), methyl magnesium iodide (Mg (CH) ₃ ) I), ethyl magnesium iodide (Mg (C) ₂ H ₅ ) I), propyl magnesium iodide (Mg (C) ₃ H ₇ ) I), n-butyl magnesium iodide (Mg (C) ₄ H ₉ ) I) and magnesium isobutyl iodide (Mg (I-C) ₄ H ₉ ) I), etc., among which methyl magnesium chloride, ethyl magnesium chloride and isobutyl magnesium chloride are preferred.

Examples of the alkylalkoxymagnesium include methylmagnesium (Mg (OCH) ₃ )(CH ₃ ) Magnesium methylethoxy (Mg (OC) ₂ H ₅ )(CH ₃ ) Magnesium methylpropionate (Mg)(OC ₃ H ₇ )(CH ₃ ) Methyl n-butoxymagnesium (Mg (OC) ₄ H ₉ )(CH ₃ ) Magnesium methyl isobutoxide (Mg (i-OC) ₄ H ₉ )(CH ₃ ) Ethyl methoxymagnesium (Mg (OCH) ₃ )(C ₂ H ₅ ) Magnesium ethyl ethoxide (Mg (OC) ₂ H ₅ )(C ₂ H ₅ ) Magnesium ethylpropoxide (Mg (OC) ₃ H ₇ )(C ₂ H ₅ ) Magnesium ethyl n-butoxide (Mg (OC) ₄ H ₉ )(C ₂ H ₅ ) Magnesium ethyl isobutoxide (Mg (i-OC) ₄ H ₉ )(C ₂ H ₅ ) Propyl methoxy magnesium (Mg (OCH) ₃ )(C ₃ H ₇ ) Magnesium propyl ethoxy (Mg (OC) ₂ H ₅ )(C ₃ H ₇ ) Magnesium propylpropoxide (Mg (OC) ₃ H ₇ )(C ₃ H ₇ ) Propyl magnesium n-butoxide (Mg (OC) ₄ H ₉ )(C ₃ H ₇ ) Magnesium propyl isobutoxide (Mg (i-OC) ₄ H ₉ )(C ₃ H ₇ ) N-butyl methoxy magnesium (Mg (OCH) ₃ )(C ₄ H ₉ ) N-butyl ethoxymagnesium (Mg (OC) ₂ H ₅ )(C ₄ H ₉ ) N-butyl-propoxy magnesium (Mg (OC) ₃ H ₇ )(C ₄ H ₉ ) N-butyl n-butoxymagnesium (Mg (OC) ₄ H ₉ )(C ₄ H ₉ ) N-butyl magnesium isobutoxide (Mg (i-OC) ₄ H ₉ )(C ₄ H ₉ ) Isobutyl methoxymagnesium (Mg (OCH) ₃ )(i-C ₄ H ₉ ) Isobutyl ethoxymagnesium (Mg (OC) ₂ H ₅ )(i-C ₄ H ₉ ) Magnesium isopropoxide (Mg (OC) ₃ H ₇ ) (i-C ₄ H ₉ ) Isobutyl n-butoxymagnesium (Mg (OC) ₄ H ₉ ) (i-C ₄ H ₉ ) And isobutylmagnesium isobutoxide (Mg (i-OC) ₄ H ₉ ) (i-C ₄ H ₉ ) Butyl ethoxy magnesium is preferred among others.

These magnesium compounds may be used alone or in combination of two or more thereof, and are not particularly limited.

When used in a plurality of mixed forms, the molar ratio between the two magnesium compounds in the magnesium compound mixture is, for example, 0.25 to 4:1, preferably 0.5 to 3:1, more preferably 1 to 2:1.

The procedure for obtaining the magnesium compound solution will be specifically described below.

According to this step, a magnesium compound is dissolved in a first solvent (hereinafter, also referred to as a solvent for dissolving a magnesium compound) in the presence of an alcohol, thereby obtaining the magnesium compound solution.

Examples of the first solvent include C _6-12 Aromatic hydrocarbons, halogenated C _6-12 Aromatic hydrocarbon, C _5-12 Alkanes, esters, and ethers.

As said C _6-12 Examples of the aromatic hydrocarbon include toluene, xylene, trimethylbenzene, ethylbenzene and diethylbenzene.

As said halogenated C _6-12 Examples of the aromatic hydrocarbon include chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene and the like.

As said C _5-12 Examples of the alkane include pentane, hexane, heptane, octane, nonane and decane, and among them, hexane, heptane and decane are preferable, and hexane is most preferable.

Examples of the ester 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.

Examples of the ether include diethyl ether, methylethyl ether, and tetrahydrofuran.

Of these, C is preferred _6-12 Aromatic hydrocarbon, C _5-12 Paraffinic hydrocarbons and tetrahydrofuran, most preferably tetrahydrofuran.

These solvents may be used alone or in combination of two or more thereof in any ratio.

According to the invention, the term "alcohol" refers to a hydrocarbon chain (such as C _1-30 Hydrocarbon) in which at least one hydrogen atom is substituted with a hydroxyl group. Which may be one or more selected from the group consisting of aliphatic alcohols, aromatic alcohols and alicyclic alcohols.

Examples of the alcohol include C _1-30 Fatty alcohols (preferably C) _1-30 Aliphatic monohydric alcohol), C _6-30 Aromatic alcohols (preferably C) _6-30 Aromatic monohydric alcohol) and C _4-30 Alicyclic alcohols (preferably C) _4-30 Alicyclic monohydric alcohols), of which C is preferred _1-30 Aliphatic monohydric alcohols or C _2-8 Aliphatic monohydric alcohols, more preferably ethanol and butanol. In addition, the alcohol may optionally be selected from halogen atoms or C _1-6 The substituent of the alkoxy group is substituted.

As said C _1-30 Examples of the aliphatic alcohol include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, 2-methylpentanol, 2-ethylpentanol, 2-hexylbutanol, hexanol, and 2-ethylhexanol, and among them, ethanol, butanol, and 2-ethylhexanol are preferable.

As said C _6-30 Aromatic alcohols include benzyl alcohol, phenethyl alcohol, and methylbenzyl alcohol, and phenethyl alcohol is preferable.

As said C _4-30 Examples of alicyclic alcohols include cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, propylcyclooctanol and the like, and among these, cyclohexanol and methylcyclohexanol are preferable.

Examples of the alcohol substituted with a halogen atom include trichloromethanol, trichloroethanol, and trichlorohexanol, and among them, trichloromethanol is preferable.

Examples of the alcohol substituted with an alkoxy group include ethylene glycol-diethyl ether, ethylene glycol-n-butyl ether, and 1-butoxy-2-propanol, and among them, ethylene glycol-diethyl ether is preferable.

These alcohols may be used alone or in combination of two or more. When used in a plurality of mixed forms, the ratio between any two alcohols in the alcohol mixture may be arbitrarily determined, and is not particularly limited.

In order to prepare the magnesium compound solution, the magnesium compound may be added to a mixed solvent formed of the first solvent and the alcohol to be dissolved, or the magnesium compound may be added to the first solvent and simultaneously or subsequently added with the alcohol to be dissolved, but is not limited thereto. The preparation time of the magnesium compound solution (i.e., the dissolution time of the magnesium compound) is not particularly limited, but is generally 0.5 to 24 hours, preferably 4 to 24 hours. During this preparation, stirring may be used to promote dissolution of the magnesium compound. The stirring may take any form, such as a paddle (typically at 10-1000 rpm), or the like. Dissolution may sometimes be promoted by appropriate heating (but the highest temperature must be below the boiling point of the first solvent and the alcohol), as desired.

According to the invention, a porous support, optionally subjected to a thermal activation treatment and/or a chemical activation treatment, is mixed with the magnesium compound solution to obtain a first mixed slurry.

The porous support is specifically described below.

According to the present invention, as the porous carrier, there may be mentioned, for example, organic or inorganic porous solids conventionally used in the art as carriers in the production of supported olefin polymerization catalysts.

Specifically, examples of the organic porous solid include olefin homo-or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, (co) polyester, (co) polyamide, vinyl chloride homo-or copolymer, acrylate homo-or copolymer, methacrylate homo-or copolymer, and styrene homo-or copolymer, and the like, and partially crosslinked forms of these homo-or copolymers, among which a partially crosslinked (for example, a degree of crosslinking of at least 2% but less than 100%) styrene polymer is preferable.

According to a preferred embodiment of the present invention, it is preferable that the organic porous solid has on its surface a reactive functional group such as any one or more selected from the group consisting of a hydroxyl group, a primary amino group, a secondary amino group, a sulfonic acid group, a carboxyl group, an amide group, an N-monosubstituted amide group, a sulfonamide group, an N-monosubstituted sulfonamide group, a mercapto group, an imide group and a hydrazide group, wherein at least one of a carboxyl group and a hydroxyl group is preferable.

According to one embodiment of the invention, the organic porous solid is subjected to a thermal and/or chemical activation treatment prior to use.

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

The heat activation treatment may be performed in a usual manner. Such as heat treating the organic porous solid under reduced pressure or under an inert atmosphere. The inert atmosphere as used herein means that the gas contains only very small amounts or no components that can react with the organic porous solid. Examples of the inert atmosphere include a nitrogen gas atmosphere and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Since the organic porous solid is poor in heat resistance, the heat activation process is premised on not damaging the structure and basic composition of the organic porous solid itself. Typically, the temperature of the thermal activation is 50-400 ℃, preferably 100-250 ℃, and the thermal activation time is 1-24 hours, preferably 2-12 hours.

After thermal/chemical activation, the organic porous solid needs to be stored under positive pressure in an inert atmosphere for later use.

As the inorganic porous solid, for example, there may be mentioned refractory oxides of metals of group IIA, IIIA, IVA or IVB of the periodic Table (such as silica (also referred to as silica or silica gel), alumina, magnesia, titania, zirconia or thoria, etc.), or any refractory composite oxides of these metals (such as silica alumina, magnesia alumina, titania silica, titania magnesia and titania alumina, etc.), as well as clays, molecular sieves (such as ZSM-5 and MCM-41), mica, montmorillonite, bentonite and diatomaceous earth, etc. The inorganic porous solid may be an oxide formed by high-temperature hydrolysis of a gaseous metal halide or a gaseous silicon compound, such as silica gel obtained by high-temperature hydrolysis of silicon tetrachloride, alumina obtained by high-temperature hydrolysis of aluminum trichloride, or the like.

As the inorganic porous solid, silica, alumina, magnesia, silica alumina, magnesia alumina, titania silica, titania, molecular sieves, montmorillonite and the like are preferable, and silica is particularly preferable.

Suitable silicas according to the invention can be produced by conventional methods or can be any commercially available product, such as Grace 955, grace 948, grace SP9-351, grace SP9-485, grace SP9-10046, grace 2480D, grace 2212D, grace 2485, davision Syloid 245 and Aerosil812, ES70X, ES70Y, ES, W, ES757, EP10X and EP11 from Grace, and CS-2133 and MS-3040 from PQ.

According to a preferred embodiment of the present invention, the inorganic porous solid preferably has a reactive functional group such as a hydroxyl group on the surface thereof.

According to the present invention, in one embodiment, the inorganic porous solid is subjected to a thermal activation treatment and/or a chemical activation treatment prior to use.

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

The heat-activation treatment may be carried out in a usual manner, such as heat-treating the inorganic porous solid under reduced pressure or an inert atmosphere. The inert atmosphere as used herein means that the gas contains only an extremely small amount or no component that can react with the inorganic porous solid. Examples of the inert atmosphere include a nitrogen gas atmosphere and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Typically, the temperature of the thermal activation is from 200 to 800 ℃, preferably from 400 to 700 ℃, most preferably from 400 to 650 ℃, and the heating time is for example from 0.5 to 24 hours, preferably from 2 to 12 hours, most preferably from 4 to 8 hours.

After thermal/chemical activation, the inorganic porous solid needs to be stored under positive pressure in an inert atmosphere for later use.

According to the present invention, the chemical activation treatment for the organic porous solid or the inorganic porous solid may be performed in a usual manner. For example, a method of chemically activating the organic porous solid or the inorganic porous solid using a chemical activator may be mentioned.

According to the invention, a group IVB metal compound is used as the chemical activator.

Examples of the group IVB metal compound include at least one selected from the group consisting of a group IVB metal halide, a group IVB metal alkyl compound, a group IVB metal alkoxide compound, a group IVB metal alkyl halide and a group IVB metal alkoxide halide.

As the group IVB metal compound, the group IVB metal halide is preferable, and TiCl is more preferable ₄ 、TiBr ₄ 、ZrCl ₄ 、ZrBr ₄ 、HfCl ₄ And HfBr ₄ TiCl is most preferred ₄ And ZrCl ₄ 。

These group IVB metal compounds may be used singly or in combination of plural kinds in any ratio.

When the chemical activator is in a liquid state at normal temperature, the chemical activator may be used by directly dropping a predetermined amount of the chemical activator into an organic porous solid or an inorganic porous solid to be activated with the chemical activator.

When the chemical activator is solid at ordinary temperature, it is preferable to use the chemical activator in the form of a solution for the convenience of metering and handling. Of course, when the chemical activator is in a liquid state at normal temperature, the chemical activator may be used in a solution form as needed, and is not particularly limited.

In preparing the solution of the chemical activator, the solvent used at this time is not particularly limited as long as it can dissolve the chemical activator.

Specifically, C may be mentioned _5-12 Paraffin, C _5-12 Cycloalkane, halogenated C _5-12 Paraffin, halogenated C _5-12 Cycloalkane, C _6-12 Aromatic hydrocarbons or halogenated C _6-12 Aromatic hydrocarbons and the like are exemplified by 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, chloroxylenes and the like, and among them, pentane, hexane, decane, cyclohexane, toluene and the like are preferable, and hexane and toluene are most preferable.

These solvents may be used alone or in combination of plural kinds in an arbitrary ratio.

In addition, the concentration of the chemical activator in the solution thereof is not particularly limited, and may be appropriately selected as required, as long as it can achieve the chemical activation with a predetermined amount of the chemical activator. As described above, if the chemical activator is in a liquid state, the chemical activator may be used as it is, but it may be used after being prepared into a chemical activator solution.

Conveniently, the molar concentration of the chemical activator in the solution is generally set to 0.01 to 1.0mol/L, but is not limited thereto.

As a method for performing the chemical activation, for example, in the case where a chemical activator is in a solid state (such as zirconium tetrachloride), a solution of the chemical activator is first prepared, and then the solution containing a predetermined amount of the chemical activator is added (preferably dropwise) to an organic porous solid or an inorganic porous solid to be activated to perform a chemical activation reaction. In the case where the chemical activator is in a liquid state (such as titanium tetrachloride), a predetermined amount of the chemical activator may be directly added (preferably dropwise) to the organic porous solid or inorganic porous solid to be activated to perform the chemical activation reaction, or after the chemical activator is prepared as a solution, the solution containing a predetermined amount of the chemical activator may be added (preferably dropwise) to the organic porous solid or inorganic porous solid to be activated to perform the chemical activation reaction.

In general, the chemical activation reaction (if necessary, by stirring) is carried out at a reaction temperature of-30 to 60 ℃ (preferably-20 to 30 ℃) for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours.

After the chemical activation reaction is finished, the chemically activated organic porous solid or inorganic porous solid can be obtained through filtration, washing and drying.

According to the present invention, the filtration, washing and drying may be performed using a conventional method, wherein the washing solvent may be the same solvent as used in dissolving the chemical activator. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times, as required.

The drying may be performed by a conventional method such as an inert gas drying method, a vacuum drying method or a vacuum heating drying method, preferably an inert gas drying method or a vacuum heating drying method, and most preferably a vacuum heating drying method. The drying temperature is generally in the range of normal temperature to 140 ℃, and the drying time is generally 2-20 hours, but is not limited thereto.

According to the invention, the chemical activator is used in an amount such that the ratio of the porous support to the chemical activator in terms of group IVB metal element is from 1g to 100mmol, preferably from 1g to 2 to 50mmol, more preferably from 1g to 10 to 25mmol.

According to the present invention, the surface area of the porous support is not particularly limited, but is generally 10 to 1000m ² Per gram (BET method), preferably 100-600m ² /g; the porous carrier has a pore volume (measured by nitrogen adsorption) of generally 0.1-4cm ³ Per g, preferably 0.2-2cm ³ And its average particle diameter (measured by a laser particle sizer) is preferably 1 to 500mm, more preferably 1 to 100mm.

According to the invention, the porous support may be in any form, such as a micro-powder, a granulate, a sphere, an aggregate or other form.

A first mixed slurry is obtained by mixing the porous support (optionally via thermal and/or chemical activation) with the magnesium compound solution.

According to the present invention, the mixing process of the porous support and the magnesium compound solution may be performed by a general method, and is not particularly limited. For example, the porous support may be metered into the magnesium compound solution at a temperature ranging from room temperature to the preparation temperature of the magnesium compound solution, or the magnesium compound solution may be metered into the porous support and mixed for 0.1 to 8 hours, preferably 0.5 to 4 hours, and most preferably 1 to 2 hours (with stirring if necessary).

According to the present invention, the porous carrier is used in such an amount that the mass ratio of the magnesium compound (based on the magnesium compound solid contained in the magnesium compound solution) to the porous carrier is 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 5.

At this time, the obtained first mixed slurry is a slurry-like system. Although not necessary, in order to ensure uniformity of the system, the first mixed slurry is preferably subjected to closed standing for a certain period of time (2 to 48 hours, preferably 4 to 24 hours, and most preferably 6 to 18 hours) after the preparation.

According to the present invention, by directly drying the first mixed slurry, a solid product having good fluidity, i.e., the composite carrier of the present invention, can be obtained.

At this time, the direct drying may be performed by a conventional method such as drying under an inert gas atmosphere, drying under a vacuum atmosphere, or heat drying under a vacuum atmosphere, etc., with heat drying under a vacuum atmosphere being preferred. The drying temperature is generally 30 to 160 ℃, preferably 60 to 130 ℃, and the drying time is generally 2 to 24 hours, but is not limited thereto in some cases.

Alternatively, according to the present invention, the solid matter is precipitated from the first mixed slurry by metering a precipitant into the first mixed slurry, thereby obtaining a composite carrier.

The precipitant is specifically described below.

According to the present invention, the term "precipitant" is used in the general sense of the art to refer to a chemically inert liquid capable of reducing the solubility of a solid solute (such as the magnesium compound, porous support, non-metallocene ligand or non-metallocene complex, etc.) in its solution and thereby precipitating it from the solution in solid form.

According to the present invention, examples of the precipitant include a solvent which is a poor solvent for a solid solute to be precipitated (for example, the magnesium compound, porous support, non-metallocene ligand, non-metallocene complex, etc.), and a solvent which is a good solvent for the solvent for dissolving the solid solute (for example, magnesium compound), for example, C _5-12 Paraffin, C _5-12 Cycloalkane, halogenated C _1-10 Paraffins and halogenated C _5-12 Cycloalkanes.

As said C _5-12 Examples of cycloalkanes include cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, and cyclohexane is most preferred.

As said halogenated C _1-10 Examples of the alkane include methylene chloride, dichlorohexane, dichloroheptane, chloroform, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane.

As said halogenated C _5-12 Examples of cycloalkanes include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.

These precipitants may be used alone or in combination of two or more kinds in any ratio.

The precipitant may be added in one-time or dropwise, preferably in one-time. During this precipitation process, agitation may be used to facilitate the dispersion of the precipitant and to facilitate the final precipitation of the solid product. The stirring may take any form (e.g., paddles) and is typically at a rotational speed of 10-1000 revolutions per minute, etc.

The amount of the precipitant is not particularly limited, but generally the ratio of the precipitant to the solvent for dissolving the magnesium compound is 1:0.2 to 5, preferably 1:0.5 to 2, more preferably 1:0.8 to 1.5 by volume.

The temperature of the precipitant is not particularly limited, but is generally preferably from room temperature to a temperature lower than the boiling point of any solvent and precipitant used (preferably 20 to 80 ℃, more preferably 40 to 60 ℃), but is not limited thereto in some cases. Moreover, the precipitation process is also generally preferably carried out at a temperature ranging from ambient temperature to a temperature lower than the boiling point of any solvent and precipitant used (preferably 20 to 80 ℃, more preferably 40 to 60 ℃) for 0.3 to 12 hours, but is sometimes not limited thereto, and is based on substantially complete precipitation of the solid product.

After complete precipitation, the solid product obtained is filtered, washed and dried. The method of filtering, washing and drying is not particularly limited, and those conventionally used in the art may be used as required.

The washing is generally performed 1 to 6 times, preferably 3 to 4 times, as needed. Among them, the same solvent as the precipitant is preferably used for the washing solvent, but may be different.

The drying may be performed by a conventional method such as an inert gas drying method, a vacuum drying method or a vacuum heating drying method, preferably an inert gas drying method or a vacuum heating drying method, and most preferably a vacuum heating drying method.

The temperature of the drying is generally in the range of normal temperature to 140 ℃. The drying time is generally 2 to 20 hours, but may be varied depending on the specific solvent used for dissolving the magnesium compound. For example, when tetrahydrofuran is used as a solvent for dissolving the magnesium compound, the drying temperature is generally about 80 ℃, and the drying is performed under vacuum for 2 to 12 hours, whereas when toluene is used as a solvent for dissolving the magnesium compound, the drying temperature is generally about 100 ℃, and the drying is performed under vacuum for 4 to 24 hours.

According to the present invention, a modified composite carrier is obtained by contacting the composite carrier obtained as described above with a chemical treatment agent selected from group IVB metal compounds.

The chemical treatment agent is specifically described below.

According to the invention, a group IVB metal compound is used as the chemical treatment agent.

Examples of the group IVB metal halide, the group IVB metal alkyl compound, the group IVB metal alkoxy compound, the group IVB metal alkyl halide and the group IVB metal alkoxy halide include compounds having the following general structures:

M(OR ¹ ) _m X _n R ² _4-m-n

wherein:

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, such as titanium, zirconium, hafnium, etc.;

x is halogen, such as F, cl, br and I; and is also provided with

R ¹ And R is ² Each independently selected from C ₁ - ₁₀ Alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R ¹ And R is ² May be the same or different.

Specifically, examples of the group IVB metal halide include titanium Tetrafluoride (TiF) ₄ ) Titanium tetrachloride (TiCl) ₄ ) Titanium tetrabromide (TiBr) ₄ ) Titanium Tetraiodide (TiI) ₄ ）；

Zirconium tetrafluoride (ZrF) ₄ ) Zirconium tetrachloride (ZrCl) ₄ ) Zirconium tetrabromide (ZrBr) ₄ ) Zirconium tetraiodide (ZrI) ₄ ）；

Hafnium tetrafluoride (HfF) ₄ ) Hafnium tetrachloride (HfCl) ₄ ) Fourth stepHafnium bromide (HfBr) ₄ ) Hafnium tetraiodide (HfI) ₄ ）。

Examples of the group IVB metal alkyl compound include tetramethyl titanium (Ti (CH) ₃ ) ₄ ) Titanium tetraethyl (Ti (CH) ₃ CH ₂ ) ₄ ) Titanium tetraisobutyl (Ti (i-C) ₄ H ₉ ) ₄ ) Tetra-n-butyl titanium (Ti (C) ₄ H ₉ ) ₄ ) Triethylmethyl titanium (Ti (CH) ₃ )(CH ₃ CH ₂ ) ₃ ) Diethyl dimethyl titanium (Ti (CH) ₃ ) ₂ (CH ₃ CH ₂ ) ₂ ) Trimethylethyl titanium (Ti (CH) ₃ ) ₃ (CH ₃ CH ₂ ) Triisobutyl methyl titanium (Ti (CH) ₃ )(i-C ₄ H ₉ ) ₃ ) Diisobutyldimethyl titanium (Ti (CH) ₃ ) ₂ (i-C ₄ H ₉ ) ₂ ) Trimethyl isobutyl titanium (Ti (CH) ₃ ) ₃ (i-C ₄ H ₉ ) Triisobutyl ethyl titanium (Ti (CH) ₃ CH ₂ )(i-C ₄ H ₉ ) ₃ ) Diisobutyldiethyl titanium (Ti (CH) ₃ CH ₂ ) ₂ (i-C ₄ H ₉ ) ₂ ) Triethylisobutyl titanium (Ti (CH) ₃ CH ₂ ) ₃ (i-C ₄ H ₉ ) Tri-n-butyl methyl titanium (Ti (CH) ₃ )(C ₄ H ₉ ) ₃ ) Di-n-butyldimethyl titanium (Ti (CH) ₃ ) ₂ (C ₄ H ₉ ) ₂ ) Trimethyl n-butyl titanium (Ti (CH) ₃ ) ₃ (C ₄ H ₉ ) Tri-n-butyl ethyl titanium (Ti (CH) ₃ CH ₂ )(C ₄ H ₉ ) ₃ ) Di-n-butyl diethyl titanium (Ti (CH) ₃ CH ₂ ) ₂ (C ₄ H ₉ ) ₂ ) Triethyl n-butyl titanium (Ti (CH) ₃ CH ₂ ) ₃ (C ₄ H ₉ ) Etc.;

zirconium tetramethyl (Zr (CH) ₃ ) ₄ ) Zirconium tetraethyl (Zr (CH) ₃ CH ₂ ) ₄ ) Zirconium tetraisobutyl (Zr (i-C) ₄ H ₉ ) ₄ ) Tetra-n-butylzirconium (Zr (C) ₄ H ₉ ) ₄ ) Zirconium triethyl (Zr (CH) ₃ )(CH ₃ CH ₂ ) ₃ ) Zirconium diethyl (Zr (CH) ₃ ) ₂ （CH ₃ CH ₂ ) ₂ ) Trimethylethylzirconium (Zr (CH) ₃ ) ₃ (CH ₃ CH ₂ ) Triisobutyl methyl zirconium (Zr (CH) ₃ )(i-C ₄ H ₉ ) ₃ ) Diisobutylzirconium dimethyl (Zr (CH) ₃ ) ₂ (i-C ₄ H ₉ ) ₂ ) Trimethylzirconium isobutyl (Zr (CH) ₃ ) ₃ (i-C ₄ H ₉ ) Triisobutylethylzirconium (Zr (CH) ₃ CH ₂ )(i-C ₄ H ₉ ) ₃ ) Diisobutyldiethylzirconium (Zr (CH) ₃ CH ₂ ) ₂ (i-C ₄ H ₉ ) ₂ ) Triethylisobutyl zirconium (Zr (CH) ₃ CH ₂ ) ₃ (i-C ₄ H ₉ ) Tri-n-butyl methyl zirconium (Zr (CH) ₃ )(C ₄ H ₉ ) ₃ ) Di-n-butylzirconium dimethyl (Zr (CH) ₃ ) ₂ (C ₄ H ₉ ) ₂ ) Trimethyl n-butyl zirconium (Zr (CH) ₃ ) ₃ (C ₄ H ₉ ) Tri-n-butyl ethyl zirconium (Zr (CH) ₃ CH ₂ )(C ₄ H ₉ ) ₃ ) Di-n-butyl-diethyl-zirconium (Zr (CH) ₃ CH ₂ ) ₂ (C ₄ H ₉ ) ₂ ) Triethyl n-butyl zirconium (Zr (CH) ₃ CH ₂ ) ₃ (C ₄ H ₉ ) Etc.;

hafnium tetramethyl (Hf (CH) ₃ ) ₄ ) Hafnium tetraethyl (Hf (CH) ₃ CH ₂ ) ₄ ) Hafnium tetraisobutyl (Hf (i-C) ₄ H ₉ ) ₄ ) Tetra-n-butylhafnium (Hf (C) ₄ H ₉ ) ₄ ) Hafnium triethylmethyl (Hf (CH) ₃ )(CH ₃ CH ₂ ) ₃ ) Hafnium dimethyl diethyl (Hf (CH) ₃ ) ₂ (CH ₃ CH ₂ ) ₂ ) Trimethylhafnium ethyl (Hf (CH) ₃ ) ₃ (CH ₃ CH ₂ ) Hafnium triisobutyl (Hf (CH) ₃ )(i-C ₄ H ₉ ) ₃ ) Hafnium diisobutyldimethyl (Hf (CH) ₃ ) ₂ (i-C ₄ H ₉ ) ₂ ) Trimethylhafnium isobutyl (Hf (CH) ₃ ) ₃ (i-C ₄ H ₉ ) Hafnium triisobutyl ethyl (Hf (CH) ₃ CH ₂ )(i-C ₄ H ₉ ) ₃ ) Diisobutylhafnium diethyl (Hf (CH) ₃ CH ₂ ) ₂ (i-C ₄ H ₉ ) ₂ ) Triethylisobutylhafnium (Hf (CH) ₃ CH ₂ ) ₃ (i-C ₄ H ₉ ) (1), tri-n-butylhafnium methyl (Hf (CH) ₃ )(C ₄ H ₉ ) ₃ ) Di-n-butylhafnium dimethyl (Hf (CH) ₃ ) ₂ (C ₄ H ₉ ) ₂ ) Trimethyl n-butyl hafnium (Hf (CH) ₃ ) ₃ (C ₄ H ₉ ) Tri-n-butylhafnium ethyl (Hf (CH) ₃ CH ₂ )(C ₄ H ₉ ) ₃ ) Di-n-butylhafnium diethyl (Hf (CH) ₃ CH ₂ ) ₂ (C ₄ H ₉ ) ₂ ) Triethylhafnium n-butyl (Hf (CH) ₃ CH ₂ ) ₃ (C ₄ H ₉ ) And the like.

Examples of the group IVB metal alkoxide include tetramethoxytitanium (Ti (OCH) ₃ ) ₄ ) Titanium tetraethoxide (Ti (OCH) ₃ CH ₂ ) ₄ ) Titanium tetraisobutoxide (Ti (i-OC) ₄ H ₉ ) ₄ ) Titanium tetra-n-butoxide (Ti (OC) ₄ H ₉ ) ₄ ) Triethoxy methoxy titanium (Ti (OCH) ₃ )(OCH ₃ CH ₂ ) ₃ ) Diethoxydimethoxy titanium (Ti (OCH) ₃ ) ₂ (OCH ₃ CH ₂ ) ₂ ) Trimethoxyethoxytitanium (Ti (OCH) ₃ ) ₃ (OCH ₃ CH ₂ ) Triisobutoxy methyl ester)Titanium oxide (Ti (OCH) ₃ )(i-OC ₄ H ₉ ) ₃ ) Diisobutoxy dimethoxy titanium (Ti (OCH) ₃ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Titanium trimethoxyisobutoxy (Ti (OCH) ₃ ) ₃ (i-OC ₄ H ₉ ) Titanium triisobutoxide (Ti (OCH) ₃ CH ₂ )(i-OC ₄ H ₉ ) ₃ ) Diisobutoxy diethoxy titanium (Ti (OCH) ₃ CH ₂ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Titanium triethoxy isobutoxide (Ti (OCH) ₃ CH ₂ ) ₃ (i-OC ₄ H ₉ ) Titanium tri-n-butoxymethoxide (Ti (OCH) ₃ )(OC ₄ H ₉ ) ₃ ) Di-n-Butoxydimethoxy titanium (Ti (OCH) ₃ ) ₂ (OC ₄ H ₉ ) ₂ ) Trimethoxy-n-butoxytitanium (Ti (OCH) ₃ ) ₃ (OC ₄ H ₉ ) Titanium tri-n-butoxyethoxy (Ti (OCH) ₃ CH ₂ )(OC ₄ H ₉ ) ₃ ) di-n-Butoxydiethoxy titanium (Ti (OCH) ₃ CH ₂ ) ₂ (OC ₄ H ₉ ) ₂ ) Titanium n-butoxide triethoxide (Ti (OCH) ₃ CH ₂ ) ₃ (OC ₄ H ₉ ) Etc.;

zirconium tetramethoxyl (Zr (OCH) ₃ ) ₄ ) Zirconium tetraethoxide (Zr (OCH) ₃ CH ₂ ) ₄ ) Zirconium tetraisobutoxide (Zr (i-OC) ₄ H ₉ ) ₄ ) Zirconium tetra-n-butoxide (Zr (OC) ₄ H ₉ ) ₄ ) Zirconium triethoxy methoxide (Zr (OCH) ₃ )(OCH ₃ CH ₂ ) ₃ ) Zirconium dimethoxy diethoxide (Zr (OCH) ₃ ) ₂ (OCH ₃ CH ₂ ) ₂ ) Zirconium trimethoxyethoxide (Zr (OCH) ₃ ) ₃ （OCH ₃ CH ₂ ) Zirconium triisobutoxide methoxide (Zr (OCH) ₃ )(i-OC ₄ H ₉ ) ₃ ) Zirconium diisobutoxide dimethoxy (Zr (OCH) ₃ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Zirconium trimethoxy isobutoxy (Zr (OCH) ₃ ) ₃ (i-C ₄ H ₉ ) Zirconium triisobutoxide (Zr (OCH) ₃ CH ₂ )(i-OC ₄ H ₉ ) ₃ ) Zirconium diisobutoxide (Zr (OCH) ₃ CH ₂ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Zirconium triethoxy isobutoxide (Zr (OCH) ₃ CH ₂ ) ₃ (i-OC ₄ H ₉ ) Zirconium tri-n-butoxymethoxide (Zr (OCH) ₃ )(OC ₄ H ₉ ) ₃ ) Di-n-Butoxydimethoxyzirconium (Zr (OCH) ₃ ) ₂ (OC ₄ H ₉ ) ₂ ) Zirconium trimethoxy-n-butoxide (Zr (OCH) ₃ ) ₃ (OC ₄ H ₉ ) Zirconium tri-n-butoxyethoxy (Zr (OCH) ₃ CH ₂ )(OC ₄ H ₉ ) ₃ ) di-n-Butoxydiethoxy zirconium (Zr (OCH) ₃ CH ₂ ) ₂ (OC ₄ H ₉ ) ₂ ) Zirconium triethoxy n-butoxide (Zr (OCH) ₃ CH ₂ ) ₃ (OC ₄ H ₉ ) Etc.;

hafnium tetramethoxyate (Hf (OCH) ₃ ) ₄ ) Hafnium tetraethoxide (Hf (OCH) ₃ CH ₂ ) ₄ ) Hafnium tetra-isobutoxide (Hf (i-OC) ₄ H ₉ ) ₄ ) Hafnium tetra-n-butoxide (Hf (OC) ₄ H ₉ ) ₄ ) Hafnium triethoxy methoxy (Hf (OCH) ₃ )(OCH ₃ CH ₂ ) ₃ ) Hafnium dimethoxy diethoxide (Hf (OCH) ₃ ) ₂ (OCH ₃ CH ₂ ) ₂ ) Hafnium trimethoxyethoxide (Hf (OCH) ₃ ) ₃ (OCH ₃ CH ₂ ) Hafnium triisobutoxide (Hf (OCH) ₃ )(i-OC ₄ H ₉ ) ₃ ) Hafnium diisobutoxide (Hf (OCH) ₃ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Hafnium trimethoxy isobutoxide (Hf (OCH) ₃ ) ₃ (i-OC ₄ H ₉ ) Hafnium triisobutoxide (Hf (OCH) ₃ CH ₂ )(i-OC ₄ H ₉ ) ₃ ) Hafnium diisobutoxide (Hf (OCH) ₃ CH ₂ ) ₂ (i-OC ₄ H ₉ ) ₂ ) Hafnium triethoxy isobutoxide (Hf (OCH) ₃ CH ₂ ) ₃ (i-C ₄ H ₉ ) Hafnium tri-n-butoxymethoxide (Hf (OCH) ₃ )(OC ₄ H ₉ ) ₃ ) Di-n-Butoxydimethoxy hafnium (Hf (OCH) ₃ ) ₂ (OC ₄ H ₉ ) ₂ ) Hafnium trimethoxy-n-butoxide (Hf (OCH) ₃ ) ₃ (OC ₄ H ₉ ) Hafnium tri-n-butoxyethoxide (Hf (OCH) ₃ CH ₂ )(OC ₄ H ₉ ) ₃ ) Hafnium di-n-butoxide (Hf (OCH) ₃ CH ₂ ) ₂ (OC ₄ H ₉ ) ₂ ) Hafnium triethoxy n-butoxide (Hf (OCH) ₃ CH ₂ ) ₃ (OC ₄ H ₉ ) And the like.

Examples of the group IVB metal alkyl halide include trimethyltitanium chloride (TiCl (CH) ₃ ) ₃ ) Titanium triethylchloride (TiCl (CH) ₃ CH ₂ ) ₃ ) Triisobutyltitanium chloride (TiCl (i-C) ₄ H ₉ ) ₃ ) Tri-n-butyl titanium chloride (TiCl (C) ₄ H ₉ ) ₃ ) Dimethyl titanium dichloride (TiCl) ₂ (CH ₃ ) ₂ ) Titanium diethyl dichloride (TiCl) ₂ (CH ₃ CH ₂ ) ₂ ) Diisobutyl titanium dichloride (TiCl) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butyl titanium chloride (TiCl (C) ₄ H ₉ ) ₃ ) Titanium methyl trichloride (Ti (CH) ₃ )Cl ₃ ) Titanium ethyl trichloride (Ti (CH) ₃ CH ₂ )Cl ₃ ) Titanium isobutyl trichloride (Ti (i-C) ₄ H ₉ )Cl ₃ ) N-butyl titanium trichloride (Ti (C) ₄ H ₉ )Cl ₃ ）；

Trimethyl titanium bromide (TiBr (CH) ₃ ) ₃ ) Triethyltitanium bromide (TiBr (CH) ₃ CH ₂ ) ₃ ) Triisobutyl titanium bromide (TiBr (i-C) ₄ H ₉ ) ₃ ) Tri-n-butyl titanium bromide (TiBr (C) ₄ H ₉ ) ₃ ) Dimethyl titanium dibromide (TiBr) ₂ (CH ₃ ) ₂ ) Titanium diethyl dibromide (TiBr) ₂ (CH ₃ CH ₂ ) ₂ ) Diisobutyl titanium dibromide (TiBr) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butyl titanium bromide (TiBr (C) ₄ H ₉ ) ₃ ) Methyl titanium tribromide (Ti (CH) ₃ )Br ₃ ) Titanium ethyltribromide (Ti (CH) ₃ CH ₂ )Br ₃ ) Titanium isobutyl tribromide (Ti (i-C) ₄ H ₉ )Br ₃ ) N-butyl titanium tribromide (Ti (C) ₄ H ₉ )Br ₃ ）；

Trimethylzirconium chloride (ZrCl (CH) ₃ ) ₃ ) Zirconium triethyl chloride (ZrCl (CH) ₃ CH ₂ ) ₃ ) Triisobutylzirconium chloride (ZrCl (i-C) ₄ H ₉ ) ₃ ) Tri-n-butylzirconium chloride (ZrCl (C) ₄ H ₉ ) ₃ ) Zirconium dimethyldichloride (ZrCl) ₂ (CH ₃ ) ₂ ) Zirconium diethyl dichloride (ZrCl) ₂ (CH ₃ CH ₂ ) ₂ ) Diisobutylzirconium dichloride (ZrCl) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butylzirconium chloride (ZrCl (C) ₄ H ₉ ) ₃ ) Zirconium methyl trichloride (Zr (CH) ₃ )Cl ₃ ) Zirconium ethyl trichloride (Zr (CH) ₃ CH ₂ )Cl ₃ ) Zirconium isobutyl trichloride (Zr (i-C) ₄ H ₉ )Cl ₃ ) N-butyl zirconium trichloride (Zr (C) ₄ H ₉ )Cl ₃ ）；

Zirconium trimethyl bromide (ZrBr (CH) ₃ ) ₃ ) Zirconium triethylbromide (ZrBr (CH) ₃ CH ₂ ) ₃ ) Zirconium triisobutylbromide (ZrBr (i-C) ₄ H ₉ ) ₃ ) Tri-n-butylzirconium bromide (ZrBr (C) ₄ H ₉ ) ₃ ) Zirconium dimethyl dibromide (ZrBr) ₂ (CH ₃ ) ₂ ) Zirconium diethyl bromide (ZrBr) ₂ (CH ₃ CH ₂ ) ₂ ) Diisobutyl zirconium dibromide (ZrBr) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butylzirconium bromide (ZrBr (C) ₄ H ₉ ) ₃ ) Zirconium methyl tribromide (Zr (CH) ₃ )Br ₃ ) Zirconium ethyl tribromide (Zr (CH) ₃ CH ₂ )Br ₃ ) Zirconium isobutyl tribromide (Zr (i-C) ₄ H ₉ )Br ₃ ) Zirconium n-butyl tribromide (Zr (C) ₄ H ₉ )Br ₃ ）；

Hafnium trimethyl chloride (HfCl (CH) ₃ ) ₃ ) Hafnium triethylchloride (HfCl (CH) ₃ CH ₂ ) ₃ ) Hafnium triisobutyl chloride (HfCl (i-C) ₄ H ₉ ) ₃ ) Tri-n-butyl hafnium chloride (HfCl (C) ₄ H ₉ ) ₃ ) Hafnium dimethyl dichloride (HfCl) ₂ (CH ₃ ) ₂ ) Hafnium diethyl dichloride (HfCl) ₂ (CH ₃ CH ₂ ) ₂ ) Hafnium diisobutyl dichloride (HfCl) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butyl hafnium chloride (HfCl (C) ₄ H ₉ ) ₃ ) Hafnium methyltrichloride (Hf (CH) ₃ )Cl ₃ ) Hafnium ethyl trichloride (Hf (CH) ₃ CH ₂ )Cl ₃ ) Hafnium isobutyl trichloride (Hf (i-C) ₄ H ₉ )Cl ₃ ) N-butyl hafnium trichloride (Hf (C) ₄ H ₉ )Cl ₃ ）；

Hafnium trimethyl bromide (HfBr (CH) ₃ ) ₃ ) Hafnium triethylbromide (HfBr (CH) ₃ CH ₂ ) ₃ ) Hafnium triisobutyl bromide (HfBr (i-C) ₄ H ₉ ) ₃ ) Tri-n-butyl hafnium bromide (HfBr (C) ₄ H ₉ ) ₃ ) Hafnium dimethyl bromide (HfBr) ₂ (CH ₃ ) ₂ ) Hafnium diethyl bromide (HfBr) ₂ (CH ₃ CH ₂ ) ₂ ) Hafnium diisobutyl dibromide (HfBr) ₂ (i-C ₄ H ₉ ) ₂ ) Tri-n-butyl hafnium bromide (HfBr (C) ₄ H ₉ ) ₃ ) Hafnium methyl tribromide (Hf (CH) ₃ )Br ₃ ) Hafnium ethyltribromide (Hf (CH) ₃ CH ₂ )Br ₃ ) Hafnium isobutyl tribromide (Hf (i-C) ₄ H ₉ )Br ₃ ) N-butyl hafnium tribromide (Hf (C) ₄ H ₉ )Br ₃ ）。

Examples of the group IVB metal alkoxyhalides include titanium trimethoxychloride (TiCl (OCH) ₃ ) ₃ ) Titanium triethoxy chloride (TiCl (OCH) ₃ CH ₂ ) ₃ ) Titanium triisobutoxide chloride (TiCl (i-OC) ₄ H ₉ ) ₃ ) Titanium tri-n-butoxide chloride (TiCl (OC) ₄ H ₉ ) ₃ ) Titanium dimethoxy dichloride (TiCl) ₂ (OCH ₃ ) ₂ ) Titanium diethoxy dichloride (TiCl) ₂ (OCH ₃ CH ₂ ) ₂ ) Titanium diisobutoxide dichloride (TiCl) ₂ (i-OC ₄ H ₉ ) ₂ ) Titanium tri-n-butoxide chloride (TiCl (OC) ₄ H ₉ ) ₃ ) Titanium methoxytrichloride (Ti (OCH) ₃ )Cl ₃ ) Titanium ethoxytrichloride (Ti (OCH) ₃ CH ₂ )Cl ₃ ) Titanium isobutoxy trichloride (Ti (i-C) ₄ H ₉ )Cl ₃ ) Titanium n-butoxide trichloride (Ti (OC) ₄ H ₉ )Cl ₃ ）；

Trimethoxytitanium bromide (TiBr (OCH) ₃ ) ₃ ) Titanium triethoxybromide (TiBr (OCH) ₃ CH ₂ ) ₃ ) Titanium triisobutoxide bromide (TiBr (i-OC) ₄ H ₉ ) ₃ ) Titanium tri-n-butoxide bromide (TiBr (OC) ₄ H ₉ ) ₃ ) Titanium dimethoxy dibromide (TiBr) ₂ (OCH ₃ ) ₂ ) Titanium diethoxy dibromide (TiBr) ₂ (OCH ₃ CH ₂ ) ₂ ) Second partTitanium dibromide isobutoxide (TiBr) ₂ (i-OC ₄ H ₉ ) ₂ ) Titanium tri-n-butoxide bromide (TiBr (OC) ₄ H ₉ ) ₃ ) Titanium methoxytribromide (Ti (OCH) ₃ )Br ₃ ) Titanium ethoxytribromide (Ti (OCH) ₃ CH ₂ )Br ₃ ) Titanium isobutoxy tribromide (Ti (i-C) ₄ H ₉ )Br ₃ ) n-Butoxytitanium tribromide (Ti (OC) ₄ H ₉ )Br ₃ ）；

Zirconium trimethoxychloride (ZrCl (OCH) ₃ ) ₃ ) Zirconium triethoxy chloride (ZrCl (OCH) ₃ CH ₂ ) ₃ ) Zirconium triisobutoxide chloride (ZrCl (i-OC) ₄ H ₉ ) ₃ ) Zirconium tri-n-butoxide chloride (ZrCl (OC) ₄ H ₉ ) ₃ ) Zirconium dimethoxy dichloride (ZrCl) ₂ (OCH ₃ ) ₂ ) Zirconium diethoxy dichloride (ZrCl) ₂ (OCH ₃ CH ₂ ) ₂ ) Zirconium diisobutoxy dichloride (ZrCl) ₂ (i-OC ₄ H ₉ ) ₂ ) Zirconium tri-n-butoxide chloride (ZrCl (OC) ₄ H ₉ ) ₃ ) Zirconium methoxytrichloride (Zr (OCH) ₃ )Cl ₃ ) Zirconium ethoxy trichloride (Zr (OCH) ₃ CH ₂ )Cl ₃ ) Zirconium isobutoxy trichloride (Zr (i-C) ₄ H ₉ )Cl ₃ ) Zirconium trichloride n-butoxy (Zr (OC) ₄ H ₉ )Cl ₃ ）；

Zirconium trimethoxybromide (ZrBr (OCH) ₃ ) ₃ ) Zirconium triethoxy bromide (ZrBr (OCH) ₃ CH ₂ ) ₃ ) Zirconium triisobutoxide bromide (ZrBr (i-OC) ₄ H ₉ ) ₃ ) Zirconium tri-n-butoxide bromide (ZrBr (OC) ₄ H ₉ ) ₃ ) Zirconium dimethoxy dibromide (ZrBr) ₂ (OCH ₃ ) ₂ ) Zirconium diethoxy dibromide (ZrBr) ₂ (OCH ₃ CH ₂ ) ₂ ) Zirconium diisobutoxy dibromide (ZrBr) ₂ (i-OC ₄ H ₉ ) ₂ ) Boc (Tri-n-Butoxygen)Zirconium yl bromide (ZrBr (OC) ₄ H ₉ ) ₃ ) Zirconium methoxytribromide (Zr (OCH) ₃ )Br ₃ ) Zirconium ethoxy tribromide (Zr (OCH) ₃ CH ₂ )Br ₃ ) Zirconium isobutoxy tribromide (Zr (i-C) ₄ H ₉ )Br ₃ ) Zirconium tribromide of n-butoxy (Zr (OC) ₄ H ₉ )Br ₃ ）；

Hafnium trimethoxychloride (HfCl (OCH) ₃ ) ₃ ) Hafnium chloride triethoxide (HfCl (OCH) ₃ CH ₂ ) ₃ ) Hafnium triisobutoxide chloride (HfCl (i-OC) ₄ H ₉ ) ₃ ) Hafnium tri-n-butoxide chloride (HfCl (OC) ₄ H ₉ ) ₃ ) Hafnium dimethoxy dichloride (HfCl) ₂ (OCH ₃ ) ₂ ) Hafnium diethoxy dichloride (HfCl) ₂ (OCH ₃ CH ₂ ) ₂ ) Hafnium diisobutoxy dichloride (HfCl) ₂ (i-OC ₄ H ₉ ) ₂ ) Hafnium tri-n-butoxide chloride (HfCl (OC) ₄ H ₉ ) ₃ ) Hafnium methoxytrichloride (Hf (OCH) ₃ )Cl ₃ ) Hafnium ethoxy trichloride (Hf (OCH) ₃ CH ₂ )Cl ₃ ) Hafnium isobutoxy trichloride (Hf (i-C) ₄ H ₉ )Cl ₃ ) Hafnium n-butoxide trichloride (Hf (OC) ₄ H ₉ )Cl ₃ ）；

Hafnium trimethoxybromide (HfBr (OCH) ₃ ) ₃ ) Hafnium triethoxy bromide (HfBr (OCH) ₃ CH ₂ ) ₃ ) Hafnium triisobutoxide bromide (HfBr (i-OC) ₄ H ₉ ) ₃ ) Hafnium tri-n-butoxide bromide (HfBr (OC) ₄ H ₉ ) ₃ ) Hafnium dimethoxy dibromide (HfBr) ₂ (OCH ₃ ) ₂ ) Hafnium di-ethoxy dibromide (HfBr) ₂ (OCH ₃ CH ₂ ) ₂ ) Hafnium diisobutylbromide (HfBr) ₂ (i-OC ₄ H ₉ ) ₂ ) Hafnium tri-n-butoxide bromide (HfBr (OC) ₄ H ₉ ) ₃ ) Hafnium methoxytribromide (Hf (OCH) ₃ )Br ₃ ) Hafnium ethoxy tribromide (Hf (OCH) ₃ CH ₂ )Br ₃ ) Hafnium isobutoxy tribromide (Hf (i-C) ₄ H ₉ )Br ₃ ) Hafnium n-butoxide tribromide (Hf (OC) ₄ H ₉ )Br ₃ ）。

When the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment reaction may be directly performed using the chemical treatment agent. When the chemical treatment agent is solid at ordinary temperature, it is preferable to use the chemical treatment agent in the form of a solution for the convenience of metering and handling. Of course, when the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment agent may be used in a solution form as needed, and is not particularly limited.

In preparing the solution of the chemical treatment agent, the solvent used at this time is not particularly limited as long as it can dissolve the chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the composite carrier.

Specifically, C may be mentioned _5-12 Paraffin, C _5-12 Cycloalkane, halogenated C _5-12 Paraffins and 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, and among these, pentane, hexane, decane, and cyclohexane are preferable, and hexane is most preferable.

The concentration of the chemical treatment agent in the solution is not particularly limited, and may be appropriately selected as required, as long as it can perform the chemical treatment reaction with a predetermined amount of the chemical treatment agent. As described above, if the chemical treatment agent is in a liquid state, the treatment may be performed directly using the chemical treatment agent, but it may be used after being prepared as a solution of the chemical treatment agent.

Generally, the molar concentration of the chemical treatment agent in the solution is set to 0.01 to 1.0mol/L, but the chemical treatment agent is not limited thereto.

According to the present invention, the chemical treatment reaction may be performed by, for example, bringing the composite support into contact with the chemical treatment agent in the presence of a solvent (also referred to as a chemical treatment solvent).

According to the present invention, the chemical treatment solvent is not particularly limited as long as it can dissolve the chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the composite carrier.

Specifically, the solvent for chemical treatment includes C _5-12 Paraffin, C _5-12 Cycloalkane, halogenated C _5-12 Paraffins and 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, and among these, pentane, hexane, decane, and cyclohexane are preferable, and hexane is most preferable.

According to the present invention, the amount of the chemical treatment solvent to be used may be such that the ratio of the composite carrier to the chemical treatment solvent is 1 g/1 to 100ml, preferably 1 g/2 to 40ml, but is not limited thereto. In addition, when the chemical treatment agent is used in the form of a solution as described above, the amount of the chemical treatment solvent may be appropriately reduced according to the actual situation, but is not particularly limited.

According to the invention, the chemical treatment agent is used in such an amount that the molar ratio of the composite support in terms of Mg element to the chemical treatment agent in terms of group IVB metal element is 1:0.01 to 1, preferably 1:0.01 to 0.50, more preferably 1:0.10 to 0.30.

According to one embodiment of the present invention, the chemical treatment reaction is performed by contacting the composite support with the chemical treatment agent in the presence of the solvent for chemical treatment.

The contacting may be performed by, for example, adding the composite carrier to the chemical treatment solvent with stirring, simultaneously or subsequently adding (preferably, dropwise) the chemical treatment agent or a solution of the chemical treatment agent, and after the completion of the addition, continuing stirring and reacting at 0 to 100 ℃ (preferably, 20 to 80 ℃). The reaction time in this case is not particularly limited, and examples thereof include 0.5 to 8 hours, preferably 1 to 4 hours.

After the chemical treatment reaction is finished, a product (modified composite carrier) subjected to chemical treatment can be obtained through filtration, washing and drying.

According to the present invention, the filtration, washing and drying may be performed using a conventional method, wherein the washing solvent may be the same solvent as the chemical treatment solvent. The washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times, as required.

According to the present invention, the supported non-metallocene catalyst is obtained by contacting a non-metallocene complex with the modified composite support in the presence of a second solvent.

According to the present invention, the term "non-metallocene complex" is a single-site olefin polymerization catalyst with respect to a metallocene catalyst, which does not contain cyclopentadienyl groups such as a metallocene ring, fluorene ring or indene ring or derivatives thereof in the structure, and which is capable of exhibiting olefin polymerization catalytic activity when combined with a cocatalyst such as those described below (thus the non-metallocene complex is sometimes also referred to as a non-metallocene olefin polymerizable complex). The compound comprises a central metal atom and at least one multidentate ligand (preferably a tridentate ligand or more) bound to the central metal atom in a coordination bond, and the term "non-metallocene ligand" is the aforementioned multidentate ligand.

According to the invention, the non-metallocene complex is selected from compounds having the following chemical formula:

。

according to the chemical formula, the ligands forming a coordination bond with the central metal atom M include n groups X and M multidentate ligands (structural formulas in brackets). Depending on the chemical structure of the polydentate ligand, groups A, D and E (coordinating groups) form a coordination bond with the central metal atom M through the coordinating atoms (e.g., N, O, S, se and P heteroatoms) contained in these groups. In the present invention, the central metal atom M is also referred to as active metal, and the amount of catalyst is generally expressed as the amount of central metal atom M in the non-metallocene complex.

According to the invention, the total number of negative charges carried by all ligands (including the group X and the multidentate ligand) is the same absolute value as the positive charge carried by the central metal atom M.

In a more specific embodiment, the non-metallocene complex is selected from the group consisting of compounds (a) and (B) having the following chemical structural formula.

In a more specific embodiment, the non-metallocene complex is selected from the group consisting of compounds (A-1) to (A-4) and compounds (B-1) to (B-4) having the following chemical structural formula.

/>

In all of the above chemical structural formulas,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

m is a central metal atom selected from the group consisting of metal atoms of groups III to XI of the periodic Table of elements, preferably a metal atom of group IVB, for example, ti (IV), zr (IV), hf (IV), cr (III), fe (III), ni (II), pd (II) or Co (II);

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

x is selected from halogen, hydrogen atom, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ A 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, or a tin-containing group, and a plurality of X's may be the same or different, or may be bonded or looped to each other;

A is selected from oxygen atom, sulfur atom, seleniumAn atom(s),、-NR ²³ R ²⁴ 、-N(O)R ²⁵ R ²⁶ 、/>、-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ OR ³¹ Of sulfone, sulfoxide or-Se (O) R ³⁹ Wherein N, O, S, se and P are each an atom for coordination;

b is selected from nitrogen atom, nitrogen-containing group, phosphorus-containing group or C ₁ -C ₃₀ A hydrocarbon group;

d is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C ₁ -C ₃₀ A hydrocarbyl, sulfone, or sulfoxide group, wherein N, O, S, se and P are each a coordinating atom;

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 a cyano group (-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 an atom for coordination;

g is selected from C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon or inert functional groups;

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, wherein N, O, S, se and P are each an atom for coordination;

z is selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, phosphorus-containing groups or cyano groups (-CN), for example, -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 or-Se (O) R ³⁹ Wherein N, O, S, se and P are each an atom for coordination;

-represents a single bond or a double bond;

-represents a covalent bond or an ionic bond;

-represents a coordinate bond, a covalent bond or an ionic bond.

R ¹ To R ⁴ 、R ⁶ To R ²¹ Each independently selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred ₂ Cl and-CH ₂ CH ₂ Cl) or inert functional groups. R is R ²² To R ³⁶ 、R ³⁸ And R is ³⁹ Each independently selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred ₂ Cl and-CH ₂ CH ₂ Cl). The above groups may be the same or different from each other, wherein adjacent groups such as R ¹ And R is R ² ，R ⁶ And R is R ⁷ ，R ⁷ And R is R ⁸ ，R ⁸ And R is R ⁹ ，R ¹³ And R is R ¹⁴ ，R ¹⁴ And R is R ¹⁵ ，R ¹⁵ And R is R ¹⁶ ，R ¹⁸ And R is R ¹⁹ ，R ¹⁹ And R is R ²⁰ ，R ²⁰ And R is R ²¹ ，R ²³ And R is R ²⁴ Or R ²⁵ And R is R ²⁶ Etc. may be bonded to each other to form a bond or a ring, preferably an aromatic ring, such as an unsubstituted benzene ring or a ring having 1 to 4C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ Hydrocarbyl (of which halogenated hydrocarbyl groups such as-CH are preferred ₂ Cl and-CH ₂ CH ₂ Cl) substituted benzene ring, and

R ⁵ selected from lone pair electrons on nitrogen, hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, selenium-containing groups, or phosphorus-containing groups. When R is ⁵ R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group ⁵ The N, O, S, P and Se of (a) may be used as the coordinating atom (coordinating with the central metal atom M).

At the bookIn the context of the present invention, examples of inert functional groups include groups selected from the group consisting of halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C ₁ -C ₁₀ Ester or nitro (-NO) ₂ ) At least one of (C) and the like, but generally does not include C ₁ -C ₃₀ Hydrocarbyl and substituted C ₁ -C ₃₀ A hydrocarbon group.

In the context of the present invention, the inert functional group has the following characteristics, limited by the chemical structure of the multidentate ligand of the present invention:

(1) Does not interfere with the coordination process of the group A, D, E, F, Y or Z with the central metal atom M, and

(2) The ability to coordinate to the central metal atom M is lower than the A, D, E, F, Y and Z groups and does not displace the existing coordination of these groups to the central metal atom M.

In accordance with the invention, in all of the formulae described above, any adjacent two or more groups, such as R, as the case may be ²¹ With a group Z, or R ¹³ With a group Y, which may be bound to each other to form a ring, preferably C comprising heteroatoms from said group Z or Y ₆ -C ₃₀ Aromatic heterocyclic ring such as pyridine ring and the like, wherein the aromatic heterocyclic ring is optionally substituted with 1 or more groups selected from C ₁ -C ₃₀ Hydrocarbyl and substituted C ₁ -C ₃₀ The substituent of the hydrocarbon group is substituted.

In the context of the present invention, the halogen is selected from F, cl, br or I. The nitrogen-containing group is selected from、-NR ²³ R ²⁴ 、-T-NR ²³ R ²⁴ or-N (O) R ²⁵ R ²⁶ . The phosphorus-containing group is selected from->、-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ R ³¹ or-P (O) R ³² (OR ³³ ). The said containsThe oxygen radical is selected from hydroxy, -OR ³⁴ and-T-OR ³⁴ . The sulfur-containing group is selected from the group consisting of-SR ³⁵ 、-T-SR ³⁵ 、-S(O)R ³⁶ or-T-SO ₂ R ³⁷ . The selenium-containing group is selected from the group consisting of-Ser ³⁸ 、-T-SeR ³⁸ 、-Se(O)R ³⁹ or-T-Se (O) R ³⁹ . The radicals T being selected from C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group. The R is ³⁷ Selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group.

In the context of the present invention, the C ₁ -C ₃₀ The hydrocarbon radical being selected from C ₁ -C ₃₀ Alkyl (preferably C ₁ -C ₆ Alkyl, such as isobutyl), C ₇ -C ₃₀ Alkylaryl groups (such as tolyl, xylyl, diisobutylphenyl, and the like), C ₇ -C ₃₀ Aralkyl (e.g. benzyl), C ₃ -C ₃₀ Cyclic alkyl, C ₂ -C ₃₀ Alkenyl, C ₂ -C ₃₀ Alkynyl, C ₆ -C ₃₀ Aryl (e.g., phenyl, naphthyl, anthracenyl, etc.), C ₈ -C ₃₀ Condensed ring groups or C ₄ -C ₃₀ A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from nitrogen atoms, oxygen atoms, or sulfur atoms, such as pyridyl, pyrrolyl, furyl, thienyl, or the like.

According to the invention, in the context of the present invention, the said C, depending on the specific case of the relevant group to which it is bound ₁ -C ₃₀ Hydrocarbyl is sometimes referred to as C ₁ -C ₃₀ Hydrocarbadiyl (divalent radicals, otherwise known as C ₁ -C ₃₀ Hydrocarbylene) or C ₁ -C ₃₀ Hydrocarbon tri (trivalent groups), as will be apparent to those skilled in the art.

In the context of the present invention, the substituted C ₁ -C ₃₀ Hydrocarbyl refers to C bearing one or more inert substituents ₁ -C ₃₀ A hydrocarbon group. By inert substituents is meant that these substituents are substituted for the aforementioned coordinating groups (meaning the aforementioned groups A, D, E, F, Y and Z, or optionally alsoComprising a group R ⁵ ) No substantial interference with the coordination process of the central metal atom M; in other words, these substituents have no ability or opportunity (e.g., affected by steric hindrance, etc.) to undergo a coordination reaction with the central metal atom M to form a coordination bond, as limited by the chemical structure of the polydentate ligand of the present invention. In general, the inert substituents are selected, for example, from halogen or C ₁ -C ₃₀ Alkyl (preferably C ₁ -C ₆ Alkyl groups such as isobutyl).

In the context of the present invention, the boron-containing group is selected from BF ₄ ^- 、(C ₆ F ₅ ) ₄ B ^- Or (R) ⁴⁰ BAr ₃ ) ^- The method comprises the steps of carrying out a first treatment on the surface of the The aluminum-containing group is selected from aluminum alkyls, alPh ₄ ^- 、AlF ₄ ^- 、AlCl ₄ ^- 、AlBr ₄ ^- 、AlI ₄ ^- Or R is ⁴¹ AlAr ₃ ^- The method comprises the steps of carrying out a first treatment on the surface of the The silicon-containing group is selected from-SiR ⁴² R ⁴³ R ⁴⁴ or-T-SiR ⁴⁵ The method comprises the steps of carrying out a first treatment on the surface of the The germanium-containing group is selected from-GeR ⁴⁶ R ⁴⁷ R ⁴⁸ or-T-GeR ⁴⁹ The method comprises the steps of carrying out a first treatment on the surface of the The tin-containing group is selected from-SnR ⁵⁰ R ⁵¹ R ⁵² 、-T-SnR ⁵³ or-T-Sn (O) R ⁵⁴ Wherein Ar represents C ₆ -C ₃₀ Aryl groups. R is R ⁴⁰ To R ⁵⁴ Each independently selected from hydrogen, C as described above ₁ -C ₃₀ Hydrocarbyl or substituted C as previously described ₁ -C ₃₀ Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or a ring. Wherein the radicals T are as defined above.

Examples of the non-metallocene complex include the following compounds:

/>

。/>

the non-metallocene complex is preferably selected from the following compounds:

。

the non-metallocene complex is further preferably selected from the following compounds:

。

more preferably, the non-metallocene complex is selected from the following compounds:

。

these non-metallocene complexes may be used singly or in combination of plural kinds in any ratio.

According to the present invention, the polydentate ligand in the non-metallocene complex is not a diether compound commonly used in the art as an electron donor compound.

The non-metallocene complex or the polydentate ligand may be manufactured according to any method known to those skilled in the art. For details of the manufacturing method, see, for example, WO03/010207 and Chinese patents ZL01126323.7 and ZL02110844.7, etc., the entire contents of which are incorporated herein by reference.

According to the invention, the non-metallocene complexes are used, if necessary, in the form of solutions for metering and ease of operation.

In preparing the solution of the non-metallocene complex, the solvent used in this case is not particularly limited as long as the non-metallocene complex can be dissolved. Examples of the solvent include C _6-12 Aromatic hydrocarbons, halogenated C _6-12 Aromatic hydrocarbons, halogenated C _1-10 One or more of alkanes, esters, and ethers. Specific examples thereof include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, methylene chloride, dichloroethane, ethyl acetate, tetrahydrofuran, and the like. Of these, C is preferred _6-12 Aromatic hydrocarbons, methylene chloride and tetrahydrofuran.

In dissolving the non-metallocene complex, stirring may be used as required (the stirring speed is generally 10 to 500 rpm).

According to the invention, it is convenient, but sometimes not limited, for the proportion of the non-metallocene complex to the solvent to be generally from 0.02 to 0.30g/ml, preferably from 0.05 to 0.15 g/ml.

The non-metallocene complex and the modified composite support are contacted in the presence of a second solvent, for example, as follows.

First, the modified composite support is contacted (contact reaction) with the non-metallocene complex in the presence of a second solvent to obtain a second mixed slurry.

In the production of the second mixed slurry, the contact mode and the contact order of the modified composite support and the non-metallocene complex (and the second solvent) are not particularly limited, and examples thereof include a method in which the modified composite support and the non-metallocene complex are mixed first and then the second solvent is added thereto; or a scheme in which the non-metallocene complex is dissolved in the second solvent, thereby producing a non-metallocene complex solution, and then the modified composite support is mixed with the non-metallocene complex solution, and the like, the latter being preferable.

In addition, for producing the second mixed slurry, for example, the contact reaction (with stirring, if necessary) of the modified composite support and the non-metallocene complex in the presence of the second solvent may be carried out at a temperature of from normal temperature to below the boiling point of any solvent used for 0.5 to 24 hours, preferably 1 to 8 hours, more preferably 2 to 6 hours.

At this time, the second mixed slurry obtained is a slurry-like system. Although not necessary, in order to ensure uniformity of the system, the second mixed slurry is preferably subjected to closed standing for a certain period of time (2 to 48 hours, preferably 4 to 24 hours, most preferably 6 to 18 hours) after the preparation.

According to the present invention, the second solvent (hereinafter, sometimes referred to as a solvent for dissolving the non-metallocene complex) is not particularly limited as long as it can dissolve the non-metallocene complex when the second mixed slurry is produced or the contacting is performed.

Examples of the second solvent include C _6-12 Aromatic hydrocarbons, halogenated C _6-12 Aromatic hydrocarbon, C _5-12 Paraffin, halogenated C _1-10 One or more of paraffins and ethers. Specific examples thereof include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, hexane, methylene chloride, dichloroethane, tetrahydrofuran, and the like. Of these, C is preferred _6-12 Aromatic hydrocarbons, methylene chloride and tetrahydrofuran, most preferably methylene chloride.

In the production of the second mixed slurry or the non-metallocene complex solution, stirring may be used as required (the stirring speed is generally 10 to 500 rpm).

According to the present invention, the amount of the second solvent is not limited in any way as long as it is an amount sufficient to achieve sufficient contact of the modified composite support with the non-metallocene complex. For example, it is convenient that the proportion of the non-metallocene complex relative to the second solvent is generally in the range of 0.01 to 0.25g/ml, preferably 0.05 to 0.16g/ml, but is sometimes not limited thereto.

In one embodiment of the present invention, by directly drying the second mixed slurry, a solid product with good fluidity, i.e., the supported non-metallocene catalyst of the present invention, can be obtained.

In one embodiment of the invention, the second mixed slurry is not required to be dried and can be used directly as a supported non-metallocene catalyst.

At this time, the direct drying may be performed by a conventional method such as drying under an inert gas atmosphere, drying under a vacuum atmosphere, or heat drying under a vacuum atmosphere, etc., with heat drying under a vacuum atmosphere being preferred. The drying is generally carried out at a temperature 5 to 15 ℃ lower (generally 30 to 160 ℃, preferably 60 to 130 ℃) than the boiling point of any solvent contained in the mixed slurry, and the drying time is generally 2 to 24 hours, but is not limited thereto in some cases.

According to the present invention, as the amount of the first solvent, the ratio of the magnesium compound to the first solvent is made to be 1 mol:75-400 ml, preferably 1 mol:150-300 ml, more preferably 1 mol:200-250 ml.

According to the invention, as the amount of the alcohol, the molar ratio of the magnesium compound to the alcohol in terms of Mg element is 1:0.02-4.00, preferably 1:0.05-3.00, more preferably 1:0.10-2.50.

According to the present invention, the porous carrier is used in such an amount that the mass ratio of the magnesium compound to the porous carrier, calculated as a solid of the magnesium compound, is 1:0.1 to 20, preferably 1:0.5 to 10, more preferably 1:1 to 5.

According to the invention, the precipitant is used in an amount such that the volume ratio of the precipitant to the first solvent is 1:0.2-5, preferably 1:0.5-2, more preferably 1:0.8-1.5.

According to the present invention, the chemical treatment agent is used in such an amount that the molar ratio of the composite support in terms of Mg element to the chemical treatment agent in terms of group IVB metal element is 1:0.01 to 1, preferably 1:0.01 to 0.50, more preferably 1:0.10 to 0.30.

According to the invention, the non-metallocene complex is used in such an amount that the molar ratio of the composite support to the non-metallocene complex, calculated as Mg element, is 1:0.01 to 1, preferably 1:0.04 to 0.4, more preferably 1:0.08 to 0.2.

It is known to those skilled in the art that all of the process steps described above are preferably carried out under substantially anhydrous and oxygen-free conditions. As used herein, substantially anhydrous and oxygen-free means that the water and oxygen content of the system is continuously less than 100ppm. Moreover, the supported non-metallocene catalysts of the present invention are typically required to be stored for use after preparation in the presence of a micro-positive pressure inert gas (such as nitrogen, argon, helium, etc.) under closed conditions.

In the present invention, unless otherwise specified, the amount of the supported non-metallocene catalyst is expressed as the amount of the group IVB active metal element.

According to the invention, the cocatalyst is selected from one or more of aluminoxanes, alkylaluminums or haloalkylaluminums.

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

In the above formula, the radicals R are identical or different (preferably identical) from one another and are each independently selected from C ₁ -C ₈ Alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl; n is any integer in the range of 1-50, preferably any integer in the range of 10-30.

As the aluminoxane, methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane are preferred, methylaluminoxane and isobutylaluminoxane are further preferred, and methylaluminoxane is most preferred.

These aluminoxanes may be used singly or in combination of plural kinds in any ratio.

Examples of the aluminum alkyl include compounds represented by the following general formula (III):

Al(R) ₃ （III）

wherein the radicals R are identical or different (preferably identical) from one another and are each independently selected from C ₁ -C ₈ Alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl.

Specifically, examples of the aluminum alkyl include trimethylaluminum (Al (CH) ₃ ) ₃ ) Triethylaluminum (Al (CH) ₃ CH ₂ ) ₃ ) Tri-n-propylaluminum (Al (C) ₃ H ₇ ) ₃ ) Triisopropylaluminum (Al (i-C) ₃ H ₇ ) ₃ ) Triisobutylaluminum (Al (i-C) ₄ H ₉ ) ₃ ) Tri-n-butyl aluminum (Al (C) ₄ H ₉ ) ₃ ) Triisopentylaluminum (Al (i-C) ₅ H ₁₁ ) ₃ ) Tri-n-pentylaluminum (Al (C) ₅ H ₁₁ ) ₃ ) Tri-n-hexylaluminum (Al (C) ₆ H ₁₃ ) ₃ ) Triisohexylaluminum (Al (i-C) ₆ H ₁₃ ) ₃ ) Diethyl methylaluminum (Al (CH) ₃ )(CH ₃ CH ₂ ) ₂ ) And dimethylethylaluminum (Al (CH) ₃ CH ₂ ）(CH ₃ ) ₂ ) Among these, trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable, and triethylaluminum and triisobutylaluminum are most preferable.

These aluminum alkyls may be used alone or in combination of plural kinds in any ratio.

Examples of the haloalkylaluminum include a compound represented by the following general formula (III'):

Al(R) _n X _3-n （III'）

Wherein the radicals R are identical or different (preferably identical) from one another and are each independently selected from C ₁ -C ₈ Alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl; x represents fluorine, chlorine, bromine or iodine; n meterEither 1 or 2.

Specifically, examples of the haloalkylaluminum include dimethylaluminum chloride (Al (CH) ₃ ) ₂ Cl), aluminum dichloromethyl (Al (CH) ₃ )Cl ₂ ) Diethylaluminum chloride (Al (CH) ₃ CH ₂ ) ₂ Cl), ethylaluminum dichloride (Al (CH) ₃ CH ₂ )Cl ₂ ) Dipropylaluminum chloride (Al (C) ₃ H ₇ ) ₂ Cl), aluminum dichloropropylate (Al (C) ₃ H ₇ )Cl ₂ ) Di-n-butylaluminum monochloride (Al (C) ₄ H ₉ ) ₂ Cl), n-butylaluminum dichloride (Al (C) ₄ H ₉ )Cl ₂ ) Diisobutylaluminum chloride (Al (i-C) ₄ H ₉ ) ₂ Cl), isobutyl aluminum dichloride (Al (i-C) ₄ H ₉ )Cl ₂ ) Di-n-pentylaluminum monochloride (Al (C) ₅ H ₁₁ ) ₂ Cl), n-pentylaluminum dichloride (Al (C) ₅ H ₁₁ )Cl ₂ ) Diisoamyl aluminum monochloride (Al (i-C) ₅ H ₁₁ ) ₂ Cl), isoamyl aluminum dichloride (Al (i-C) ₅ H ₁₁ )Cl ₂ ) Di-n-hexylaluminum monochloride (Al (C) ₆ H ₁₃ ) ₂ Cl), n-hexylaluminum dichloride (Al (C) ₆ H ₁₃ )Cl ₂ ) Diisohexylaluminum monochloride (Al (i-C) ₆ H ₁₃ ) ₂ Cl), isohexylaluminum dichloride (Al (i-C) ₆ H ₁₃ )Cl ₂ ) Chloromethylethylaluminum (Al (CH) ₃ )(CH ₃ CH ₂ ) Cl), chloromethyl propyl aluminum (Al (CH) ₃ )(C ₃ H ₇ ) Cl), chloromethyl n-butylaluminum (Al (CH) ₃ )(C ₄ H ₉ ) Cl), chloromethyl isobutyl aluminum (Al (CH) ₃ )(i-C ₄ H ₉ ) Cl), ethyl propyl aluminum monochloride (Al (CH) ₂ CH ₃ )(C ₃ H ₇ ) Cl), ethyl-n-butyl-aluminum monochloride (AlCH) ₂ CH ₃ )(C ₄ H ₉ ) Cl), chloromethyl isobutyl aluminum (Al (CH) ₂ CH ₃ )(i-C ₄ H ₉ ) Cl), etc., of which diethylaluminum chloride, ethylene dichloride are preferredPolyaluminum chloride, di-n-butylaluminum chloride, n-butylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, di-n-hexylaluminum chloride, n-hexylaluminum dichloride, further preferably diethylaluminum chloride, ethylaluminum dichloride and di-n-hexylaluminum chloride, and most preferably diethylaluminum chloride.

These haloalkylaluminum may be used alone or in combination of plural kinds in an arbitrary ratio.

In addition, according to the present invention, one kind of the above-mentioned cocatalysts may be used alone, or a plurality of kinds of the above-mentioned cocatalysts may be used in combination in an arbitrary ratio as required, without particular limitation.

In the present invention, unless otherwise specified, the amount of the cocatalyst is expressed as the content of Al element.

According to the present invention, in the process for producing ultra-high molecular weight polyethylene, the polymerization solvent is selected from the group consisting of alkane solvents having a boiling point of 5 to 55℃or mixed alkane solvents having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃.

According to the present invention, examples of the alkane solvent having a boiling point of 5 to 55℃include 2, 2-dimethylpropane (also known as neopentane, having a saturated vapor pressure of 146.63KPa at 20℃and a saturated vapor pressure of 76.7KPa at 20℃and a saturated vapor pressure of 27.83℃and a saturated vapor pressure of 56.5KPa at 20℃and a saturated vapor pressure of cyclopentane (having a boiling point of 49.26℃and a saturated vapor pressure of 34.6KPa at 20 ℃) and a normal pentane (having a boiling point of 25 to 52 ℃) and a saturated vapor pressure of cyclopentane (having a boiling point of 49.26 ℃) are given.

The mixed alkane solvent with saturated vapor pressure of 20-150KPa (preferably 40-110 KPa) at 20 ℃ is mixed solvent formed by mixing different alkane solvents according to proportion, such as hexane and isomer solvents thereof, pentane and isomer solvents thereof, or may be obtained from a solvent rectifying device for cutting the extracted alkane mixture according to the distillation range, preferably pentane and isomer solvents thereof. Specifically, 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 n-pentane, a combination of n-pentane-isopentane-cyclopentane, a combination of n-pentane-n-hexane-isopentane, and the like can be cited. But is not limited thereto. So long as the saturated vapor pressure is 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃.

In one embodiment of the present invention, as the mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃, a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃ which is a mixture of two or more alkanes selected from the group consisting of n-pentane, isopentane, neopentane and cyclopentane, a combination of n-pentane and neopentane, a combination of isopentane and cyclopentane, a combination of neopentane and n-pentane, a combination of n-pentane-isopentane-cyclopentane, a combination of neopentane-isopentane-n-pentane, and the like are preferable. For the ratio of each alkane in the mixed alkane, for example, the molar ratio may be 0.01 to 100:1, preferably 0.1 to 10:1 when two alkane solvents are mixed, and the molar ratio may be 0.01 to 100:1, preferably 0.1 to 10:0.1 to 10:1 when three alkane solvents are mixed, as long as the resulting mixed alkane solvent has a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃. In one embodiment of the present invention, only an alkane solvent having a boiling point of 5 to 55℃or a mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa at 20℃is used as the polymerization solvent.

In the process for the preparation of ultra-high molecular weight polyethylene according to the invention, the ethylene slurry polymerization is carried out at a polymerization temperature of 50-100℃and preferably 60-90 ℃. Wherein, if the ethylene slurry polymerization is carried out at a higher polymerization temperature, a solvent with a higher boiling point can be selected, whereas if the ethylene slurry polymerization is carried out at a lower polymerization temperature, a solvent with a lower boiling point can be selected. It is known that the viscosity average molecular weight of the ultra-high molecular weight polyethylene thus obtained is increased and then decreased with an increase in the polymerization temperature within the polymerization temperature range described in the present invention under the conditions of the ethylene slurry polymerization under the conditions that the polymerization pressure, the main catalyst, the cocatalyst, the solvent, and the like are similarly comparable, and thus the viscosity average molecular weight of the ultra-high molecular weight polyethylene obtained by the ethylene slurry polymerization can be regulated and controlled by the polymerization temperature according to the present invention.

In the process for producing an ultra-high molecular weight polyethylene of the present invention, the polymerization pressure is 0.4 to 4.0MPa, preferably 1.0 to 3.0MPa, more preferably 1.5 to 3.0MPa. Wherein, if the ethylene slurry polymerization is carried out at a higher polymerization temperature, a lower polymerization pressure may be selected, whereas if the ethylene slurry polymerization is carried out at a lower polymerization temperature, a higher polymerization pressure may be selected. Under the condition of ethylene slurry polymerization, under the condition that the polymerization temperature, a main catalyst, a cocatalyst, a solvent and other conditions are similar and comparable, the viscosity average molecular weight of the ultra-high molecular weight polyethylene obtained by the ethylene slurry polymerization is also increased and then reduced along with the increase of the polymerization pressure in the polymerization pressure range disclosed by the invention, so that the viscosity average molecular weight of the ultra-high molecular weight polyethylene obtained by the ethylene slurry polymerization can be regulated and controlled by the polymerization pressure according to the invention.

The alkane solvent with the boiling point of 5-55 ℃ or the mixed alkane solvent with the saturated vapor pressure of 20-150KPa at 20 ℃ is used as a polymerization solvent, thereby providing opportunities and choices for preparing the ultra-high molecular weight polyethylene with different viscosity average molecular weights through ethylene slurry polymerization. For example, an alkane solvent with a lower boiling point (such as n-pentane, isopentane or cyclopentane, etc.) or a mixed alkane solvent with a higher saturated vapor pressure at 20 ℃ (such as a combination of n-pentane and neopentane, a combination of isopentane and neopentane, etc.) is adopted, so that the ethylene slurry polymerization reaction can be easily carried out at a higher polymerization pressure and a lower polymerization temperature, while the alkane solvent with a higher boiling point or a mixed alkane solvent with a lower saturated vapor pressure at 20 ℃ can be adopted, so that the polymerization reaction can be effectively carried out at a lower polymerization pressure and a higher polymerization temperature.

In one embodiment of the present invention, there is provided an ultra-high viscosity average molecular weight polyethylene, wherein the ultra-high viscosity average molecular weight polyethylene has a viscosity average molecular weight of 150 to 1000 Wanke/mol and a bulk density of 0.30 to 0.55g/cm ³ The true density is 0.910-0.950g/cm ³ Titanium content0-3ppm, 0-5ppm of calcium, 0-10ppm of magnesium, 0-30ppm of aluminum, 0-50ppm of chlorine, less than 200ppm of total ash content, 140-152 ℃ of melting point, 40-70% of crystallinity, more than 22MPa of tensile yield strength, more than 32MPa of tensile strength at break, more than 350% of elongation at break and more than 70KJ/m of impact strength ² Young's modulus greater than 300MPa.

In one embodiment of the present invention, there is provided an ultra-high viscosity average molecular weight polyethylene having a viscosity average molecular weight of 300 to 800 Wanke/mol and a bulk density of 0.33 to 0.52g/cm ³ The true density is 0.915-0.945g/cm ³ 0-2ppm of titanium, 0-3ppm of calcium, 0-5ppm of magnesium, 0-20ppm of aluminum, 0-30ppm of chlorine, less than 150ppm of total ash, 142-150 ℃ of melting point, 45-65% of crystallinity, more than 25MPa of tensile yield strength, more than 35MPa of tensile strength at break, more than 400% of elongation at break and more than 75KJ/m of impact strength ² Young's modulus greater than 350MPa.

In one embodiment of the invention, a polymerization preparation method of ultra-high viscosity average molecular weight polyethylene is provided, wherein a supported non-metallocene catalyst is used as a main catalyst, one or more of aluminoxane, aluminum alkyl and aluminum haloalkane is used as a cocatalyst, an alkane solvent with a boiling point of 5-55 ℃ or a mixed alkane solvent with a saturated vapor pressure of 20-150KPa at 20 ℃ is used as a polymerization solvent, the polymerization temperature is 50-100 ℃, the polymerization pressure is 0.4-4.0MPa, ethylene is subjected to slurry polymerization under the condition of ethylene slurry polymerization, and the ethylene slurry polymerization activity is higher than 2-ten-thousand grams of polyethylene per gram of main catalyst.

In one embodiment of the invention, in the polymerization preparation method of the ultra-high viscosity average molecular weight polyethylene, ethylene is subjected to slurry polymerization under the condition of ethylene slurry polymerization at a polymerization temperature of 60-90 ℃ and a polymerization pressure of 1.0-3.0MPa, and the ethylene slurry polymerization activity is higher than 3 ten thousand grams of polyethylene per gram of main catalyst.

In the method for preparing ultra-high molecular weight polyethylene of the present invention, the ethylene slurry polymerization reactor is not limited as long as the ethylene can be brought into contact with the main catalyst and the cocatalyst in the solvent within the polymerization pressure and temperature range described in the present invention, and in order to effectively avoid the adhesion and aggregation of materials, stirring of the kettle-type ethylene slurry may be used. The stirring rate of the stirred tank is not particularly limited as long as the slurry in the reactor can be normally dispersed, and the stirring rate is related to the reactor volume, and in general, the stirring rate is 10 to 1000 rpm, preferably 20 to 500 rpm, as the reactor volume is smaller and the stirring rate is required to be larger.

In the method for producing ultra-high molecular weight polyethylene of the present invention, the polymerization time is not particularly limited, and in a certain polymerization time, the polymerization activity of ethylene slurry polymerization is higher than 2 g of polyethylene per g of main catalyst, preferably the polymerization activity of ethylene slurry polymerization is higher than 3 g of polyethylene per g of main catalyst, and most preferably the polymerization activity is higher than 4 g of polyethylene per g of main catalyst, based on the main catalyst of the present invention.

According to the present invention, the supported non-metallocene catalyst as the main catalyst and one or more of aluminoxane, alkyl aluminum or halogenoalkyl aluminum as the cocatalyst may be added to the polymerization reaction system by adding the main catalyst first, then adding the cocatalyst, or adding the cocatalyst first, then adding the main catalyst, or adding both of them together after contact and mixing, or adding them simultaneously, respectively. When the main catalyst and the cocatalyst are added respectively, the main catalyst and the cocatalyst can be added in the same feeding pipeline in sequence or in multiple feeding pipelines in sequence, and when the main catalyst and the cocatalyst are added respectively and simultaneously, multiple feeding pipelines are selected.

In the preparation of the ultra-high molecular weight polyethylene with low metal element content, in order to reduce the metal element content in the polymer, the polymerization activity of the main catalyst for catalyzing ethylene needs to be fully released and exerted, and the ultra-high molecular weight polyethylene with low metal element content and low ash content can be obtained by adopting the supported non-metallocene catalyst under the polymerization conditions of polymerization pressure, polymerization temperature and polymerization solvent participation.

According to the present invention, it was found that the polymerization pressure and the polymerization solvent of the present invention are advantageous for achieving high activity of the catalyst and thus obtaining ultra-high molecular weight polyethylene having a low content of metal elements, and the polymerization temperature of the present invention is advantageous for achieving high activity of the catalyst but affects the viscosity average molecular weight of the polyethylene thus obtained, and in addition, a long polymerization time is advantageous for achieving high activity of the catalyst.

The ultra-high molecular weight polyethylene is ultra-high molecular weight polyethylene with low metal element content and low ash content, and has mechanical properties such as high tensile yield strength, tensile breaking strength, impact strength and the like. Therefore, the polyethylene of the invention can be suitable for preparing high-strength ultrahigh molecular weight polyethylene fibers, artificial medical joints and other high-end materials.

Examples

The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.

The bulk density of the ultra-high molecular weight polyethylene is measured according to the standard GB 1636-79, and the true density is measured according to the gradient column method in a density tube of the standard GB/T1033-86.

The polymerization activity of the procatalyst was calculated as follows: after the polymerization reaction is completed, the polymerization product in the reaction vessel is filtered and dried, and then the mass of the polymerization product is weighed, and the polymerization activity of the catalyst (unit is kg polymer/g catalyst or kgPE/gCat) is expressed as a ratio of the mass of the polymerization product divided by the mass of the polyethylene main catalyst (supported non-metallocene catalyst) used.

The content of active metal elements in the supported non-metallocene catalyst and elements such as titanium, magnesium, calcium, aluminum, silicon, chlorine and the like in the ultra-high molecular weight polyethylene is measured by adopting an ICP-AES method.

Ash in ultra-high molecular weight polyethylene is measured by a direct calcination method according to the national standard GBT 9345.1-2008. The polymer was burned in a muffle furnace and its residue was treated at high temperature to constant weight, dividing the residual mass by the initial polymer mass.

The viscosity average molecular weight of the ultra-high molecular weight ethylene is calculated according to the following method: the intrinsic viscosity of the polymer was measured according to the standard ASTM D4020-00 using a high temperature dilution Ubbelohde viscometer (capillary inner diameter of 0.44mm, constant temperature bath medium of 300 # silicone oil, solvent for dilution of decalin, measurement temperature of 135 ℃ C.), and then the viscosity average molecular weight Mv of the polymer was calculated according to the following formula.

Mv=5.37×10 ⁴ ×[η] ^1.37

Wherein η is the intrinsic viscosity.

The determination of the solvent residual content ratio in the wet material after the polymerization reaction is that the ethylene slurry polymer powder obtained after the polymerization reaction in the polymerization reactor is directly filtered by a 100-mesh filter screen, the mass m1 of the wet polymer is weighed, the mass m2 of the dry polymer powder is weighed after the wet polymer is completely dried under the vacuum of 20mBar at 80 ℃, and then the solvent residual content ratio is calculated.

The melting point and crystallinity of the ultra-high molecular weight polyethylene are determined by differential scanning calorimetry, the instrument is a Q1000 type DSC differential scanning calorimeter of the company TA in the United states, and the measurement is carried out by referring to standards YYT 0815-2010; tensile yield strength, breaking strength and elongation at break were determined according to standards GB/T1040.2-2006; the impact strength of the polymers was determined according to GB/T1043-1993; the Young modulus is measured by a universal testing machine, the tabletting condition is that the pre-pressing temperature is 80 ℃, the pressure is 7.0MPa, the hot pressing temperature is 190 ℃, the pressure is 7.0MPa, the cold pressing temperature is normal temperature, and the pressure is 15.0MPa.

EXAMPLE 1 preparation of procatalyst

Example 1-1

The magnesium compound adopts anhydrous magnesium chloride, the first solvent adopts tetrahydrofuran, the alcohol adopts ethanol, the porous carrier adopts silicon dioxide, namely silica gel, the model is ES757 of Ineos company, and the silica gel is continuously roasted for 4 hours at 600 ℃ under nitrogen atmosphere to be thermally activated. Titanium tetrachloride (TiCl) ₄ ) The second solvent adopts dichloromethane, and the non-metallocene complex adopts the structure as followsIs a compound of (a).

Weighing 5g of magnesium compound, adding the magnesium compound into a first solvent, adding alcohol, completely dissolving at normal temperature to obtain a magnesium compound solution, adding a porous carrier, stirring for 2 hours to obtain a first mixed slurry, uniformly heating to 90 ℃, and directly vacuumizing and drying to obtain the composite carrier.

Adding the prepared composite carrier into a hexane solvent, dropwise adding an IVB group chemical treating agent at normal temperature for 30min, uniformly heating to 60 ℃ for reacting for 2h at constant temperature, filtering, washing the hexane solvent for 3 times, wherein the dosage of the hexane solvent is the same as the dosage of the solvent added before, and finally vacuumizing and drying at 60 ℃ to obtain the modified composite carrier.

And (3) adding the non-metallocene complex into a second solvent at room temperature, then adding the modified composite carrier, stirring for 4 hours, sealing, standing for 12 hours, and directly vacuumizing and drying at normal temperature to obtain the supported non-metallocene catalyst.

Wherein the mass ratio of the magnesium compound to the porous carrier is 1:2; the molar ratio of the magnesium compound to the alcohol calculated by Mg element is 1:2; the ratio of the magnesium compound to the first solvent is 1 mol:210 ml; the molar ratio of the composite carrier calculated as Mg element to the chemical treating agent calculated as IVB metal element is 1:0.20; the molar ratio of the composite carrier to the non-metallocene complex calculated by Mg element is 1:0.08; the proportion of non-metallocene complex relative to the second solvent is 0.1g/ml.

The supported non-metallocene catalyst was designated CAT-1.

Examples 1 to 2

Substantially the same as in example 1-1, except that the following changes were made:

Magnesium compound was changed to ethoxymagnesium (Mg (OC) ₂ H ₅ ) ₂ ) The alcohol was changed to n-butanol and the first solvent was changed to toluene, and the porous support was made of partially crosslinked (30% crosslinking) polystyrene. The polystyrene was continuously dried at 85℃under a nitrogen atmosphere for 12 hours. The chemical treating agent is changed into zirconium tetrachloride (ZrCl) ₄ ）。

Non-metallocene complexes are usedThe second solvent is changed into toluene, the first mixed slurry is changed into hexane which is added with a precipitant to completely precipitate, and the mixture is filtered and washed three times with the precipitant, and then the mixture is dried by vacuum pumping at 60 ℃.

Wherein the mass ratio of the magnesium compound to the porous carrier is 1:1; the molar ratio of the magnesium compound to the alcohol is 1:1 based on Mg element; the proportion of the magnesium compound and the first solvent is 1mol to 150ml; the molar ratio of the composite carrier calculated as Mg element to the chemical treatment agent calculated as IVB metal element is 1:0.30; the molar ratio of the composite carrier to the non-metallocene complex calculated by Mg element is 1:0.10; the volume ratio of the precipitant to the first solvent is 1:1; the proportion of non-metallocene complex relative to the second solvent is 0.06g/ml.

The supported non-metallocene catalyst was designated CAT-2.

Examples 1 to 3

The magnesium compound is changed into anhydrous magnesium bromide (MgBr) ₂ ) The alcohol is changed into 2-ethylhexanol, the first solvent and the second solvent are changed into hexane, and the montmorillonite is adopted as the porous carrier. Montmorillonite was continuously calcined at 300 ℃ under nitrogen atmosphere for 6 hours. The chemical treating agent is changed into titanium tetrabromide (TiBr) ₄ ），

Non-metallocene complexes are used. The first mixed slurry was changed to be directly vacuum dried at 105 ℃.

Wherein the mass ratio of the magnesium compound to the porous carrier is 1:5; the molar ratio of the magnesium compound to the alcohol calculated by Mg element is 1:0.7; the proportion of the magnesium compound and the first solvent is 1 mol:280 ml; the molar ratio of the composite carrier calculated as Mg element to the chemical treatment agent calculated as IVB metal element is 1:0.10; the molar ratio of the composite carrier to the non-metallocene complex calculated by Mg element is 1:0.05. The proportion of non-metallocene complex relative to the second solvent is 0.05g/ml.

The supported non-metallocene catalyst was designated CAT-3.

EXAMPLE 2 preparation of ultra high molecular weight ethylene homopolymer

The main catalyst (supported non-metallocene catalyst CAT-1-CAT-3) and the cocatalyst prepared in example 1 of the present invention were added under stirring (300 rpm) on a 5L polymerization autoclave, purged with high purity nitrogen at 100℃for 2 hours, then the autoclave was purged with the solvent, 2.5L of the solvent was added, after the temperature was raised to a predetermined temperature, ethylene was continuously fed and maintained at a constant pressure and temperature, after the predetermined polymerization time had been reached, the ethylene feeding was stopped, the autoclave was purged with the pressure, cooled to room temperature, the polymer was discharged from the autoclave together with the solvent, after the supernatant solvent was removed, the material was dried and the final mass was weighed, the specific conditions of the ethylene slurry homopolymerization reaction were as shown in Table 1, the basic properties of the ultra-high molecular weight polyethylene thus obtained were as shown in Table 2, and the results of the metal element content, ash content and mechanical properties of the ultra-high molecular weight polyethylene prepared by ethylene slurry polymerization were as shown in Table 3.

Comparative example 2-1

Substantially the same as in example 2, the polymerization solvent was changed to n-hexane as the solvent, the polymer No. was UHMWPE15, the specific conditions of the ethylene slurry polymerization reaction were shown in Table 1, the results of the properties of the ultra high molecular weight polyethylene produced by the ethylene slurry polymerization reaction thus obtained were shown in Table 2, and the results of the metal element content, ash content and crystallinity of the ultra high molecular weight polyethylene produced by the ethylene slurry polymerization reaction are shown in Table 3.

Comparative example 2-2

Substantially the same as in example 2, the polymerization solvent was changed to n-heptane as the solvent, the polymer No. was UHMWPE16, the specific conditions of the ethylene slurry polymerization reaction were shown in Table 1, the results of the properties of the ultra high molecular weight polyethylene produced by the ethylene slurry polymerization reaction thus obtained were shown in Table 2, and the results of the metal element content, ash content and crystallinity of the ultra high molecular weight polyethylene produced by the ethylene slurry polymerization reaction are shown in Table 3.

Comparative examples 2 to 3

Substantially the same as in example 2, the catalyst was changed to a silica gel supported zirconocene dichloride type metallocene catalyst, and after 6 hours of polymerization with methylaluminoxane as a cocatalyst, the polymerization activity was found to be extremely low (less than 2kg PE/gCat), and the viscosity average molecular weight of the polymer was found to be less than 60 Wan g/mol.

Comparative examples 2 to 4

Substantially the same as in example 2, the catalyst was changed to a CM type ziegler-natta catalyst (carrier is magnesium compound, no silicon, also called CMU catalyst) of beijing alda division, chinese petrochemical catalyst limited, the polymer number is UHMWPE17, the specific conditions of the ethylene slurry polymerization reaction are shown in table 1, the performance results of the ultra-high molecular weight polyethylene prepared by the ethylene slurry polymerization thus obtained are shown in table 2, and the metal element content, ash content and crystallinity results of the ultra-high molecular weight polyethylene prepared by the ethylene slurry polymerization are shown in table 3.

/>

As is clear from the comparison of the effects obtained by the numbers 1 and 2 in Table 1, the polymerization activities obtained at the conditions of the catalyst active metal molar ratios 40 and 100 are equivalent to the cocatalysts required for the polymerization process, thereby indicating that the catalyst provided by the present invention requires a smaller amount of cocatalysts when used for olefin polymerization, and thus the amount of cocatalysts can be reduced.

As can be seen from the numbers 1 and 2 in Table 2, increasing the amount of cocatalyst decreases the viscosity average molecular weight of the polymer under otherwise identical polymerization conditions. Therefore, by adopting the preparation method of the ultra-high molecular weight polyethylene, the viscosity average molecular weight and the performance of the ultra-high molecular weight polyethylene can be regulated by changing the proportion and the dosage of the cocatalyst and the cocatalyst.

As is clear from the comparison of the effects obtained in tables 1 and 2, it is possible to obtain a high ethylene slurry polymerization activity by increasing the polymerization pressure, increasing the polymerization temperature and extending the polymerization time, and further to reduce the metal element content in the obtained ultra-high molecular weight polyethylene.

As can be seen from the comparison of the effects obtained in tables 1 and 2, the ultra-high molecular weight polyethylene properties obtained in this way can be adjusted by using the present invention by selecting different performance catalysts under ethylene slurry polymerization conditions such as proper polymerization pressure, polymerization temperature, polymerization solvent, polymerization time, co-catalyst to co-catalyst molar ratio, etc.

Based on the comparison of the effects obtained by the sequence numbers 1, 15, 16 and 17 in the tables 1-3, the preparation method of the ultra-high molecular weight polyethylene is adopted, the ethylene slurry polymer powder obtained after the polymerization is very easy to dry, the solvent residue content ratio in the wet polymer is less than 20wt% after the direct filtration after the polymerization is finished, and the solvent residue content ratio is lower than 25wt% in the wet polymer when n-hexane and n-heptane are used as the polymerization solvents, thereby being very beneficial to shortening the drying time of the polyethylene material and saving the post-treatment cost of the polyethylene.

And as can be seen from tables 2 and 3, under the condition of preparing ultra-high molecular weight polyethylene by slurry polymerization of ethylene according to the present invention, the ultra-high molecular weight polyethylene prepared by the polymerization according to the present invention has a high bulk density, a high viscosity average molecular weight, low contents of elements such as titanium, calcium, magnesium, aluminum, silicon, chlorine, and ash, and the like, and the thus obtained ultra-high molecular weight ethylene homopolymer has a high tensile yield strength, tensile strength at break, elongation at break, impact strength, and young's modulus, as compared with the case where n-hexane and n-heptane are used as solvents.

In addition, based on the effects obtained by the numbers 10 to 14 in tables 1 to 3, it is understood that the method for producing ultra-high molecular weight polyethylene according to the present invention is used, and in the case of using a mixed alkane solvent, the obtained polyethylene has a higher bulk density, a higher viscosity average molecular weight, a lower content of elements such as titanium, calcium, magnesium, aluminum, silicon, chlorine, and ash, and the ultra-high molecular weight ethylene homopolymer obtained therefrom has a higher tensile yield strength, tensile strength at break, elongation at break, impact strength, and young's modulus.

While the embodiments of the present invention have been described in detail with reference to the examples, it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims. Those skilled in the art can make appropriate modifications to these embodiments without departing from the technical spirit and scope of the present invention, and it is apparent that these modified embodiments are also included in the scope of the present invention.

Claims

1. A process for preparing ultra-high molecular weight polyethylene with viscosity average molecular weight of 150-1000 Wanke/mole, characterized in that under the condition of no hydrogen, the supported non-metallocene catalyst is used as main catalyst, one or more of aluminoxane, alkyl aluminum and halogenated alkyl aluminum is used as cocatalyst, alkane solvent with boiling point of 5-55 ℃ or mixed alkane solvent with saturated vapor pressure of 20-150KPa at 20 ℃ is used as polymerization solvent to make ethylene undergo the slurry polymerization,

under the conditions of 50-100 ℃ and 0.4-4.0MPa of polymerization temperature, kettle-type slurry polymerization is carried out, the polymerization activity is higher than 2 g of polyethylene per g of main catalyst,

the non-metallocene complex is selected from one or more of a compound (A) and a compound (B) having the following chemical structural formula:

in all of the above chemical formulas,

q is 0 or 1;

d is 0 or 1;

m is 1, 2 or 3;

m is a central metal atom selected from the group consisting of group III to group XI metal atoms of the periodic Table of elements;

n is 1, 2, 3 or 4, depending on the valence of the central metal atom M;

A is selected from oxygen atom, sulfur atom, selenium atom,-NR ²³ R ²⁴ 、-N(O)R ²⁵ R ²⁶ 、/>-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ OR ³¹ Of sulfone, sulfoxide or-Se (O) R ³⁹ Wherein N, O, S, se and P are each an atom for coordination;

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 a cyano group, wherein N, O, S, se and P are each a coordinating atom;

g is selected from C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon or inertA functional group;

-represents a covalent bond or an ionic bond;

-represents a coordinate bond, a covalent bond or an ionic bond;

R ¹ to R ³ Each independently selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ A hydrocarbon group or an inert functional group selected from the group consisting of halogen, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C ₁ -C ₁₀ An ester group or a nitro group,

the substituted C ₁ -C ₃₀ The hydrocarbon radical being selected from the group consisting of with one or more halogens or C ₁ -C ₃₀ C with alkyl as substituent ₁ -C ₃₀ A hydrocarbon group.

2. The process for preparing ultra-high molecular weight polyethylene according to claim 1, wherein the kettle-type slurry polymerization is carried out at a polymerization temperature of 60 to 90℃and a polymerization pressure of 1.0 to 3.0MPa, and the polymerization activity is higher than 3 g of polyethylene per g of main catalyst.

3. The process for producing an ultra-high molecular weight polyethylene according to claim 1 or 2, wherein the polymerization solvent is one selected from the group consisting of n-pentane, isopentane, neopentane and cyclopentane; or a mixed alkane solvent of two or more selected from n-pentane, isopentane, neopentane and cyclopentane.

4. The process for producing ultra-high molecular weight polyethylene according to claim 1 or 2, wherein the cocatalyst aluminoxane is one or more selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, the cocatalyst alkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum, and the cocatalyst haloalkylaluminum is one or more selected from the group consisting of dimethylaluminum chloride, diethylaluminum chloride, ethylaluminum dichloride, dipropylaluminum chloride, propylaluminum dichloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, isobutylaluminum dichloride, di-n-hexylaluminum chloride, diisohexylaluminum chloride and diisohexylaluminum chloride.

5. The method for producing ultra-high molecular weight polyethylene according to claim 1, wherein the polymerization solvent is one selected from the group consisting 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-cyclopentane and a combination of neopentane-isopentane-n-pentane.

6. The method for producing an ultra-high molecular weight polyethylene according to claim 1, wherein the non-metallocene complex is selected from one or more of the compounds (a-1) to (a-4) and the compounds (B-1) to (B-4) having the following chemical structural formula:

m is selected from Ti (IV) and Zr (IV),

R ⁴ 、R ⁶ to R ²¹ Each independently selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbyl or inert functional group, R ⁵ Selected from lone pair electrons on nitrogen, hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon, oxygen-containing, sulfur-containing, nitrogen-containing, selenium-containing or phosphorus-containing groups, when R ⁵ Is an oxygen-containing group,When the sulfur-containing group, the nitrogen-containing group, the selenium-containing group or the phosphorus-containing group, R ⁵ N, O, S, P and Se of (A) can be used as coordinating atoms to coordinate R with the central metal atom M ⁴ 、R ⁶ To R ²¹ Each independently selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon or inert functional groups;

R ⁵ selected from lone pair electrons on nitrogen, hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, selenium-containing groups, or phosphorus-containing groups; when R is ⁵ R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group ⁵ N, O, S, P and Se of (A) can be used as the coordinating atoms.

7. A process according to claim 1, wherein,

the halogen is selected from F, cl, br or I;

the nitrogen-containing group is selected from-NR ²³ R ²⁴ 、-T-NR ²³ R ²⁴ or-N (O) R ²⁵ R ²⁶ ；

The phosphorus-containing groups are selected from-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ R ³¹ or-P (O) R ³² (OR ³³ )；

The oxygen-containing group is selected from the group consisting of hydroxy, -OR ³⁴ and-T-OR ³⁴ ；

The sulfur-containing group is selected from the group consisting of-SR ³⁵ 、-T-SR ³⁵ 、-S(O)R ³⁶ or-T-SO ₂ R ³⁷ ；

The selenium-containing group is selected from the group consisting of-Ser ³⁸ 、-T-SeR ³⁸ 、-Se(O)R ³⁹ or-T-Se (O) R ³⁹ ；

The group T is selected fromFrom C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group;

the R is ³⁷ Selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group;

the C is ₁ -C ₃₀ The hydrocarbon radical being selected from C ₁ -C ₃₀ Alkyl, C ₇ -C ₃₀ Alkylaryl, C ₇ -C ₃₀ Aralkyl, C ₃ -C ₃₀ Cyclic alkyl, C ₂ -C ₃₀ Alkenyl, C ₂ -C ₃₀ Alkynyl, C ₆ -C ₃₀ Aryl, C ₈ -C ₃₀ Condensed ring groups or C ₄ -C ₃₀ A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom;

the boron-containing group is selected from BF ₄ ^- 、(C ₆ F ₅ ) ₄ B ^- Or (R) ⁴⁰ BAr ₃ ) ^- ；

The aluminum-containing group is selected from aluminum alkyls, alPh ₄ ^- 、AlF ₄ ^- 、AlCl ₄ ^- 、AlBr ₄ ^- 、AlI ₄ ^- Or R is ⁴¹ AlAr ₃ ^- ；

The silicon-containing group is selected from-SiR 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 ；

Ar represents C ₆ -C ₃₀ An aryl group;

R ⁴⁰ to R ⁵⁴ Each independently selected from hydrogen, the foregoing C ₁ -C ₃₀ Hydrocarbyl or substituted C as previously described ₁ -C ₃₀ Hydrocarbyl groups, wherein the groups may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or a ring, and wherein the groups T are as defined above.

8. The process for producing ultra-high molecular weight polyethylene according to claim 1, wherein the group IVB metal compound is one or more selected from the group consisting of group IVB metal halides, group IVB metal alkyls, group IVB metal alkoxides, group IVB metal alkyl halides and group IVB metal alkoxyhalides.

9. The process for preparing ultra-high molecular weight polyethylene according to claim 1, wherein the non-metallocene complex is selected from one or more of the compounds having the following chemical structural formula:

10. the process for producing ultra-high molecular weight polyethylene according to claim 8, wherein said group IVB metal compound is selected from TiCl ₄ 、TiBr ₄ 、ZrCl ₄ 、ZrBr ₄ 、HfCl ₄ And HfBr ₄ One or more of the following.

11. The process for producing ultra-high molecular weight polyethylene according to claim 1, wherein the cocatalyst aluminoxane is one or more selected from the group consisting of methylaluminoxane and isobutylaluminoxane, the cocatalyst alkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, and the cocatalyst haloalkylaluminum is one or more selected from the group consisting of diethylaluminum chloride, ethylaluminum dichloride, di-n-butylaluminum chloride, n-butylaluminum dichloride, diisobutylaluminum chloride, isobutylaluminum dichloride, di-n-hexylaluminum chloride and n-hexylaluminum dichloride.

12. The ultra-high molecular weight polyethylene prepared according to the process for preparing ultra-high molecular weight polyethylene according to any one of claims 1 to 11, wherein the ultra-high molecular weight polyethylene has a viscosity average molecular weight of 150 to 1000 g/mol, a metal element content of 0 to 50ppm, and a young's modulus of the polyethylene is more than 300MPa.

13. Ultra high molecular weight polyethylene according to claim 12, wherein the bulk density of the polyethylene is 0.30-0.55g/cm ³ The true density is 0.900-0.940g/cm ³ Melting point 140-152 deg.c and crystallinity 40-75%.

14. The ultra high molecular weight polyethylene according to claim 12 or 13, wherein the polyethylene has a titanium content of 0-3ppm, a calcium content of 0-5ppm, a magnesium content of 0-10ppm, an aluminum content of 0-30ppm, a silicon content of 0-10ppm, and a chlorine content of 0-50ppm.

15. The ultra-high molecular weight polyethylene according to claim 12 or 13, wherein the polyethylene satisfies at least one of the following conditions (1) to (4):

the tensile yield strength of the condition (1) is more than 22MPa,

the breaking tensile strength of the condition (2) is more than 32MPa,

the elongation at break of the condition (3) is more than 350 percent,

condition (4) impact strength of more than 70KJ/m ² 。

16. Ultra high molecular weight polyethylene according to claim 12 or 13, characterized in that the ash content of the polyethylene is less than 200ppm.