CN114507310A

CN114507310A - Ultra-high molecular weight ethylene copolymer and preparation method thereof

Info

Publication number: CN114507310A
Application number: CN202210092170.1A
Authority: CN
Inventors: 李传峰; 景昆; 汪文睿; 卞政; 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: 2022-05-17
Anticipated expiration: 2042-01-26
Also published as: CN114507310B

Abstract

The invention relates to an ultra-high molecular weight polyethylene and a preparation method thereof, wherein the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-1000 ten-thousand g/mol, the content of metal elements is 0-50ppm, and the bulk density is 0.30-0.55g/cm³The true density is 0.900-0.940g/cm³The melting point is 140-152 ℃, the crystallinity is 40-75%, and the tensile elastic modulus of the polyethylene is more than 250MPa, preferably more than 280MPa, and more preferably more than 300 MPa. The ultra-high molecular weight polyethylene has high tensile elastic modulus, 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 copolymer and preparation method thereof

Technical Field

The invention relates to an ultra-high molecular weight ethylene copolymer with low metal element content and high mechanical property, and a slurry preparation method of the ethylene copolymer by taking alkane or mixed alkane as a polymerization solvent and taking a catalyst system containing a supported non-metallocene catalyst as a main catalyst.

Background

The ultra-high molecular weight polyethylene (UHMWPE) generally refers to linear structure polyethylene with a relative molecular mass of more than 150 million g/mol, has the advantages of excellent wear resistance, extremely high impact strength, excellent self-lubricating property, excellent chemical resistance and low temperature resistance, excellent adhesion resistance, sanitation, no toxicity, no pollution, recyclability and the like which are not possessed by common polyethylene, and is widely applied to the fields of textile, paper making, food, chemical industry, packaging, agriculture, architecture, medical treatment, water purification, sports, entertainment, military and the like.

In high-end application, the ultra-high molecular weight polyethylene with ultra-high viscosity average molecular weight (viscosity average molecular weight is generally required to be more than 400 ten thousand grams/mole) and low ash content can be used for gel or jelly spinning of a dry method or a wet method to obtain the high-strength ultra-high molecular weight polyethylene fiber which is used for bulletproof materials, anti-cutting fabrics, parachutes, fishing box fishing nets and the like. And 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 and the like.

At present, the preparation method of the ultra-high molecular weight polyethylene is mainly obtained 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 polymerizing ethylene with a mixed catalyst comprising an organoaluminum compound and a titanium component. CN200410054344.7 discloses an ultra-high molecular weight polyethylene catalyst, a preparation method and an application thereof, the catalyst is composed of a magnesium compound loaded titanium-containing component and a silicon-containing component, and the 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 a magnesium halide with an alcohol to form a magnesium compound; (2) reacting a magnesium compound with a silicon compound having at least one halogen group to form an intermediate product; and (3) reacting the intermediate product with a titanium compound to prepare a catalyst main component; in each reaction step, a benzoate compound may be optionally added. The ultrahigh molecular weight polyethylene catalyst has high activity, and the obtained ultrahigh 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, wherein the catalyst main component 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 alkyl aluminum chloride compound to obtain an intermediate product, and (3) the intermediate product reacts with titanium compound and electron donor, the activity of the ultra-high molecular weight polyethylene catalyst 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 the mutual reaction between the reaction product of a magnesium halide compound and a titanium alcoholate and the reaction product of an aluminum halide and a silicon alcoholate. US 5587440 discloses a process for the preparation of titanium (IV) halides by reduction of organoaluminum compounds and subsequent work-up to obtain ultra high molecular weight polyethylene with narrow particle size distribution and high bulk density, but the activity of the catalyst is low.

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

To obtain ultra-high molecular weight polyethylene, it is common practice to carry out the polymerization of ethylene in hexane or heptane solvents at polymerization temperatures and polymerization pressures as low as possible. High polymerization temperature is prone to chain transfer, which limits the growth of polyethylene molecular chains, and thus it is 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 difficult to even produce an ultra-high molecular weight ethylene copolymer having a viscosity average molecular weight higher than 150 micrograms/mole.

Patent CN201480057309.2 discloses the use of a magnesium support to support an organometallic compound (R)³ ₃P = N-TiCpXn) has lower catalytic activity and higher ash content in the copolymer.

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

Patents CN201610892732.5, CN201610892836.6, CN201610892837.0 and CN201610892424.2 disclose respectively ultrahigh molecular weight polyethylene, its manufacturing method and its application, which adopts a supported non-metallocene catalyst to perform ethylene homopolymerization and ethylene and α -olefin copolymerization in stages, and the molecular chain of the obtained ultrahigh molecular weight polyethylene has at least two segments (homopolymerized segment a and copolymerized segment B), and is a block copolymer with wider molecular weight distribution.

In order to obtain the ultra-high molecular weight polyethylene with low metal element content, the general method comprises the following steps: selecting or preparing a proper catalytic system, and obtaining high polymerization activity as far as possible under the condition of ethylene polymerization, which requires that the catalyst has high polymerization activity inherently; or under the condition of ethylene slurry intermittent polymerization, the polymerization reaction time is prolonged as much as possible so as to realize high polymerization activity, which requires that the catalyst has long polymerization activity life, the instantaneous consumption of the polymerized monomer ethylene is increased, unchanged or reduced gradually along with the time, but the instantaneous consumption cannot be quickly reduced or even quickly reduced to an extremely low value, and the significance of prolonging the reaction is lost; or post-treating the polymerized ultra-high molecular weight polyethylene. 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, sieving, etc., but the treatment process is complicated, the requirement of the treatment process on the impurity content of the washing solvent is high, and the washing and drying costs are high.

Chinese patent 201610747653.5 discloses a continuous washing device and method for ultra-high molecular weight polyethylene, wherein it is pointed out that in the polymerization process of ultra-high molecular weight polyethylene, the catalyst and alkyl aluminum form an active center to initiate the polymerization reaction of ethylene, and at the same time, a small amount of metal acid is generated, if no washing is performed, the metal acid will corrode processing equipment in the subsequent processing of powder, in addition, the excessive presence of high boiling point alkyl aluminum in the polymerization process reacts with a small amount of oxygen and a small amount of water in the solvent to generate aluminum hydroxide, which results in high content of aluminum in polyethylene, thereby reducing the tensile strength, impact strength, wear resistance and the like of the product.

Therefore, the present state of the art is that it is still desirable to develop a high and controllable viscosity average molecular weight polyethylene having adjustable viscosity average molecular weight, high bulk density and mechanical properties, low content of metallic elements and ash content, high mechanical properties, and a method for preparing the ultra high molecular weight polyethylene satisfying the following characteristics: under the condition of ethylene slurry polymerization, the catalyst has long active life, high polymerization activity and flexible and adjustable polymerization preparation process, and is suitable for large-scale implementation, and the prepared ultrahigh molecular weight polyethylene has high bulk density, and the ethylene copolymer has high tensile elastic modulus, thereby being beneficial to product packaging, storage, transportation, filling and downstream processing application.

Disclosure of Invention

The present inventors have conducted extensive studies based on the prior art, and as a result, have found that an ultrahigh molecular weight polyethylene (ethylene copolymer) having a low metal element content and high mechanical properties can be prepared by slurry-polymerizing a raw material comprising ethylene and a comonomer 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 ethylene slurry polymerization, using a supported non-metallocene catalyst as a main catalyst, and using one or more of aluminoxane, alkylaluminum, and alkylaluminum halide as a cocatalyst, thereby solving the aforementioned existing problems, thereby completing the present invention.

That is, the ultra-high molecular weight polyethylene with low metal element content and high mechanical property and the preparation method thereof of the invention can provide the ultra-high molecular weight polyethylene with low metal element content and high mechanical property without harsh ethylene slurry polymerization reactor configuration, polymerization reaction conditions and complex post-treatment steps. In particular, the obtained polyethylene has mechanical properties such as high tensile elastic modulus and the like, is very suitable for industrial scale production, and can be suitable for subsequent preparation of high-strength ultrahigh molecular weight polyethylene fibers, artificial medical joints and other high-end materials.

Specifically, the invention provides an ultrahigh molecular weight polyethylene (ethylene copolymer), wherein the viscosity average molecular weight of the ultrahigh molecular weight polyethylene is 150-800 ten-thousand g/mol, preferably 200-700-ten-thousand g/mol, more preferably 300-700-ten-thousand g/mol, the content of metal elements is 0-50ppm, preferably 0-30ppm, and the tensile elastic modulus of the polyethylene is more than 250MPa, preferably more than 280MPa, more preferably more than 300 MPa.

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, and a tensile modulus of elasticity of more than 250MPa, preferably more than 280MPa, more preferably more than 300 MPa.

The invention also provides a preparation method of the ultra-high molecular weight polyethylene, wherein the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-800 ten-million g/mol, preferably 200-700-million g/mol, more preferably 300-700-million g/mol, wherein under the condition of no hydrogen, a supported non-metallocene catalyst is used as a main catalyst, one or more of aluminoxane, aluminum alkyl and halogenated aluminum alkyl is used as a cocatalyst, and a paraffin solvent with the boiling point of 5-55 ℃ or a mixed paraffin solvent with the saturated vapor pressure of 20-150KPa (preferably 40-110 KPa) at 20 ℃ is used as a polymerization solvent, so that the raw material containing ethylene and comonomer is subjected to slurry polymerization, and the ultra-high molecular weight polyethylene with low metal element content is obtained.

Technical effects

The ultra-high molecular weight polyethylene of the present invention has a high viscosity average molecular weight, a low content of metal elements, a low content of ash, and excellent mechanical properties, and particularly, the polyethylene has a high tensile elastic modulus, which is very useful for improving the tensile strength, impact strength, abrasion resistance, etc. of a product made of the polyethylene.

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

In addition, according to the polymerization method of the present invention, the alkane solvent having a boiling point of 5 to 55 ℃ or the mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa at 20 ℃ is used 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 a wide choice. Further, the post-treatment of the obtained ultrahigh molecular weight polyethylene is easy. And the non-metallocene catalyst is used in a matched manner, so that the obtained ultrahigh molecular weight polyethylene has low solvent residue content, thereby being very beneficial to shortening the drying time of polyethylene materials and saving the post-treatment cost of polyethylene, and further being beneficial to the subsequent industrial application of ethylene polymers. Further, the polyethylene having a low metal element content and a low ash content and excellent mechanical properties can be realized.

In addition, 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 other solvents such as a dispersant and a diluent are not required, so that the reaction system is single, and the post-treatment is simple and easy.

Detailed Description

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

In the context of the present invention, unless otherwise explicitly defined, or the meaning is beyond the understanding of those skilled in the art, a hydrocarbon or hydrocarbon derivative group of 3 or more carbon atoms (e.g., propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) has the same meaning when not headed "plus" as when headed "plus". For example, propyl is generally understood to be n-propyl, and butyl is generally understood to be n-butyl, unless otherwise specified.

In the present specification, in order to avoid complicated expressions, it is not clear for each substituent or group of a compound whether the valence bond condition thereof is monovalent, divalent, trivalent, tetravalent, or the like, and those skilled in the art can specifically judge the position where these substituents or groups (such as groups G, D, B, A, F, and the like described or defined in the present specification) are located on the structural formula of the corresponding compound or the substitution case expressed, and select a suitable definition of the valence bond condition at the position or the substitution case from the definitions given for these substituents or groups in the present 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 same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.

In the context of the present specification, anything or things which are not mentioned, except where explicitly stated, are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or concepts resulting therefrom are considered part of the original disclosure or original disclosure of the invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such a combination to be clearly unreasonable.

Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.

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

As a result of intensive studies, the inventors of the present invention have confirmed that, in the polymerization method of the present invention, by 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 (preferably 40 to 110 KPa) at 20 ℃ as a polymerization solvent, the difference in boiling points between the specific polymerization solvent of the present invention and ethylene and a copolymerized olefin (for example, propylene, 1-butene, 1-hexene, 1-octene) as reactants is more significant than that of a conventional polymerization solvent, so that the post-treatment of the obtained ultra-high molecular weight polyethylene powder can be conveniently and efficiently performed, and the solvent residual content in the obtained ultra-high molecular weight polyethylene powder is low, which is advantageous for shortening the drying time of the polyethylene powder and saving the post-treatment cost of the polyethylene powder. In 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 other solvents such as a dispersant and a diluent are not required, so that the reaction system is simple and the post-treatment is 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 can be further improved, the polymerization process is stable, the ethylene is stably consumed in real time, and the polyethylene with ultra-high viscosity-average molecular weight can be obtained at higher polymerization temperature. In addition, when the slurry polymerization system of the present invention is used for copolymerization, a high insertion rate of copolymerized olefin can be obtained.

Thus, the ultra-high molecular weight polyethylene obtained by the method of the present invention exhibits a high viscosity average molecular weight, a low content of metal elements, a low content of ash, and the resulting polyethylene is excellent in mechanical properties and has a large tensile elastic modulus. Therefore, the product obtained by using the ultra-high molecular weight polyethylene of the present invention has excellent mechanical strength and low impurity content, and thus, the product obtained by using the ultra-high molecular weight polyethylene of the present invention is suitable for application in fields with strict requirements on quality, such as aerospace, medical materials, and the like.

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

In the present invention, the ethylene copolymer is also referred to as an ethylene polymer or polyethylene. The ultra-high molecular weight polyethylene of the present invention is not a block copolymer, and its structure is a random copolymer structure.

The invention provides an ultra-high molecular weight polyethylene, which is characterized in that the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-800 ten-thousand g/mol, preferably 200-700-thousand g/mol, more preferably 300-700-ten-thousand g/mol, the content of metal elements is 0-50ppm, preferably 0-30ppm, and the tensile elastic modulus of the polyethylene is more than 250MPa, preferably more than 280MPa, more preferably more than 300 MPa.

In one embodiment of the invention, the polyethylene has a bulk density of 0.30 to 0.55g/cm³Preferably 0.33 to 0.52g/cm³More preferably 0.40 to 0.50g/cm³. In one embodiment of the invention, the polyethylene has a true density of from 0.900 to 0.940g/cm³Preferably 0.905 to 0.935g/cm³More preferably 0.915 to 0.930g/cm³. In one embodiment of the invention, the melting point of the polyethylene is 140-. In one embodiment of the invention, the polyethylene has a crystallinity of 40 to 75%, preferably 45 to 70%.

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

In one embodiment of the invention, the polyethylene is a random copolymer with a comonomer molar insertion of 0.05 to 4.0%, preferably 0.10 to 2.0%.

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

In one embodiment of the invention, the viscosity average molecular weight of the polyethylene is 150-800 ten-thousand g/mol, preferably 200-700 ten-thousand g/mol, more preferably 300-700 ten-thousand g/mol.

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, 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, and a chlorine content of 0 to 50ppm, preferably 0 to 30 ppm.

In one embodiment of the invention, the polyethylene has a bulk density of 0.30 to 0.55g/cm³Preferably 0.33 to 0.52g/cm³More preferably 0.41 to 0.50g/cm³The true density is 0.900-0.940g/cm³Preferably 0.905 to 0.935g/cm³More preferably 0.910 to 0.930g/cm³The melting point is 140-152 ℃, preferably 142-150 ℃, and the crystallinity is 40-75%, preferably 45-70%.

In one embodiment of the invention, the polyethylene is of a random copolymeric structure with a comonomer molar insertion of 0.05 to 4.0%, preferably 0.10 to 2.0%.

In one embodiment of the invention, the polyethylene has a tensile modulus of elasticity of greater than 250MPa, preferably greater than 280MPa, more preferably greater than 300 MPa.

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

The ultra-high molecular weight polyethylene of the present invention is obtained by the following ethylene slurry production method of the present invention.

The invention provides a preparation method of ultra-high molecular weight polyethylene, wherein under the condition of no hydrogen, a supported non-metallocene catalyst is used as a main catalyst, one or more of aluminoxane, alkyl aluminum and halogenated alkyl aluminum are used as a cocatalyst, and an alkane solvent with the boiling point of 5-55 ℃ or a mixed alkane solvent with the saturated vapor pressure of 20-150KPa (preferably 40-110 KPa) at 20 ℃ is used as a polymerization solvent, so that raw materials containing ethylene and comonomer are subjected to slurry polymerization.

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

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

In one embodiment of the present invention, the process for the preparation of ultra high molecular weight polyethylene comprises a slurry polymerization activity of ethylene higher than 2, preferably higher than 3, most preferably higher than 4, million grams of polyethylene per gram of procatalyst.

In one embodiment of the present invention, in the preparation method of the ultra-high molecular weight polyethylene, the molar ratio of the comonomer to the active metal in the catalyst is 10 to 500: 1, preferably 20 to 400: 1, and ethylene and the comonomer are fed into a polymerization vessel together for further polymerization.

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

In the present invention, the ethylene copolymer means a copolymer formed by copolymerizing ethylene with another comonomer other than ethylene.

In particular, the comonomer is selected from alpha-olefins, diolefins, cyclic olefins and other ethylenically unsaturated compounds. As the alpha-olefin, there may be mentioned C₃-C₁₀Examples of the α -olefin of (a) include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 4-methyl-1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene and styrene. Examples of the cyclic olefin include 1-cyclopentene, ethylidene norbornene, norbornene and the like. As a stationExamples of the diolefin include 1, 4-butadiene, 2, 5-pentadiene, 1, 5-hexadiene, vinylnorbornene, norbornadiene and 1, 7-octadiene. Examples of the other ethylenically unsaturated compound include vinyl acetate and (meth) acrylate. Among them, the comonomer is preferably C₃-C₁₀More preferably at least one selected from the group consisting of 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene, and still more preferably at least one selected from the group consisting of 1-butene, 1-hexene and 1-octene.

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

And, when the polymerization reaction is carried out, ethylene and a comonomer are fed into the polymerization vessel all at once to carry out the polymerization reaction. In the present invention, "ethylene and a comonomer are fed together to a polymerization reactor" means that a raw material containing ethylene and a comonomer is fed together to a reaction tank to be polymerized without a step of stepwise polymerization, that is, without a step of stepwise polymerizing ethylene, that is, without a step of adding a comonomer to polymerize after polymerizing ethylene, and without a step of stepwise polymerizing a comonomer to add ethylene to polymerize.

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

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 thermal 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;

a step of contacting the composite carrier with a chemical treatment agent selected from a group IVB metal compound to obtain a modified composite carrier;

and (3) contacting a 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 will be specifically described below.

According to the present invention, the term "magnesium compound" is used in a general concept in the art to refer to an organic or inorganic solid anhydrous magnesium-containing compound conventionally used as a support for supported olefin polymerization catalysts.

Specifically, the magnesium halide includes, for example, 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), magnesium ethoxychloride (Mg (OC)₂H₅) Cl), propoxymagnesium chloride (Mg (OC)₃H₇) Cl), n-butoxy magnesium chloride (Mg (OC)₄H₉) Cl), isobutoxy magnesium chloride (Mg (i-OC)₄H₉) Cl), methoxy magnesium bromide (Mg (OCH)₃) Br), magnesium ethoxybromide (Mg (OC)₂H₅) Br), propoxymagnesium bromide (Mg (OC)₃H₇) Br), n-butoxy magnesium bromide (Mg (OC)₄H₉) Br), isobutoxy magnesium bromide (Mg (i-OC)₄H₉) Br), methoxy magnesium iodide (Mg (OCH)₃) I), magnesium ethoxyiodide (Mg (OC)₂H₅) I), propoxyatomagnesium iodide (Mg (OC)₃H₇) I), magnesium n-butoxide iodide (Mg (OC)₄H₉) I) and isobutoxy magnesium iodide (Mg (I-OC)₄H₉) I) and the like, among which, methoxy magnesium chloride and ethoxy chloride are preferredMagnesium chloride and isobutoxy magnesium chloride.

Examples of the magnesium alkoxide include magnesium methoxide (Mg (OCH)₃)₂) Magnesium ethoxide (Mg (OC)₂H₅)₂) Magnesium propoxide (Mg (OC)₃H₇)₂) Magnesium butoxide (Mg (OC)₄H₉)₂) Isobutoxy magnesium (Mg (i-OC)₄H₉)₂) And 2-ethylhexyloxymagnesium (Mg (OCH)₂CH(C₂H₅)C₄H₈)₂) And the like, among which magnesium ethoxide and magnesium isobutoxide are preferable.

Examples of the alkyl magnesium include methyl magnesium (Mg (CH)₃)₂) Ethyl magnesium (Mg (C)₂H₅)₂) Propyl magnesium (Mg (C)₃H₇)₂) N-butylmagnesium (Mg (C)₄H₉)₂) And isobutyl magnesium (Mg (i-C)₄H₉)₂) Etc., among which ethyl magnesium and n-butyl magnesium are preferred.

Examples of the alkyl magnesium halide include methyl magnesium chloride (Mg (CH)₃) Cl), ethylmagnesium chloride (Mg (C)₂H₅) Cl), propylmagnesium chloride (Mg (C)₃H₇) Cl), n-butylmagnesium chloride (Mg (C)₄H₉) Cl), isobutyl magnesium chloride (Mg (i-C)₄H₉) Cl), methyl magnesium bromide (Mg (CH)₃) Br), ethyl magnesium bromide (Mg (C)₂H₅) Br), propyl magnesium bromide (Mg (C)₃H₇) Br), n-butylmagnesium bromide (Mg (C)₄H₉) Br), isobutyl magnesium bromide (Mg (i-C)₄H₉) Br), methyl magnesium iodide (Mg (CH)₃) I), ethyl magnesium iodide (Mg (C)₂H₅) I), propylmagnesium iodide (Mg (C)₃H₇) I), n-butyl magnesium iodide (Mg (C)₄H₉) I) and isobutyl magnesium iodide (Mg (I-C)₄H₉) I) and the like, wherein methyl magnesium chloride, ethyl magnesium chloride and isobutyl magnesium chloride are preferred.

Examples of the alkyl magnesium alkoxide includeMethylmethoxymagnesium (Mg (OCH)₃)(CH₃) Methyl magnesium ethoxide (Mg (OC)₂H₅)(CH₃) Methyl propoxy magnesium (Mg (OC))₃H₇)(CH₃) Methyl n-butoxy magnesium (Mg (OC)₄H₉)(CH₃) Methyl isobutoxy magnesium (Mg (i-OC)₄H₉)(CH₃) Ethyl methoxy magnesium (Mg (OCH)₃)(C₂H₅) Ethyl magnesium ethoxide (Mg (OC)₂H₅)(C₂H₅) Ethyl propoxy magnesium (Mg (OC)₃H₇)(C₂H₅) Ethyl n-butoxy magnesium (Mg (OC)₄H₉)(C₂H₅) Ethyl isobutoxy magnesium (Mg (i-OC)₄H₉)(C₂H₅) Propylmethoxymagnesium (Mg (OCH))₃)(C₃H₇) Propylmagnesium ethoxide (Mg (OC)₂H₅)(C₃H₇) Propylmagnesium propoxide (Mg (OC)₃H₇)(C₃H₇) Propyl n-butoxy magnesium (Mg (OC)₄H₉)(C₃H₇) Propyl iso-butoxy magnesium (Mg (i-OC)₄H₉)(C₃H₇) N-butyl methoxy magnesium (Mg (OCH)₃)(C₄H₉) N-butyl ethoxy magnesium (Mg (OC)₂H₅)(C₄H₉) N-butyl propoxy magnesium (Mg (OC)₃H₇)(C₄H₉) N-butyl n-butoxy magnesium (Mg (OC)₄H₉)(C₄H₉) N-butyl isobutoxy magnesium (Mg (i-OC)₄H₉)(C₄H₉) Isobutyl methoxy magnesium (Mg (OCH)), isobutyl methoxy magnesium (Mg)₃)(i-C₄H₉) Isobutyl ethoxy magnesium (Mg (OC)₂H₅)(i-C₄H₉) Isobutyl propoxy magnesium (Mg (OC)₃H₇) (i-C₄H₉) Isobutyl n-butoxy magnesium (Mg (OC)₄H₉) (i-C₄H₉) And isobutyl isobutoxy magnesium (Mg (i-)OC₄H₉) (i-C₄H₉) Etc.), among which butyl magnesium ethoxide is preferred.

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

When used in the form of a mixture of plural kinds, the molar ratio between 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, the magnesium compound is dissolved in a first solvent (hereinafter, also referred to as a solvent for dissolving the magnesium compound) in the presence of an alcohol, thereby obtaining the magnesium compound solution.

The first solvent includes, for example, C_6-12Aromatic hydrocarbons, halogenated C_6-12Aromatic hydrocarbon, C_5-12Alkanes, esters and ethers.

As said C_6-12Examples of the aromatic hydrocarbon include toluene, xylene, trimethylbenzene, ethylbenzene and diethylbenzene.

As said halo C_6-12Examples of the aromatic hydrocarbon include chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene and the like.

As said C_5-12Examples of the alkane include pentane, hexane, heptane, octane, nonane, decane, etc., and among them, hexane, heptane, 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.

Among them, C is preferable_6-12Aromatic hydrocarbon, C_5-12Alkanes and tetrahydrofuran, with tetrahydrofuran being most preferred.

These solvents may be used alone or in combination of two or more at an arbitrary ratio.

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

The alcohol includes, for example, C_1-30Fatty alcohol (preferably C)_1-30Aliphatic monohydric alcohol), C_6-30Aromatic alcohol (preferably C)_6-30Aromatic monohydric alcohol) and C_4-30Alicyclic alcohol (preferably C)_4-30Alicyclic monohydric alcohol), among which C is preferred_1-30Aliphatic monohydric alcohol or C_2-8Aliphatic monohydric alcohols, more preferably ethanol and butanol. In addition, the alcohol may optionally be selected from halogen atoms or C_1-6Substituent of alkoxy.

As said C_1-30Examples of the aliphatic alcohol include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, 2-methylpentanol, 2-ethylpentanol, 2-hexylbutanol, hexanol, and 2-ethylhexanol, and ethanol, butanol, and 2-ethylhexanol are preferable.

As said C_6-30Examples of the aromatic alcohol include benzyl alcohol, phenethyl alcohol, and methylbenzyl alcohol, and among them, phenethyl alcohol is preferable.

As said C_4-30Examples of the alicyclic alcohol include cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclohexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, propylcyclooctanol and the like, and among them, cyclohexanol and methylcyclohexanol are preferable.

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

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

These alcohols may be used alone or in combination of two or more. When used in the form of a plurality of mixtures, 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 for dissolution, or the magnesium compound may be added to the first solvent and dissolved with or after the addition of the alcohol, 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 facilitate the dissolution of the magnesium compound. The agitation may take any form, such as paddles (typically at 10-1000 rpm), and the like. Dissolution may sometimes be facilitated by appropriate heating (but the maximum temperature must be below the boiling point of the first solvent and the alcohol) as desired.

According to the present 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 carrier is specifically described below.

According to the present invention, as the porous support, there may be mentioned, for example, those organic or inorganic porous solids which are conventionally used in the art as a support in the production of a supported olefin polymerization catalyst.

Specifically, examples of the organic porous solid include olefin homopolymers or copolymers, polyvinyl alcohols or copolymers thereof, cyclodextrins, (co) polyesters, (co) polyamides, vinyl chloride homopolymers or copolymers, acrylate homopolymers or copolymers, methacrylate homopolymers or copolymers, and styrene homopolymers or copolymers, and partially crosslinked forms of these homopolymers or copolymers, and among these, styrene polymers that are partially crosslinked (for example, having a degree of crosslinking of at least 2% but less than 100%) are preferable.

According to a preferred embodiment of the present invention, it is preferred that the surface of the organic porous solid has 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 preferred.

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 the thermal activation treatment and the chemical activation treatment may be sequentially performed in any combination order before use, and is not particularly limited.

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 an extremely small amount of components or does not contain components that can react with the organic porous solid. Examples of the inert gas atmosphere include a nitrogen gas and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Since the organic porous solid is poor in heat resistance, this thermal activation process is premised on not destroying the structure and basic composition of the organic porous solid itself. Generally, the temperature of the thermal activation is 50-400 ℃, preferably 100-.

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

Examples of the inorganic porous solid include refractory oxides of metals of groups IIA, IIIA, IVA or IVB of the periodic Table of the elements (e.g., silica (also referred to as silica or silica gel), alumina, magnesia, titania, zirconia, thoria, etc.), or any refractory composite oxides of these metals (e.g., silica-alumina, magnesia-alumina, titania-silica, magnesia and titania-alumina, etc.), and clays, molecular sieves (e.g., ZSM-5 and MCM-41), mica, montmorillonite, bentonite and diatomaceous earth. Examples of the inorganic porous solid include oxides produced 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, and 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, for example, Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Grace 2480D, Grace 2212D, Grace 2485, Davsion Syloid 245 and Aerosil812 from Grace, ES70, ES70X, ES70Y, ES70W, ES757, EP10X and EP11 from Ineos, and CS-2133 and MS-3040 from PQ.

According to a preferred embodiment of the present invention, it is preferable that the inorganic porous solid 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 before use.

According to the present invention, the inorganic porous solid may be subjected to only the thermal activation treatment before use, or may be subjected to only the chemical activation treatment before use, or may be subjected to the thermal activation treatment and the chemical activation treatment in this order of any combination before use, and is not particularly limited.

The thermal activation treatment may be carried out in a usual manner, for example, by subjecting the inorganic porous solid to a heat treatment under reduced pressure or under an inert atmosphere. The inert gas atmosphere as used herein means that the gas contains only an extremely small amount of components or does not contain components that can react with the inorganic porous solid. Examples of the inert gas atmosphere include a nitrogen gas and a rare gas atmosphere, and a nitrogen gas atmosphere is preferable. Typically, the temperature of the thermal activation is 200-.

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

According to the present invention, the chemical activation treatment performed on 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 is given.

According to the invention, a compound of a group IVB metal 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 alkoxy halide.

The group IVB metal compound is preferably a group IVB metal halide, more preferably TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄Most preferably TiCl₄And ZrCl₄。

These group IVB metal compounds may be used singly or in combination 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 in a solid state at ordinary temperature, it is preferably used in the form of a solution for the sake of metering and handling convenience. Of course, when the chemical activator is in a liquid state at room temperature, the chemical activator may be used in the form of a solution 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_5-12Alkane, C_5-12Cycloalkanes, halogen radicals C_5-12Alkanes, halogenated C_5-12Cycloalkanes, C_6-12Aromatic hydrocarbons or halogenated C_6-12Examples of the aromatic hydrocarbon include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, toluene, ethylbenzene, xylene, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, chlorotoluene, chloroethylbenzene, chloroxylene, and chloroxylene, among which pentane, hexane, decane, cyclohexane, and toluene are preferable, and hexane and toluene are most preferable.

These solvents may be used singly or in combination in any ratio.

In addition, the concentration of the chemical activating agent in the solution thereof is not particularly limited, and may be appropriately selected as needed as long as it can achieve the chemical activation with a predetermined amount of the chemical activating agent. As described above, if the chemical activator is in a liquid state, the activation may be performed by using the chemical activator as it is, or may be performed after preparing a chemical activator solution.

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

As a method for carrying out the chemical activation, for example, in the case where the chemical activator is in a solid state (such as zirconium tetrachloride), there may be mentioned a method in which 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 the organic porous solid or inorganic porous solid to be activated to carry out the chemical activation reaction. In the case where the chemical activating agent is in a liquid state (such as titanium tetrachloride), a predetermined amount of the chemical activating agent 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 activating agent is prepared into a solution, the solution containing a predetermined amount of the chemical activating agent may be added (preferably dropwise) to the organic porous solid or inorganic porous solid to be activated to perform the chemical activation reaction.

Generally, the chemical activation reaction (with stirring if necessary) 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, filtering, washing and drying are carried out, and the chemically activated organic porous solid or inorganic porous solid can be obtained.

According to the present invention, the filtration, washing and drying may be carried out by a conventional method, wherein the solvent for washing may be the same solvent as that used for dissolving the chemical activating agent. This washing is generally carried out 1 to 8 times, preferably 2 to 6 times, most preferably 2 to 4 times, as required.

The drying can be carried out by conventional methods, such as inert gas drying, vacuum drying or heating under vacuum drying, preferably inert gas drying or heating under vacuum drying, and most preferably heating under vacuum drying. The drying temperature is generally in the range of normal temperature to 140 ℃, and the drying time is generally 2-20h, but is not limited thereto.

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

According to the present invention, the surface area of the porous carrier is not particularly limited, but is generally 10 to 1000m²Per g (determined by the BET method), preferably 100-600m²(ii)/g; the porous carrier has a pore volume (measured by nitrogen adsorption) of 0.1-4cm³In g, preferably from 0.2 to 2cm³In terms of a/g, and the average particle diameter (determined by laser granulometry) thereof is preferably from 1 to 500mm, more preferably from 1 to 100 mm.

According to the invention, the porous support may be in any form, such as a fine powder, granules, spheres, aggregates or other forms.

A first mixed slurry is obtained by mixing the porous support (optionally thermally and/or chemically activated) 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 carrier may be added to the magnesium compound solution at a temperature from room temperature to the preparation temperature of the magnesium compound solution, or the magnesium compound solution may be added to the porous carrier 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, as the amount of the porous support, the mass ratio of the magnesium compound (based on the magnesium compound solid contained in the magnesium compound solution) to the porous support is made to be 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 system. Although not necessary, in order to ensure the uniformity of the system, the first mixed slurry is preferably subjected to a closed standing for a certain time (2 to 48 hours, preferably 4 to 24 hours, most preferably 6 to 18 hours) after the preparation.

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

At this time, the direct drying may be carried out 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., wherein the heat drying under a vacuum atmosphere is preferable. The drying temperature is generally 30 to 160 ℃, preferably 60 to 130 ℃, and the drying time is generally 2 to 24 hours, but the drying time is not limited to this.

Alternatively, according to the present invention, a composite carrier is obtained by precipitating a solid substance from the first mixed slurry by metering a precipitant into the first mixed slurry.

The precipitant is specifically described below.

According to the present invention, the term "precipitant" is used in the art as a general concept and refers 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 causing it to be precipitated from the solution as a solid.

According to the present invention, the precipitating agent may be, for example, a poor solvent for a solid solute to be precipitated (for example, the magnesium compound, the porous support, the non-metallocene ligand, the non-metallocene complex, or the like), and a good solvent for the solvent for dissolving the solid solute (for example, the magnesium compound) may be, for example, C_5-12Alkane, C_5-12Cycloalkanes, halogen radicals C_1-10Alkanes and halogenated C_5-12A cycloalkane.

As said C_5-12Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane, cyclodecane and cyclononane, and cyclohexane is most preferable.

As said halo C_1-10Examples of the alkane include dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane and tribromobutane.

As said halo C_5-12Examples of the cycloalkane include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.

These precipitants may be used singly or in combination of two or more at an arbitrary ratio.

The addition mode of the precipitant can be one-time addition or dropwise addition, and preferably one-time addition. During this precipitation, agitation may be used to facilitate dispersion of the precipitant and to facilitate final precipitation of the solid product. The agitation may take any form (e.g., paddles) and is typically at a speed of 10-1000rpm, etc.

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

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

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

The washing is generally carried out 1 to 6 times, preferably 3 to 4 times, as required. Among them, the washing solvent is preferably the same solvent as the precipitant, but may be different.

The drying can be carried out by conventional methods such as inert gas drying, vacuum drying or vacuum heating drying, preferably inert gas drying or vacuum heating drying, most preferably vacuum heating drying.

The drying temperature is generally in the range of normal temperature to 140 ℃. The drying time is generally from 2 to 20 hours, but may vary depending on the particular solvent used to dissolve 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 time is 2 to 12 hours under vacuum, and when toluene is used as a solvent for dissolving the magnesium compound, the drying temperature is generally about 100 ℃ and the drying time is 4 to 24 hours under vacuum.

According to the present invention, the 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 present 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 alkoxide compound, the group IVB metal alkyl halide, and the group IVB metal alkoxide halide include compounds having the following general structures:

M(OR¹)_mX_nR² _4-m-n

wherein:

m is 0, 1, 2, 3 or 4;

n is 0, 1, 2, 3 or 4;

m is a metal of group IVB of the periodic Table of the elements, such as titanium, zirconium, hafnium, etc.;

x is halogen, such as F, Cl, Br and I; and is provided with

R¹And R²Each independently selected from C₁-₁₀Alkyl radicals, such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R¹And R²May be the same or different.

Specifically, the group IVB metal halide includes, for example, 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) Hafnium tetrabromide (HfBr)₄) Hafnium tetraiodide (HfI)₄）。

Examples of the group IVB metal alkyl compound include tetramethyltitanium (Ti (CH)₃)₄) Tetraethyl titanium (Ti (CH)₃CH₂)₄) Tetraisobutyltitanium (Ti (i-C)₄H₉)₄) Tetra-n-butyltitanium (Ti (C)₄H₉)₄) Triethylmethyltitanium (Ti (CH)₃)(CH₃CH₂)₃) Diethyl dimethyl titanium (Ti (CH)₃)₂(CH₃CH₂)₂) Trimethylethyltitanium (Ti (CH)₃)₃(CH₃CH₂) Triisobutylmethyltitanium (Ti (CH))₃)(i-C₄H₉)₃) Diisobutyldimethyltitanium (Ti (CH)₃)₂(i-C₄H₉)₂) Trimethylisobutyltitanium (Ti (CH)₃)₃(i-C₄H₉) Triisobutylethyltitanium (Ti (CH))₃CH₂)(i-C₄H₉)₃) Diisobutyl diethyl titanium (Ti (CH)₃CH₂)₂(i-C₄H₉)₂) Triethylisobutyltitanium (Ti (CH)₃CH₂)₃(i-C₄H₉) Tri (n-butyl) methyl titanium (Ti (CH))₃)(C₄H₉)₃) Di-n-butyldimethyl titanium (Ti (CH)₃)₂(C₄H₉)₂) Trimethyl n-butyltitanium (Ti (CH)₃)₃(C₄H₉) Tri (n-butyl) ethyl titanium (Ti (CH))₃CH₂)(C₄H₉)₃) Di-n-butyldiethyltitanium (Ti (CH)₃CH₂)₂(C₄H₉)₂) Triethyl n-butyltitanium (Ti (CH)₃CH₂)₃(C₄H₉) Etc.);

tetramethyl zirconium (Zr (CH)₃)₄) Tetraethyl zirconium (Zr (CH)₃CH₂)₄) Tetraisobutylzirconium (Zr (i-C)₄H₉)₄) Tetra-n-butylzirconium (Zr (C)₄H₉)₄) Triethylmethylzirconium (Zr (CH)₃)(CH₃CH₂)₃) Diethyl dimethyl zirconium (Zr (CH)₃)₂（CH₃CH₂)₂) Trimethylethylzirconium (Zr (CH)₃)₃(CH₃CH₂) Triisobutylzirconium methyl (Zr (CH))₃)(i-C₄H₉)₃) Diisobutyldimethylzirconium (Zr (CH)₃)₂(i-C₄H₉)₂) Trimethylisobutylzirconium (Zr (CH)₃)₃(i-C₄H₉) Triisobutylethylzirconium (Zr (CH))₃CH₂)(i-C₄H₉)₃) Diisobutyl diethyl zirconium (Zr (CH)₃CH₂)₂(i-C₄H₉)₂) Triethyl isobutyl zirconium (Zr (CH)₃CH₂)₃(i-C₄H₉) Tri-n-butylzirconium (Zr (CH))₃)(C₄H₉)₃) Di-n-butylzirconium dimethyl (Zr (CH)₃)₂(C₄H₉)₂) Trimethyl n-butyl zirconium (Zr (CH)₃)₃(C₄H₉) Tri-n-butyl zirconium ethyl (Zr (CH))₃CH₂)(C₄H₉)₃) Di-n-butyldiethylzirconium (Zr (CH)₃CH₂)₂(C₄H₉)₂) Triethyl n-butyl zirconium (Zr (CH)₃CH₂)₃(C₄H₉) Etc.);

tetramethylhafnium (Hf (CH)₃)₄) Tetraethyl hafnium (Hf (CH)₃CH₂)₄) Tetra isobutyl hafnium (Hf (i-C)₄H₉)₄) Tetra-n-butyl hafnium (Hf (C)₄H₉)₄) Triethyl methylHafnium base (Hf (CH)₃)(CH₃CH₂)₃) Diethyl hafnium (Hf (CH)₃)₂(CH₃CH₂)₂) Trimethylhafnium (Hf (CH)₃)₃(CH₃CH₂) Triisobutyl methyl hafnium (Hf (CH)₃)(i-C₄H₉)₃) Diisobutyldimethylhafnium (Hf (CH)₃)₂(i-C₄H₉)₂) Trimethylisobutylhafnium (Hf (CH)₃)₃(i-C₄H₉) Triisobutylethylhafnium (Hf (CH)₃CH₂)(i-C₄H₉)₃) Diisobutyl hafnium diethyl (Hf (CH)₃CH₂)₂(i-C₄H₉)₂) Triethyl isobutyl hafnium (Hf (CH)₃CH₂)₃(i-C₄H₉) Tri-n-butyl hafnium methyl (Hf (CH))₃)(C₄H₉)₃) Di-n-butyl hafnium dimethyl (Hf (CH)₃)₂(C₄H₉)₂) Trimethyl-n-butyl-hafnium (Hf (CH)₃)₃(C₄H₉) Tri-n-butyl hafnium ethyl (Hf (CH)₃CH₂)(C₄H₉)₃) Di-n-butyl hafnium diethyl (Hf (CH)₃CH₂)₂(C₄H₉)₂) Triethyl n-butyl hafnium (Hf (CH)₃CH₂)₃(C₄H₉) Etc.).

Examples of the group IVB metal alkoxide compound include tetramethoxytitanium (Ti (OCH)₃)₄) Tetraethoxytitanium (Ti (OCH)₃CH₂)₄) Titanium tetraisobutoxide (Ti (i-OC)₄H₉)₄) Titanium tetra-n-butoxide (Ti (OC)₄H₉)₄) Triethoxymethoxy titanium (Ti (OCH)₃)(OCH₃CH₂)₃) Diethoxydimethoxy titanium (Ti (OCH)₃)₂(OCH₃CH₂)₂）、Trimethoxy ethoxy titanium (Ti (OCH)₃)₃(OCH₃CH₂) Triisobutoxymethoxy titanium (Ti (OCH)₃)(i-OC₄H₉)₃) Di-isobutoxy dimethoxy titanium (Ti (OCH)₃)₂(i-OC₄H₉)₂) Trimethoxy isobutoxy titanium (Ti (OCH)₃)₃(i-OC₄H₉) Triisobutoxyethoxytitanium (Ti (OCH)₃CH₂)(i-OC₄H₉)₃) Di-isobutoxy diethoxy titanium (Ti (OCH)₃CH₂)₂(i-OC₄H₉)₂) Triethoxy isobutoxy titanium (Ti (OCH)₃CH₂)₃(i-OC₄H₉) Tri (n-butoxy) methoxy titanium (Ti (OCH)₃)(OC₄H₉)₃) Di-n-butoxy dimethoxy titanium (Ti (OCH)₃)₂(OC₄H₉)₂) Trimethoxy n-butoxy titanium (Ti (OCH)₃)₃(OC₄H₉) Titanium tri-n-butoxide ethoxide (Ti (OCH)₃CH₂)(OC₄H₉)₃) Di-n-butoxydiethoxytitanium (Ti (OCH)₃CH₂)₂(OC₄H₉)₂) Titanium triethoxy n-butoxide (Ti (OCH)₃CH₂)₃(OC₄H₉) Etc.);

tetramethoxyzirconium (Zr (OCH)₃)₄) Zirconium tetraethoxide (Zr (OCH)₃CH₂)₄) Zirconium tetraisobutoxide (Zr (i-OC)₄H₉)₄) Zirconium tetra-n-butoxide (Zr (OC)₄H₉)₄) Triethoxymethoxy zirconium (Zr (OCH)₃)(OCH₃CH₂)₃) Diethoxydimethoxy zirconium (Zr (OCH)₃)₂(OCH₃CH₂)₂) Trimethoxy zirconium ethoxide (Zr (OCH)₃)₃（OCH₃CH₂) Triisobutoxy methoxy zirconium (Zr (OCH)₃)(i-OC₄H₉)₃) Bis (isobutoxy) dimethoxy zirconium (Zr (OCH)₃)₂(i-OC₄H₉)₂) Trimethoxy isobutoxy zirconium (Zr (OCH)₃)₃(i-C₄H₉) Triisobutoxyethoxyzirconium (Zr (OCH)₃CH₂)(i-OC₄H₉)₃) Bis (isobutoxy) diethoxy zirconium (Zr (OCH)₃CH₂)₂(i-OC₄H₉)₂) Triethoxy isobutoxy zirconium (Zr (OCH)₃CH₂)₃(i-OC₄H₉) Zirconium tri (n-butoxy) methoxy (Zr (OCH)₃)(OC₄H₉)₃) Di-n-butoxy dimethoxy zirconium (Zr (OCH)₃)₂(OC₄H₉)₂) Trimethoxy n-butoxy zirconium (Zr (OCH)₃)₃(OC₄H₉) Zirconium tri (n-butoxy) ethoxide (Zr (OCH)₃CH₂)(OC₄H₉)₃) Di-n-butoxydiethoxy zirconium (Zr (OCH)₃CH₂)₂(OC₄H₉)₂) Triethoxy n-butoxy zirconium (Zr (OCH)₃CH₂)₃(OC₄H₉) Etc.);

tetramethoxyhafnium (Hf (OCH)₃)₄) Hafnium tetraethoxide (Hf (OCH)₃CH₂)₄) Tetra-isobutoxy hafnium (Hf (i-OC)₄H₉)₄) Hafnium tetra-n-butoxide (Hf (OC)₄H₉)₄) Triethoxy hafnium (Hf (OCH)₃)(OCH₃CH₂)₃) Diethoxy dimethoxy hafnium (Hf (OCH)₃)₂(OCH₃CH₂)₂) Trimethoxyhafnium ethoxide (Hf (OCH)₃)₃(OCH₃CH₂) Triisobutoxy methoxy hafnium (Hf (OCH)₃)(i-OC₄H₉)₃) Di-isobutoxy dimethoxy hafnium (Hf (OCH)₃)₂(i-OC₄H₉)₂) Trimethoxy isobutoxy hafnium (Hf (OCH)₃)₃(i-OC₄H₉) Triisobutoxyethoxyhafnium (Hf (OCH)₃CH₂)(i-OC₄H₉)₃) Di-isobutoxy diethoxy hafnium (Hf (OCH)₃CH₂)₂(i-OC₄H₉)₂) Triethoxy isobutoxy hafnium (Hf (OCH)₃CH₂)₃(i-C₄H₉) Tri (n-butoxy) methoxy hafnium (Hf (OCH)₃)(OC₄H₉)₃) Di-n-butoxy dimethoxy hafnium (Hf (OCH)₃)₂(OC₄H₉)₂) Trimethoxy hafnium n-butoxide (Hf (OCH)₃)₃(OC₄H₉) Hafnium tri-n-butoxide (Hf (OCH)₃CH₂)(OC₄H₉)₃) Di-n-butoxy hafnium diethoxide (Hf (OCH)₃CH₂)₂(OC₄H₉)₂) Hafnium triethoxy-n-butoxide (Hf (OCH)₃CH₂)₃(OC₄H₉) Etc.).

Examples of the group IVB metal alkyl halide include trimethyltitanium chloride (TiCl (CH)₃)₃) Triethyltitanium chloride (TiCl (CH))₃CH₂)₃) Triisobutyltitanium chloride (TiCl (i-C))₄H₉)₃) Tri-n-butyltitanium chloride (TiCl (C))₄H₉)₃) Dimethyl titanium dichloride (TiCl)₂(CH₃)₂) Diethyl titanium dichloride (TiCl)₂(CH₃CH₂)₂) Diisobutyl titanium dichloride (TiCl)₂(i-C₄H₉)₂) Tri-n-butyltitanium chloride (TiCl (C))₄H₉)₃) Titanium trichloride methyl (Ti (CH)₃)Cl₃) Titanium ethyltrichloride (Ti (CH)₃CH₂)Cl₃) Isobutyl titanium trichloride (Ti (i-C)₄H₉)Cl₃) N-butylTitanium trichloride (Ti (C)₄H₉)Cl₃）；

Trimethyl titanium bromide (TiBr (CH)₃)₃) Triethyltitanium bromide (TiBr (CH)₃CH₂)₃) Triisobutyl titanium bromide (TiBr (i-C)₄H₉)₃) Tri-n-butyl titanium bromide (TiBr (C)₄H₉)₃) Titanium dimethyl dibromide (TiBr)₂(CH₃)₂) Diethyl titanium dibromide (TiBr)₂(CH₃CH₂)₂) Diisobutyl titanium dibromide (TiBr)₂(i-C₄H₉)₂) Tri-n-butyl titanium bromide (TiBr (C)₄H₉)₃) Titanium methyltrubromide (Ti (CH)₃)Br₃) Titanium ethyltribromide (Ti (CH)₃CH₂)Br₃) Titanium isobutyltribromide (Ti (i-C)₄H₉)Br₃) N-butyl titanium tribromide (Ti (C)₄H₉)Br₃）；

Zirconium trimethyl chloride (ZrCl (CH)₃)₃) Triethylzirconium chloride (ZrCl (CH)₃CH₂)₃) Triisobutyl zirconium chloride (ZrCl (i-C)₄H₉)₃) Tri-n-butyl zirconium chloride (ZrCl (C)₄H₉)₃) Zirconium dimethyldichloride (ZrCl)₂(CH₃)₂) Diethyl zirconium dichloride (ZrCl)₂(CH₃CH₂)₂) Diisobutyl zirconium dichloride (ZrCl)₂(i-C₄H₉)₂) Tri-n-butyl zirconium chloride (ZrCl (C)₄H₉)₃) Zirconium methyltrichloride (Zr (CH)₃)Cl₃) Zirconium ethyl trichloride (Zr (CH)₃CH₂)Cl₃) Isobutyl zirconium trichloride (Zr (i-C)₄H₉)Cl₃) N-butyl zirconium trichloride (Zr (C)₄H₉)Cl₃）；

Zirconium trimethyl bromide (ZrBr (CH)₃)₃) Triethylzirconium bromide (ZrBr (CH)₃CH₂)₃) Triisobutyl zirconium bromide (ZrBr (i-C)₄H₉)₃) Tri-n-butyl zirconium bromide (ZrBr (C)₄H₉)₃) Zirconium dimethyl dibromide (ZrBr)₂(CH₃)₂) Diethyl zirconium dibromide (ZrBr)₂(CH₃CH₂)₂) Diisobutyl zirconium dibromide (ZrBr)₂(i-C₄H₉)₂) Tri-n-butyl zirconium bromide (ZrBr (C)₄H₉)₃) Methyl zirconium tribromide (Zr (CH)₃)Br₃) Zirconium ethyl tribromide (Zr (CH)₃CH₂)Br₃) Isobutyl zirconium tribromide (Zr (i-C)₄H₉)Br₃) N-butyl zirconium tribromide (Zr (C)₄H₉)Br₃）；

Trimethyl hafnium chloride (HfCl (CH)₃)₃) Triethyl hafnium chloride (HfCl (CH)₃CH₂)₃) Triisobutylhafnium chloride (HfCl (i-C)₄H₉)₃) Tri-n-butyl hafnium chloride (HfCl (C)₄H₉)₃) Hafnium dimethyl dichloride (HfCl)₂(CH₃)₂) Hafnium diethyldichloride (HfCl)₂(CH₃CH₂)₂) Diisobutyldimethium chloride (HfCl)₂(i-C₄H₉)₂) Tri-n-butyl hafnium chloride (HfCl (C)₄H₉)₃) Hafnium methyl trichloride (Hf (CH)₃)Cl₃) Hafnium ethyl trichloride (Hf (CH)₃CH₂)Cl₃) Isobutyl hafnium trichloride (Hf (i-C)₄H₉)Cl₃) N-butyl hafnium trichloride (Hf (C)₄H₉)Cl₃）；

Trimethyl hafnium bromide (HfBr (CH)₃)₃) Triethyl hafnium bromide (HfBr (CH)₃CH₂)₃) Triisobutylbromide hafnium (HfBr (i-C)₄H₉)₃) Tri-n-butyl hafnium bromide (HfBr (C)₄H₉)₃) Hafnium dimethyl dibromide (f) ((ii))HfBr₂(CH₃)₂) Hafnium diethyl dibromide (HfBr)₂(CH₃CH₂)₂) Diisobutyl hafnium dibromide (HfBr)₂(i-C₄H₉)₂) Tri-n-butyl hafnium bromide (HfBr (C)₄H₉)₃) Hafnium methyl tribromide (Hf (CH)₃)Br₃) Hafnium ethyl tribromide (Hf (CH)₃CH₂)Br₃) Isobutyl hafnium tribromide (Hf (i-C)₄H₉)Br₃) N-butyl hafnium tribromide (Hf (C)₄H₉)Br₃）。

Examples of the alkoxy halide of a group IVB metal include trimethoxy titanium chloride (TiCl (OCH)₃)₃) Titanium triethoxide chloride (TiCl (OCH)₃CH₂)₃) Triisobutoxy titanium chloride (TiCl (i-OC)₄H₉)₃) Titanium tri-n-butoxide (TiCl (OC)₄H₉)₃) Dimethoxy titanium dichloride (TiCl)₂(OCH₃)₂) Diethoxytitanium dichloride (TiCl)₂(OCH₃CH₂)₂) Bis (isobutoxy) titanium dichloride (TiCl)₂(i-OC₄H₉)₂) Titanium tri-n-butoxide (TiCl (OC)₄H₉)₃) Titanium methoxytrichloride (Ti (OCH)₃)Cl₃) Titanium ethoxide trichloride (Ti (OCH)₃CH₂)Cl₃) Titanium (Ti (i-C)) trichloride (isobutoxy group)₄H₉)Cl₃) Titanium (Ti (OC) chloride n-butoxide₄H₉)Cl₃）；

Trimethoxy titanium bromide (TiBr (OCH)₃)₃) Titanium triethoxy bromide (TiBr (OCH)₃CH₂)₃) Triisobutoxytitanium bromide (TiBr (i-OC)₄H₉)₃) Titanium tri-n-butoxide bromide (TiBr (OC)₄H₉)₃) Titanium dibromide dimethoxy (TiBr)₂(OCH₃)₂) DiethoxybromineTitanium (TiBr)₂(OCH₃CH₂)₂) Titanium diisobutoxy dibromide (TiBr)₂(i-OC₄H₉)₂) Titanium tri-n-butoxide bromide (TiBr (OC)₄H₉)₃) Titanium methoxytribromide (Ti (OCH)₃)Br₃) Titanium ethoxytribromide (Ti (OCH)₃CH₂)Br₃) Titanium (Ti (i-C)) isobutoxy tribromide₄H₉)Br₃) Titanium n-butoxide tribromide (Ti (OC)₄H₉)Br₃）；

Trimethoxy zirconium chloride (ZrCl (OCH)₃)₃) Zirconium triethoxy chloride (ZrCl (OCH)₃CH₂)₃) Triisobutoxy zirconium chloride (ZrCl (i-OC)₄H₉)₃) Zirconium tri-n-butoxide chloride (ZrCl (OC)₄H₉)₃) Dimethoxy zirconium dichloride (ZrCl)₂(OCH₃)₂) Diethoxy zirconium dichloride (ZrCl)₂(OCH₃CH₂)₂) Bis (isobutoxy) zirconium dichloride (ZrCl)₂(i-OC₄H₉)₂) Zirconium tri-n-butoxide chloride (ZrCl (OC)₄H₉)₃) Zirconium oxychloride (Zr (OCH)₃)Cl₃) Zirconium ethoxytrichloride (Zr (OCH)₃CH₂)Cl₃) Isobutoxy zirconium trichloride (Zr (i-C)₄H₉)Cl₃) N-butoxy zirconium trichloride (Zr (OC)₄H₉)Cl₃）；

Trimethoxy zirconium bromide (ZrBr (OCH)₃)₃) Zirconium triethoxy bromide (ZrBr (OCH)₃CH₂)₃) Triisobutoxy zirconium bromide (ZrBr (i-OC)₄H₉)₃) Zirconium tri-n-butoxide bromide (ZrBr (OC)₄H₉)₃) Zirconium dimethoxydibromide (ZrBr)₂(OCH₃)₂) Diethoxy zirconium dibromide (ZrBr)₂(OCH₃CH₂)₂) Zirconium diisobutoxy dibromide (ZrBr)₂(i-OC₄H₉)₂) Zirconium tri-n-butoxide bromide (ZrBr (OC)₄H₉)₃) Zirconium (Zr) (OCH) tribromide₃)Br₃) Zirconium ethoxy tribromide (Zr (OCH)₃CH₂)Br₃) Isobutoxy zirconium tribromide (Zr (i-C)₄H₉)Br₃) N-butoxy zirconium tribromide (Zr (OC)₄H₉)Br₃）；

Trimethoxyhafnium chloride (HfCl (OCH)₃)₃) Hafnium triethoxide chloride (HfCl (OCH)₃CH₂)₃) Triisobutoxy hafnium chloride (HfCl (i-OC)₄H₉)₃) Hafnium tri-n-butoxide chloride (HfCl (OC)₄H₉)₃) Hafnium dimethoxy dichloride (HfCl)₂(OCH₃)₂) Hafnium dichloride diethoxy (HfCl)₂(OCH₃CH₂)₂) Bis (isobutoxy) hafnium dichloride (HfCl)₂(i-OC₄H₉)₂) Hafnium tri-n-butoxide chloride (HfCl (OC)₄H₉)₃) Hafnium methoxy trichloride (Hf (OCH)₃)Cl₃) Ethoxy hafnium trichloride (Hf (OCH)₃CH₂)Cl₃) Isobutoxy hafnium trichloride (Hf (i-C)₄H₉)Cl₃) N-butoxy hafnium trichloride (Hf (OC)₄H₉)Cl₃）；

Trimethoxy hafnium bromide (HfBr (OCH)₃)₃) Hafnium triethoxide bromide (HfBr (OCH)₃CH₂)₃) Triisobutoxy hafnium bromide (HfBr (i-OC)₄H₉)₃) Hafnium tri-n-butoxide bromide (HfBr (OC)₄H₉)₃) Hafnium dimethoxy dibromide (HfBr)₂(OCH₃)₂) Hafnium diethoxy dibromide (HfBr)₂(OCH₃CH₂)₂) Hafnium bis (isobutoxy) bromide (HfBr)₂(i-OC₄H₉)₂) Hafnium tri-n-butoxide bromide (HfBr (OC)₄H₉)₃) Hafnium methoxy tribromide (Hf (OCH)₃)Br₃) Hafnium ethoxy tribromide (Hf (OCH)₃CH₂)Br₃) Isobutoxy hafnium tribromide (Hf (i-C)₄H₉)Br₃) Hafnium n-butoxide tribromide (Hf (OC)₄H₉)Br₃）。

When the chemical treatment agent is in a liquid state at normal temperature, the chemical treatment reaction can be carried out directly using the chemical treatment agent. When the chemical treatment agent is in a solid state at ordinary temperature, it is preferably used in the form of a solution for the sake of metering and handling convenience. Of course, when the chemical treatment agent is in a liquid state at ordinary temperature, the chemical treatment agent may be used in the form of a solution 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 support structure of the composite support.

Specifically, C may be mentioned_5-12Alkane, C_5-12Cycloalkanes, halogen radicals C_5-12Alkanes and halogenated C_5-12Examples of the cycloalkane include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, with pentane, hexane, decane and cyclohexane being preferred, and hexane being most preferred.

These solvents may be used singly or in combination in any ratio.

In addition, the concentration of the chemical treatment agent in the solution thereof is not particularly limited, and may be appropriately selected as needed as long as it can achieve 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 chemical treatment agent may be used as it is, or may be prepared as a solution of the chemical treatment agent and then used.

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

According to the present invention, the chemical treatment reaction is carried out, for example, by bringing the composite carrier into contact with the chemical treatment agent in the presence of a solvent (also referred to as a solvent for chemical treatment).

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

Specifically, the solvent for chemical treatment includes C_5-12Alkane, C_5-12Cycloalkanes, halogen radicals C_5-12Alkanes and halogenated C_5-12Examples of the cycloalkane include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, with pentane, hexane, decane and cyclohexane being preferred, and hexane being most preferred.

These solvents may be used singly or in combination in any ratio.

According to the present invention, the amount of the chemical treatment solvent 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 some cases. 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 to be used may be appropriately reduced according to the actual situation, but is not particularly limited.

According to the present invention, as the chemical treatment agent, the amount is used so 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 an embodiment of the present invention, the chemical treatment reaction is performed by contacting the composite carrier with the chemical treatment agent in the presence of the solvent for chemical treatment.

The contact may be carried out, for example, by adding the composite carrier to the solvent for chemical treatment 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 the reaction with stirring at 0 to 100 ℃ (preferably 20 to 80 ℃). The reaction time in this case is not particularly limited, and may be, for example, 0.5 to 8 hours, preferably 1 to 4 hours.

After the chemical treatment reaction is finished, a product (modified composite carrier) after chemical treatment can be obtained by filtering, washing and drying.

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

The drying can be carried out by conventional methods such as inert gas drying, vacuum drying or vacuum heating drying, preferably inert gas drying or vacuum heating drying, most preferably vacuum heating drying. The drying temperature is generally in the range of normal temperature to 140 ℃, and the drying time is generally 2-20h, but is not limited thereto.

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 relative to a metallocene catalyst, a metallo-organic compound which does not contain a cyclopentadienyl group such as a metallocene ring, a fluorene ring or an indene ring or a derivative thereof in the structure and is capable of exhibiting an 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 polydentate ligand (preferably a tridentate or more) coordinately bound to said central metal atom, whereas the term "non-metallocene ligand" is the aforementioned polydentate ligand.

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

。

according to this chemical formula, the ligands forming coordination bonds with the central metal atom M comprise n groups X and M multidentate ligands (formula in parentheses). According to the chemical structure of the polydentate ligand, groups A, D and E (coordinating groups) form coordinate bonds with the central metal atom M through coordinating atoms (e.g., heteroatoms such as N, O, S, Se and P) contained in these groups. In the present invention, the central metal atom M is also referred to as active metal, and the amount of catalyst is generally expressed in terms of the amount of central metal atom M in the non-metallocene complex.

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

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

And

　　　　　　（A）（B）。

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 formulae.

、

、

　　　　　（A-1）　　　　　　　　　　（A-2）

、

、

　　　　（A-3）　　　　　　　（A-4）

、

、

　　　　　　（B-1）　　　　　　　　　　　　（B-2）

And

，

　　　　　　（B-3）　　　　　　　　（B-4）

in all of the above chemical structural formulae,

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 the group III to group XI metal atoms of the periodic Table of the elements, preferably a group IVB metal atom, such as 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, C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀A 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, wherein a plurality of xs may be the same or different and may form a bond or a ring with each other;

a is selected from oxygen atom, sulfur atom, selenium atom,

、-NR²³R²⁴、-N(O)R²⁵R²⁶、

、-PR²⁸R²⁹、-P(O)R³⁰OR³¹Sulfone group, sulfoxide group or-Se (O) R³⁹Wherein N, O, S, Se and P are each coordinating atoms;

b is selected from nitrogen atom, nitrogen-containing group, phosphorus-containing group or C₁-C₃₀A hydrocarbyl group;

d is selected from nitrogen atom, oxygen atom, sulfur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing group, C₁-C₃₀A 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 nitrogen atom, nitrogen-containing group, oxygen atom, sulfur atom, selenium atom or phosphorus-containing group, wherein N, O, S, Se and P are coordination atoms respectively;

g is selected from C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀A hydrocarbyl or inert functional group;

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 a coordinating atom;

z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group (-CN), and examples thereof include-NR²³R²⁴、-N(O)R²⁵R²⁶、-PR²⁸R²⁹、-P(O)R³⁰R³¹、-OR³⁴、-SR³⁵、-S(O)R³⁶、-SeR³⁸or-Se (O) R³⁹Wherein N, O, S, Se and P are each coordinating atoms;

→ represents a single bond or a double bond;

-represents a covalent or ionic bond;

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

R¹To R⁴、R⁶To R²¹Each independently selected from hydrogen and C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)₂Cl and-CH₂CH₂Cl) or inert functional groups. R²²To R³⁶、R³⁸And R³⁹Each independently selected from hydrogen and C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)₂Cl and-CH₂CH₂Cl). The above groups may be the same or different from each other, wherein adjacent groups such as R¹And R²，R⁶And R⁷，R⁷And R⁸，R⁸And R⁹，R¹³And R¹⁴，R¹⁴And R¹⁵，R¹⁵And R¹⁶，R¹⁸And R¹⁹，R¹⁹And R²⁰，R²⁰And R²¹，R²³And R²⁴Or R is²⁵And R²⁶Etc. 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 substituted aromatic ring having 1 to 4 carbon atoms₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀Hydrocarbyl (of which halogenated hydrocarbyl is preferred, such as-CH)₂Cl and-CH₂CH₂Cl) substituted benzene ring, and

R⁵selected from lone pair of electrons on nitrogen, hydrogen, C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀A hydrocarbyl group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group. When R is⁵When it is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R⁵N, O, S, P and Se in (1) can be used as a coordinating atom (coordinating with the central metal atom M).

In the context of the present invention, examples of said inert functional groups are selected from the group consisting of halogens, oxygen-containing groups, nitrogen-containing groups, silicon-containing groups, germanium-containing groups, sulfur-containing groups, tin-containing groups, C₁-C₁₀Ester group or nitro group (-NO)₂) And (C) and the like, but generally does not include C₁-C₃₀Hydrocarbyl and substituted C₁-C₃₀A hydrocarbyl group.

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

(1) does not interfere with the process of coordination of the group A, D, E, F, Y or Z to 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 existing coordination of these groups to the central metal atom M.

According to the present invention, in all the aforementioned chemical structural formulae, any two adjacent ones are optionallyPlural or more radicals, e.g. R²¹With the group Z, or R¹³Together with the group Y, may be joined to each other to form a ring, preferably forming C containing a heteroatom from said group Z or Y₆-C₃₀Aromatic heterocyclic ring, such as pyridine ring, etc., wherein said aromatic heterocyclic ring is optionally substituted with 1 or more selected from C₁-C₃₀Hydrocarbyl and substituted C₁-C₃₀Substituent of hydrocarbyl.

In the context of the present invention, the halogen is selected from F, Cl, Br or I. The nitrogen-containing group is selected from

、-NR²³R²⁴、-T-NR²³R²⁴or-N (O) R²⁵R²⁶. The phosphorus-containing group is selected from

、-PR²⁸R²⁹、-P(O)R³⁰R³¹or-P (O) R³²(OR³³). The oxygen-containing group is selected from hydroxyl, -OR³⁴and-T-OR³⁴. The sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶or-T-SO₂R³⁷. The selenium-containing group is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹or-T-Se (O) R³⁹. The group T is selected from C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀A hydrocarbyl group. The R is³⁷Selected from hydrogen, C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀A hydrocarbyl group.

In the context of the present invention, said C₁-C₃₀The hydrocarbon radical being selected from C₁-C₃₀Alkyl (preferably C)₁-C₆Alkyl, e.g. isobutyl), C₇-C₃₀Alkaryl (e.g., tolyl, xylyl, diisobutylphenyl, etc.), C₇-C₃₀Aralkyl (e.g. benzyl), C₃-C₃₀Cyclic alkyl, C₂-C₃₀Alkenyl radical, C₂-C₃₀Alkynyl, alkynyl,C₆-C₃₀Aryl (e.g. phenyl, naphthyl, anthracyl, etc.), C₈-C₃₀Condensed ring radicals or C₄-C₃₀A heterocyclic group, wherein the heterocyclic group contains 1 to 3 hetero atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom, such as a pyridyl group, a pyrrolyl group, a furyl group, a thienyl group or the like.

According to the invention, in the context of the present invention, said C is defined as being specific to the relevant group to which it is bound₁-C₃₀Hydrocarbyl radicals are sometimes referred to as C₁-C₃₀Hydrocarbon diyl (divalent radical, otherwise known as C)₁-C₃₀Alkylene) or C₁-C₃₀Hydrocarbon triyl (trivalent radical), as will be apparent to those skilled in the art.

In the context of the present invention, said substituted C₁-C₃₀By hydrocarbyl is meant C bearing one or more inert substituents₁-C₃₀A hydrocarbyl group. By inert substituents, it is meant that these substituents are paired with the aforementioned coordinating groups (meaning the aforementioned groups A, D, E, F, Y and Z, or optionally also including the group R⁵) The coordination process with the central metal atom M is not substantially interfered; in other words, these substituents have no ability or opportunity (e.g., 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, for example, selected from halogen or C₁-C₃₀Alkyl (preferably C)₁-C₆Alkyl groups such as isobutyl).

In the context of the present invention, the boron-containing group is selected from BF₄ ^-、(C₆F₅)₄B^-Or (R)⁴⁰BAr₃)^-(ii) a The aluminum-containing group is selected from alkyl aluminum and AlPh₄ ^-、AlF₄ ^-、AlCl₄ ^-、AlBr₄ ^-、AlI₄ ^-Or R⁴¹AlAr₃ ^-(ii) a The silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴or-T-SiR⁴⁵(ii) a The germanium-containing group is selected from-GeR⁴⁶R⁴⁷R⁴⁸or-T-GeR⁴⁹(ii) a The tin-containing group is selected from-SnR⁵⁰R⁵¹R⁵²、-T-SnR⁵³or-T-Sn (O) R⁵⁴Wherein Ar represents C₆-C₃₀And (4) an aryl group. R⁴⁰To R⁵⁴Each independently selected from hydrogen, C₁-C₃₀Hydrocarbyl or substituted C of the foregoing₁-C₃₀The hydrocarbon group may be the same or different from each other, and adjacent groups may be bonded to each other to form a bond or form a ring. Wherein the group T is as defined above.

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

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

、

and

。

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

、

、

、

、

、

、

、

and

。

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

、

、

、

、

and

。

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

and

。

these non-metallocene complexes may be used singly or in combination of two or more in an arbitrary 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 the details of the manufacturing method, see, for example, WO03/010207 and chinese patents ZL01126323.7 and ZL02110844.7, etc., which are incorporated herein by reference in their entirety.

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

When 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. The solvent includes, for example, C_6-12Aromatic hydrocarbons, halogenated C_6-12Aromatic hydrocarbons, halogenated C_1-10One 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. Among them, preferred isC_6-12Aromatic hydrocarbons, dichloromethane and tetrahydrofuran.

These solvents may be used singly or in combination in any ratio.

When dissolving the non-metallocene complex, stirring may be used as needed (the rotation speed of the stirring is generally 10 to 500 rpm).

According to the invention, it is convenient that the ratio of the non-metallocene complex relative to the solvent is generally from 0.02 to 0.30g/ml, preferably from 0.05 to 0.15g/ml, but in some cases it is not limited thereto.

Examples of the mode for contacting the non-metallocene complex with the modified composite support in the presence of the second solvent include the following modes.

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

In the production of the second mixed slurry, the contact manner 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, wherein the latter is 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 room 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 obtained second mixed slurry is a slurry system. Although not necessary, in order to ensure the uniformity of the system, the second mixed slurry is preferably subjected to a closed standing for a certain 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 a 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 contact is performed.

The second solvent includes, for example, C_6-12Aromatic hydrocarbons, halogenated C_6-12Aromatic hydrocarbon, C_5-12Alkanes, halogenated C_1-10One or more of alkanes and ethers. Specific examples thereof include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, hexane, dichloromethane, dichloroethane, tetrahydrofuran, and the like. Among them, C is preferable_6-12Aromatic hydrocarbons, dichloromethane and tetrahydrofuran, dichloromethane being most preferred.

These solvents may be used singly or in combination in any ratio.

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

According to the present invention, the amount of the second solvent is not limited, as long as it is an amount sufficient to achieve sufficient contact between the modified composite support and the non-metallocene complex. For example, it is convenient that the ratio of the non-metallocene complex to the second solvent is generally 0.01 to 0.25g/ml, preferably 0.05 to 0.16g/ml, but is not limited thereto in some cases.

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

In one embodiment of the present invention, the second mixed slurry can be directly used as a supported non-metallocene catalyst without drying the second mixed slurry.

At this time, the direct drying may be carried out 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., wherein the heat drying under a vacuum atmosphere is preferable. The drying is generally carried out at a temperature of 5 to 15 ℃ lower than the boiling point of any solvent contained in the mixed slurry (generally 30 to 160 ℃, preferably 60 to 130 ℃), and the drying time is generally 2 to 24 hours, but is sometimes not limited thereto.

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

According to the invention, the alcohol is used in such an amount that the molar ratio of the magnesium compound to the alcohol, calculated as Mg element, is from 1: 0.02 to 4.00, preferably from 1: 0.05 to 3.00, more preferably from 1: 0.10 to 2.50.

According to the present invention, as the amount of the porous support, the mass ratio of the magnesium compound to the porous support based on the 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 present invention, as the amount of the precipitant, the precipitant is used in such an amount that the volume ratio of the precipitant to the first solvent is 1: 0.2 to 5, preferably 1: 0.5 to 2, more preferably 1: 0.8-1.5.

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 from 1: 0.01 to 1, preferably from 1: 0.04 to 0.4, more preferably from 1: 0.08 to 0.2.

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

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

According to the invention, the cocatalyst is selected from one or more of aluminoxanes, aluminium alkyls or halogenated aluminium alkyls.

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

In the above formula, the radicals R, equal to or different from each other (preferably equal), are each independently selected from C₁-C₈Alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl; n is any integer in the range of 1 to 50, preferably in the range of 10 to 30.

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

These aluminoxanes may be used singly or in combination 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 from one another (preferably identical) and are each independently selected from C₁-C₈Alkyl 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)₃CH₂)₃) Tri-n-propylaluminum (Al (C)₃H₇)₃) Triisopropylaluminum (Al (i-C)₃H₇)₃) Triisobutylaluminum (Al (i-C)₄H₉)₃) Tri-n-butylaluminum (Al (C)₄H₉)₃) Triisopentylaluminum (Al (i-C)₅H₁₁)₃) Tri-n-pentylaluminum (Al (C)₅H₁₁)₃) Tri-n-hexylaluminum (Al (C)₆H₁₃)₃) Triisohexylaluminum (Al (i-C)₆H₁₃)₃) Diethyl methyl aluminum (Al (CH)₃)(CH₃CH₂)₂) And dimethyl ethyl aluminum (Al (CH)₃CH₂）(CH₃)₂) And the like, among which trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable, and triethylaluminum and triisobutylaluminum are most preferable.

These alkyl aluminum compounds may be used singly or in combination in any ratio.

Examples of the halogenated alkylaluminum include compounds represented by the following general formula (III'):

Al(R)_nX_3-n　　　　　（III'）

wherein the radicals R are identical or different from one another (preferably identical) and are each independently selected from C₁-C₈Alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, most preferably methyl; x represents fluorine, chlorine, bromine or iodine; n represents 1 or 2.

Specifically, the alkyl aluminum halide includes, for example, dimethyl aluminum monochloride (Al (CH)₃)₂Cl), dichloromethylaluminum (Al (CH)₃)Cl₂) Aluminum diethyl monochloride (Al (CH)₃CH₂)₂Cl), ethyl aluminum dichloride (Al (CH)₃CH₂)Cl₂) Aluminum monochlorodipropyl (Al (C)₃H₇)₂Cl), dichloropropylaluminum (Al (C)₃H₇)Cl₂) Aluminum di-n-butyl monochloride (Al (C))₄H₉)₂Cl), n-butylaluminum dichloride (Al (C)₄H₉)Cl₂) Aluminum chlorodiisobutylaluminum (Al (i-C)₄H₉)₂Cl), isobutylaluminum dichloride (Al (i-C)₄H₉)Cl₂) Monochlorodin-pentylaluminum (Al (C)₅H₁₁)₂Cl), dichloro-n-pentylaluminum (Al (C)₅H₁₁)Cl₂) Aluminum (Al (i-C)) monochlorodiisoamyl₅H₁₁)₂Cl), dichloroisoamyl aluminum (Al (i-C)₅H₁₁)Cl₂) Aluminum di-n-hexyl monochloride (Al (C)₆H₁₃)₂Cl), dichloro-n-hexylaluminum (Al (C)₆H₁₃)Cl₂) Aluminum (Al (i-C)) monochlorodiisohexyl₆H₁₃)₂Cl), dichloroisohexylaluminum (Al (i-C)₆H₁₃)Cl₂) Chloromethyl ethyl aluminum (Al (CH)₃)(CH₃CH₂) Cl), chloromethylpropylaluminum (Al (CH)₃)(C₃H₇) Cl), chloromethyl n-butylaluminum (Al (CH)₃)(C₄H₉) Cl), chloromethyl isobutyl aluminum (Al (CH)₃)(i-C₄H₉) Cl), monochloroethylpropylaluminum (Al (CH)₂CH₃)(C₃H₇) Cl), monochloroethyl n-butylaluminum (AlCH)₂CH₃)(C₄H₉) Cl), chloromethyl isobutyl aluminum (Al (CH)₂CH₃)(i-C₄H₉) Cl), etc., among which diethylaluminum monochloride, ethylaluminum dichloroide, di-n-butylaluminum monochloride, n-butylaluminum dichloroide, diisobutylaluminum monochloride, isobutylaluminum dichloroide, di-n-hexylaluminum monochloride, n-hexylaluminum dichloroide are preferable, diethylaluminum monochloride, ethylaluminum dichloroide and di-n-hexylaluminum monochloride are further preferable, and diethylaluminum monochloride is most preferable.

These alkyl aluminum halides may be used singly or in combination in any ratio.

In addition, according to the present invention, the cocatalyst may be used singly or in combination of a plurality of the above-mentioned cocatalysts in an arbitrary ratio as required, and is not particularly limited.

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

According to the present invention, in the preparation method of the ultra-high molecular weight polyethylene, the polymerization solvent is selected from 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 ℃.

According to the present invention, examples of the alkane solvent having a boiling point of 5 to 55 ℃ include 2, 2-dimethylpropane (also referred to as neopentane having a boiling point of 9.5 ℃ and a saturated vapor pressure of 146.63KPa at 20 ℃), 2-methylbutane (also referred to as isopentane having a boiling point of 27.83 ℃ and a saturated vapor pressure of 76.7KPa at 20 ℃), n-pentane (having a boiling point of 36.1 ℃ and a saturated vapor pressure of 56.5KPa at 20 ℃), and cyclopentane (having a boiling point of 49.26 ℃ and a saturated vapor pressure of 34.6KPa at 20 ℃), and preferably an alkane solvent having a boiling point of 25 to 52 ℃.

The mixed alkane solvent having a saturated vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃ is a mixed solvent in which different alkane solvents are mixed in a ratio, for example, a solvent of hexane and its isomer, a mixed solvent of pentane and its isomer solvent, or an alkane mixture extracted by a solvent distillation apparatus by distillation cut, and preferably a mixed solvent of pentane and its isomer solvent. 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. As long as the saturated vapor pressure at 20 ℃ is from 20 to 150KPa (preferably from 40 to 110 KPa).

In one embodiment of the present invention, the mixed alkane solvent having a saturation vapor pressure of 20 to 150KPa (preferably 40 to 110 KPa) at 20 ℃, is preferably a mixed alkane solvent having a saturation 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, and more preferably a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of isopentane and cyclopentane, a combination of neopentane and n-pentane, a combination of n-pentane-isopentane-cyclopentane, a combination of neopentane-isopentane-n-pentane, and the like. Regarding 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: 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 of the present invention, the slurry polymerization of ethylene is carried out at a polymerization temperature of 50 to 100 ℃ and preferably 60 to 90 ℃. Wherein, if slurry polymerization of ethylene is carried out at a higher polymerization temperature, a higher boiling point solvent may be selected, whereas slurry polymerization of ethylene is carried out at a lower polymerization temperature, a lower boiling point solvent may be selected. It is known that under the slurry polymerization conditions of ethylene, under other conditions of similarly comparable polymerization pressure, procatalyst, cocatalyst and solvent, the viscosity average molecular weight of the ultra high molecular weight polyethylene thus obtained increases and then decreases with increasing polymerization temperature within the polymerization temperature range described in the present invention, and thus, according to the present invention, the viscosity average molecular weight of the ultra high molecular weight polyethylene obtained by slurry polymerization of ethylene can be adjusted and controlled by the polymerization temperature.

In the process for producing an ultrahigh 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 3.0 MPa. Wherein, for example, a lower polymerization pressure may be selected for slurry polymerization of ethylene at a higher polymerization temperature, whereas a higher polymerization pressure may be selected for slurry polymerization of ethylene at a lower polymerization temperature. Under the condition of slurry polymerization of ethylene, under the similar and comparable conditions of polymerization temperature, main catalyst, cocatalyst and solvent, etc. and in the polymerization pressure range described in the present invention, the viscosity-average molecular weight of the ultrahigh molecular weight polyethylene obtained by means of said polymerization process is firstly increased and then decreased with the increase of polymerization pressure, so that according to the present invention, the viscosity-average molecular weight of the ultrahigh molecular weight polyethylene obtained by means of slurry polymerization of ethylene can also be regulated and controlled by means of polymerization pressure.

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 ℃ provided by the invention is used as the polymerization solvent, thereby providing opportunities and choices for preparing the ultra-high molecular weight polyethylene with different viscosity-average molecular weights by slurry polymerization of ethylene. For example, the slurry polymerization reaction of ethylene is easily conducted at a higher polymerization pressure and a lower polymerization temperature by using an alkane solvent with a lower boiling point (such as n-pentane, isopentane or cyclopentane) 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.), while the slurry polymerization reaction of ethylene is conducted at a lower polymerization pressure and a higher polymerization temperature by using an alkane solvent with a higher boiling point or a mixed alkane solvent with a lower saturated vapor pressure at 20 ℃), in order to effectively remove the heat of polymerization reaction, the slurry polymerization reaction of ethylene is conducted at a lower polymerization pressure and a higher polymerization temperature.

In one embodiment of the present invention, there is provided an ultrahigh viscosity-average molecular weight ethylene copolymer having a viscosity-average molecular weight of 150-800 g/mol and a bulk density of 0.30 to 0.55g/cm³True density of 0.900-0.950g/cm³The molar insertion rate of the comonomer is 0.05-4.0 percent, the titanium content is 0-3ppm, the calcium content is 0-5ppm, the magnesium content is 0-10ppm, the aluminum content is 0-30ppm, the chlorine content is 0-50ppm, the total ash content is less than 200ppm, the melting point is 140-.

In one embodiment of the present invention, there is provided an ultrahigh viscosity average molecular weight ethylene copolymer having a viscosity average molecular weight of 300-700 g/mol and a bulk density of 0.33 to 0.52g/cm³The true density is 0.905-0.945g/cm³The molar insertion rate of the comonomer is 0.10-2.0%, the titanium content is 0-2ppm, the calcium content is 0-3ppm, the magnesium content is 0-5ppm, the aluminum content is 0-20ppm, the chlorine content is 0-30ppm,the total ash content is less than 150ppm, the melting point is 142-150 ℃, the crystallinity is 45-65%, and the tensile elastic modulus is more than 280 MPa.

In one embodiment of the present invention, a method for preparing an ethylene copolymer with ultra-high viscosity average molecular weight is provided, wherein a supported non-metallocene catalyst is used as a main catalyst, one or more of aluminoxane, alkylaluminum, and halogenated alkylaluminum are 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, and the molar ratio of a comonomer to active metal in the catalyst is 10-500: 1, under the condition of ethylene slurry polymerization reaction, making ethylene and comonomer implement slurry polymerization reaction under the condition of ethylene slurry polymerization reaction, and the polymerization activity of ethylene slurry is higher than 2 ten thousand grams of ethylene copolymer/gram of main catalyst.

In one embodiment of the present invention, in the preparation method of the ethylene copolymer with ultrahigh viscosity average molecular weight, the polymerization temperature is 60-90 ℃, the polymerization pressure is 1.0-3.0MPa, and the molar ratio of the comonomer to the active metal in the catalyst is 20-400: 1, under the condition of ethylene slurry polymerization reaction, making ethylene and comonomer implement slurry polymerization reaction under the condition of ethylene slurry polymerization reaction, and the polymerization activity of ethylene slurry is higher than 3 ten thousand grams of ethylene copolymer/gram of main catalyst.

In the method for preparing the ultra-high molecular weight polyethylene of the present invention, the ethylene slurry polymerization reactor is not limited as long as the ethylene and the comonomer can be contacted with the procatalyst and the cocatalyst in the solvent within the polymerization pressure and temperature range of the present invention, and the stirring of the tank-type ethylene slurry can be performed to effectively prevent the materials from being bonded and aggregated. The stirring rate of the stirring tank is not particularly limited as long as it can ensure the normal dispersion of the slurry in the reactor, and the stirring speed is related to the volume of the reactor, and in general, the stirring speed is 10 to 1000rpm, preferably 20 to 500rpm, as the stirring speed is required to be larger as the volume of the reactor is smaller.

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

According to the invention, the supported non-metallocene catalyst as the main catalyst and one or more of aluminoxane, alkyl aluminum or halogenated alkyl aluminum as the cocatalyst are added into the polymerization reaction system in a way that the main catalyst is added firstly and then the cocatalyst is added, or the cocatalyst is added firstly and then the main catalyst is added, or the supported non-metallocene catalyst and the cocatalyst are added together after being contacted and mixed firstly, or are added respectively and simultaneously. When the main catalyst and the cocatalyst are added respectively, the main catalyst and the cocatalyst can be added in sequence in the same feeding pipeline, or can be added in sequence in multiple feeding pipelines, 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 the polymerization reaction of the 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 reaction conditions of the polymerization pressure, the polymerization temperature, the polymerization solvent and the comonomer.

According to the present invention, it was found that the polymerization pressure and polymerization solvent of the present invention are advantageous in achieving high activity of the catalyst and thus obtaining ultra-high molecular weight polyethylene having a low content of metal elements, and that the polymerization temperature of the present invention is advantageous in 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 also advantageous in achieving high activity of the catalyst.

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

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

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

The contents of active metal elements in the supported non-metallocene catalyst and titanium, magnesium, calcium, aluminum, silicon, chlorine and other elements in the ultrahigh molecular weight polyethylene are determined by adopting an ICP-AES method.

The ash content in the ultra-high molecular weight polyethylene is determined by a direct calcination method according to the national standard GBT 9345.1-2008. The polymer is burned in a muffle furnace and the residue is treated at elevated temperature until constant weight, and the amount of residue is divided by the initial polymer mass.

The comonomer insertion rate in the ultra-high molecular weight ethylene copolymer is calibrated by the known content copolymer by adopting a nuclear magnetic resonance method, and is measured by adopting a 66/S type Fourier transform infrared spectrometer of Bruck company in Germany.

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

Mv=5.37×10⁴×[η]^1.37

Wherein η is the intrinsic viscosity.

The determination of the residual solvent content ratio in the wet material after the polymerization reaction was carried out by directly filtering the ethylene slurry polymer powder obtained after the polymerization reaction in the polymerization reactor with a 100-mesh filter screen, weighing the wet polymer mass m1, weighing the dry polymer powder mass m2 after completely drying at 80 ℃ under vacuum of 20mBar, and further calculating the residual solvent content ratio.

Solvent residual content ratio =

。

The melting point and crystallinity of the ultra-high molecular weight polyethylene are determined by differential scanning calorimetry, which is a DSC type Q1000 differential scanning calorimetry tester manufactured by TA of America, and is determined according to the standard YYT 0815-2010; the tensile elastic modulus of the polymer is measured by a universal tester according to the standard GB/T1040.2-2006, and the tabletting conditions are that the prepressing 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 15.0 MPa.

EXAMPLE 1 preparation of procatalyst

Examples 1 to 1

The magnesium compound is anhydrous magnesium chloride, the first solvent is tetrahydrofuran, the alcohol is ethanol, the porous carrier is silicon dioxide, namely silica gel, the model of which is ES757 of Ineos company, and the silica gel is firstly continuously roasted for 4 hours at 600 ℃ in a nitrogen atmosphere for thermal activation. The chemical treating agent of IVB group adopts titanium tetrachloride (TiCl)₄) The second solvent adopts dichloromethane, and the non-metallocene complex adopts the structure as

The compound of (1).

Weighing 5g of magnesium compound, adding the magnesium compound into a first solvent, then adding alcohol, completely dissolving at normal temperature to obtain a magnesium compound solution, then 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 chemical treatment agent within 30min at normal temperature, uniformly heating to 60 ℃, reacting for 2h at constant temperature, filtering, washing for 3 times by using the hexane solvent, wherein the dosage of each time is the same as that of the previously added solvent, and finally, vacuumizing and drying at 60 ℃ to obtain the modified composite carrier.

At room temperature, adding the non-metallocene complex into a second solvent, then adding the modified composite carrier, stirring for 4 hours, then hermetically standing for 12 hours, and directly vacuumizing and drying at room 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 in terms of Mg element to the chemical treatment agent in terms of IVB group 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 ratio of non-metallocene complex relative to the second solvent was 0.1 g/ml.

The supported non-metallocene catalyst is marked as CAT-1.

Examples 1 to 2

Basically the same as example 1-1, but with the following changes:

magnesium compound is changed into magnesium ethoxide (Mg (OC)₂H₅)₂) The alcohol was changed to n-butanol, the first solvent was changed to toluene, and the porous support was partially crosslinked (degree of crosslinking was 30%) polystyrene. The polystyrene was dried continuously at 85 ℃ for 12h under nitrogen. The chemical treating agent is changed into zirconium tetrachloride (ZrCl)₄）。

Non-metallocene complexes with

The second solvent was changed to toluene, and the first mixed slurry was changed to hexane as a precipitant to completely precipitate, filtered and washed three times with the precipitant, and then dried under vacuum 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 in terms of Mg element; the ratio of the magnesium compound to the first solvent is 1 mol: 150 ml; the molar ratio of the composite carrier in terms of Mg element to the chemical treatment agent in terms of IVB group 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 ratio of non-metallocene complex relative to the second solvent was 0.06 g/ml.

The supported non-metallocene catalyst is denoted as CAT-2.

Examples 1 to 3

Basically the same as in example 1-1, but with the following changes:

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

Non-metallocene complexes with

. The first mixed slurry was changed to direct vacuum drying 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 ratio of the magnesium compound to the first solvent is 1 mol: 280 ml; the molar ratio of the composite carrier in terms of Mg element to the chemical treatment agent in terms of IVB group 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 ratio of non-metallocene complex relative to the second solvent was 0.05 g/ml.

The supported non-metallocene catalyst is marked as CAT-3.

Example 2 preparation of ultra high molecular weight ethylene copolymer

On a 5L polymerization autoclave, purging with high-purity nitrogen at 100 ℃ for 2 hours, then discharging the pressure in the autoclave, adding 2.5L of a solvent, then adding a main catalyst (supported non-metallocene catalysts CAT-1 to CAT-3), a cocatalyst and a comonomer prepared in the embodiment 1 of the invention under stirring conditions (300 revolutions per minute), heating to a predetermined temperature, continuously introducing ethylene and maintaining the pressure and the temperature at a constant value, stopping introducing ethylene after a predetermined polymerization time, discharging the pressure in the autoclave, cooling to room temperature, discharging the polymer and the solvent from the autoclave, skimming the supernatant solvent, drying and weighing the material to obtain a final mass, wherein the concrete conditions of the ethylene slurry copolymerization reaction are shown in Table 1, and the basic performance and tensile performance results of the ultra-high molecular weight ethylene copolymer prepared by polymerizing the obtained ethylene slurry are shown in Table 2, the results of the slurry polymerization of ethylene to produce an ultra-high molecular weight ethylene copolymer are summarized in Table 3.

Comparative example 2-1

Substantially the same as example 2, the polymerization solvent was n-hexane as the solvent, the polymer number was UHMWPE35, and the details of the ethylene slurry polymerization reaction are shown in Table 1, the basic properties and tensile properties of the ultra-high molecular weight ethylene copolymer prepared by slurry polymerization of ethylene thus obtained are shown in Table 2, and the results of the contents of the metallic elements, ash contents, melting points and crystallinities of the ultra-high molecular weight ethylene copolymer prepared by slurry polymerization of ethylene are shown in Table 3.

Comparative examples 2 to 2

Substantially the same as example 2, the polymerization solvent was changed to n-heptane, the polymer number was the same as UHMWPE36, and the details of the ethylene slurry polymerization reaction are shown in Table 1, the basic properties and tensile properties of the ultra-high molecular weight ethylene copolymer prepared by the slurry polymerization of ethylene thus obtained are shown in Table 2, and the results of the contents of metallic elements, ash content, melting point and crystallinity of the ultra-high molecular weight ethylene copolymer prepared by the slurry polymerization of ethylene are shown in Table 3.

Comparative examples 2 to 3

In the same manner as in example 2, the catalyst was changed to a silica gel-supported zirconocene dichloride type metallocene catalyst, and methylaluminoxane was used as a cocatalyst, and after 6 hours of polymerization, it was found that a reaction slurry could not be obtained, i.e., the reaction could not proceed.

Comparative examples 2 to 4

Basically the same as example 2, the catalyst was changed to a CM type ziegler-natta catalyst (carrier is magnesium compound, no silicon, also called CMU catalyst) of the okada division of beijing, china petrochemical catalyst ltd), the polymer number was UHMWPE37, the details of the ethylene slurry polymerization reaction are shown in table 1, the basic properties and tensile properties of the ethylene copolymer prepared by the ethylene slurry polymerization obtained thereby are shown in table 2, and the results of the contents of metallic elements, ash contents, melting points and crystallinities of the ethylene copolymer prepared by the ethylene slurry polymerization are shown in table 3.

As is clear from comparison of the results obtained by the numbers 1 and 2 in Table 1, the polymerization activities obtained at the molar ratios of the cocatalyst to the catalytically active metal of 40 and 100 were equivalent to each other, thus indicating that the catalyst of the present invention requires a smaller amount of cocatalyst in the polymerization of olefins, and therefore, the amount of cocatalyst 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 ethylene copolymer with ultrahigh viscosity average molecular weight provided by the invention, the viscosity average molecular weight and the performance of the polyethylene with ultrahigh viscosity average molecular weight can be adjusted by changing the proportioning and using amount of the cocatalyst and the cocatalyst.

As is clear from comparison of the effects obtained in tables 1 and 2, increasing the polymerization pressure, increasing the polymerization temperature and prolonging the polymerization time enables to obtain high slurry polymerization activity of ethylene and further to reduce the content of metal elements in the obtained ultra-high viscosity average molecular weight polyethylene.

As is clear from the comparison of the effects obtained in tables 1 and 2, according to the present invention, the properties of the ultra-high viscosity-average molecular weight polyethylene obtained by the above-mentioned method can be adjusted by selecting catalysts having different properties under the appropriate slurry polymerization conditions of ethylene, such as polymerization pressure, polymerization temperature, polymerization solvent, polymerization time, and molar ratio of the cocatalyst to the cocatalyst.

Based on the comparison of the effects obtained by the serial number 1, the serial number 15, the serial number 16 and the serial number 17 in tables 1 to 3, the preparation method of the ethylene copolymer with the ultrahigh viscosity average molecular weight is adopted, the ethylene slurry polymer powder obtained after the polymerization is very easy to dry, and after the polymerization reaction is finished and the direct filtration is carried out, the solvent residue content ratio in the wet polymer is less than 20wt% and is lower than the solvent residue content ratio higher than 25wt% in the wet polymer with normal hexane or normal heptane as the polymerization solvent, so that the drying time of the polyethylene material is very favorably shortened, and the post-treatment cost of the polyethylene is very favorably saved.

And as can be seen from table 2, under the condition that the ultra-high molecular weight polyethylene is prepared by the slurry polymerization of ethylene of the present invention, compared with the case that n-hexane and n-heptane are used as solvents, the ultra-high molecular weight polyethylene prepared by the polymerization of the present invention has high bulk density, high viscosity average molecular weight, low contents of elements such as titanium, calcium, magnesium, aluminum, silicon, chlorine, and low ash content, and the ultra-high molecular weight ethylene copolymer obtained therefrom has high tensile elastic modulus.

Further, as is clear from the effects obtained by numbers 10 to 14 in tables 1 to 3, in the case of using the method for producing an ultrahigh-viscosity-average-molecular-weight ethylene copolymer of the present invention and 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 a lower ash content, and the ultrahigh-molecular-weight ethylene copolymer thus obtained has a higher tensile modulus.

Although 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 appropriately modify the embodiments without departing from the technical spirit and scope of the present invention, and it is obvious that the modified embodiments are also included in the scope of the present invention.

Claims

1. A preparation method of ultra-high molecular weight polyethylene, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-1000 ten-million g/mol, preferably 200-850-ten-million g/mol, more preferably 300-700-million g/mol, which is characterized in that under the condition of no hydrogen, a supported non-metallocene catalyst is used as a main catalyst, one or more of aluminoxane, alkyl aluminum and halogenated alkyl aluminum is used as a cocatalyst, and 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, so that raw materials containing ethylene and comonomer are subjected to slurry polymerization.

2. The process for the preparation of ultra-high molecular weight polyethylene according to claim 1, characterized in that the tank slurry polymerization is carried out 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, and the polymerization activity is higher than 2 kg polyethylene/g procatalyst, preferably higher than 3 kg polyethylene/g procatalyst, wherein the proportion of comonomer is 0.01 to 3 mol%, preferably 0.01 to 2 mol%, relative to the total moles of ethylene and comonomer, and ethylene and comonomer are fed into the polymerization tank together.

3. The process for preparing 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 the group consisting of n-pentane, isopentane, neopentane, and cyclopentane, preferably 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.

4. Process for the preparation of ultra-high molecular weight polyethylene according to any of claims 1 to 3, characterized in that the comonomer is selected from C₃-C₁₀The alpha-olefin of (a) may be selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, preferably from 1-butene and 1-hexene.

5. The process for preparing ultra-high molecular weight polyethylene according to any one of claims 1 to 4, wherein the cocatalyst aluminoxane is one or more selected from methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, preferably one or more selected from methylaluminoxane and isobutylaluminoxane, the cocatalyst alkylaluminum is one or more selected from trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum, preferably one or more selected from trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum, most preferably one or more selected from triethylaluminum and triisobutylaluminum, and the cocatalyst haloalkylaluminum is one or more selected from dimethylaluminumchloroaluminum, triethylaluminum and triisobutylaluminum, Methylaluminum dichloride, diethylaluminum dichloride, ethylaluminum dichloride, dipropylaluminum dichloride, propylaluminum dichloride, di-n-butylaluminum dichloride, diisobutylaluminum dichloride, isobutylaluminum dichloride, di-n-hexylaluminum dichloride, diisohexylaluminum monochloride, isohexylaluminum dichloride, preferably one or more selected from diethylaluminum monochloride, ethylaluminum dichloride, di-n-butylaluminum monochloride, n-butylaluminum dichloride, diisobutylaluminum monochloride, isobutylaluminum dichloride, di-n-hexylaluminum monochloride, n-hexylaluminum dichloride, further preferably one or more selected from diethylaluminum monochloride, ethylaluminum dichloride and di-n-hexylaluminum dichloride, and most preferably one or more selected from diethylaluminum monochloride and ethylaluminum dichloride.

6. The process for the preparation of ultra-high molecular weight polyethylene according to any of claims 1 to 5, characterized in that the supported non-metallocene catalyst comprises a non-metallocene complex and a group IVB metal compound.

7. The process for the preparation of ultra high molecular weight polyethylene according to any of claims 1 to 6, characterized in that the non-metallocene complex is selected from one or more of the compounds having the following chemical formula:

，

preferably one or more selected from the group consisting of compound (a) and compound (B) having the following chemical structural formula:

and

，

　　　　　　（A）　　　　　　　　　　　　（B）

more preferably one or more selected from the group consisting of compounds (A-1) to (A-4) and compounds (B-1) to (B-4) having the following chemical structural formulae:

、

、

　　　　　（A－1）　　　　　　　　　（A－2）

、

、

　　　　（A－3）　　　　　　（A－4）

、

、

　　　　　　（B－1）　　　　　　　　　　　（B－2）

and

，

　　　　　（B－3）　　　　　　　　（B－4）

in all of the above chemical structural formulae,

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 the elements, preferably a group IVB metal atom, more preferably Ti (IV) and Zr (IV);

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

x is selected from halogen, hydrogen atom, C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀Hydrocarbon group, oxygen-containing group, nitrogen-containing group, sulfur-containing group, boron-containing groupAn aluminum-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, wherein a plurality of xs may be the same or different, and may form a bond or a ring with each other;

a is selected from oxygen atom, sulfur atom, selenium atom,

、-NR²³R²⁴、-N(O)R²⁵R²⁶、

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;

z is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group or a cyano group, wherein N, O, S, Se and P are each a coordinating atom;

→ represents a single bond or a double bond;

-represents a covalent or ionic bond;

- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -, coordinate bond, covalent bond or ionic bond;

R¹to R⁴、R⁶To R²¹Each independently selected from hydrogen and C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀Hydrocarbon radicals or inert functional groups, R²²To R³⁶、R³⁸And R³⁹Each independently selected from hydrogen and C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀A hydrocarbon group, the above groups may be the same or different from each other, and adjacent groups may be bonded to each other to form a bond or a ring, preferably an aromatic ring;

the inert functional group is selected from the group consisting of halogen, oxygen-containing group, nitrogen-containing group, silicon-containing group, germanium-containing group, sulfur-containing group, tin-containing group, C₁-C₁₀An ester group or a nitro group,

R⁵selected from lone pair of electrons on nitrogen, hydrogen, C₁-C₃₀Hydrocarbyl, substituted C₁-C₃₀A hydrocarbyl group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group, or a phosphorus-containing group; when R is⁵When it is an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group, R⁵N, O, S, P and Se in (1) can be used as coordination atoms;

said substituted C₁-C₃₀The hydrocarbon radical being selected from the group containing one or more halogens or C₁-C₃₀C with alkyl as substituent₁-C₃₀A hydrocarbyl group;

the non-metallocene complex is further preferably selected from one or more of the compounds having the following chemical formula:

、

、

、

、

and

，

most preferably one or more selected from the group consisting of compounds having the following chemical structures:

and

。

8. the method according to claim 7,

the halogen is selected from F, Cl, Br or I;

the nitrogen-containing group is selected from

、-NR²³R²⁴、-T-NR²³R²⁴or-N (O) R²⁵R²⁶；

The phosphorus-containing group is selected from

、-PR²⁸R²⁹、-P(O)R³⁰R³¹or-P (O) R³²(OR³³)；

The oxygen-containing group is selected from hydroxyl, -OR³⁴and-T-OR³⁴；

The sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶or-T-SO₂R³⁷；

The selenium-containing group is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹or-T-Se (O) R³⁹；

The group T is selected from C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀A hydrocarbyl group;

the R is³⁷Selected from hydrogen, C₁-C₃₀Hydrocarbyl or substituted C₁-C₃₀A hydrocarbyl group;

said C is₁-C₃₀The hydrocarbon radical being selected from C₁-C₃₀Alkyl radical, C₇-C₃₀Alkylaryl group, C₇-C₃₀Aralkyl radical, C₃-C₃₀Cyclic alkyl, C₂-C₃₀Alkenyl radical, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl radical, C₈-C₃₀Condensed ring radicals or C₄-C₃₀A 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 BF₄ ^-、(C₆F₅)₄B^-Or (R)⁴⁰BAr₃)^-；

The aluminum-containing group is selected from alkyl aluminum and AlPh₄ ^-、AlF₄ ^-、AlCl₄ ^-、AlBr₄ ^-、AlI₄ ^-Or R⁴¹AlAr₃ ^-；

The silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴or-T-SiR⁴⁵；

The germanium-containing group is selected from-GeR⁴⁶R⁴⁷R⁴⁸or-T-GeR⁴⁹；

The tin-containing group is selected from-SnR⁵⁰R⁵¹R⁵²、-T-SnR⁵³or-T-Sn (O) R⁵⁴；

Ar represents C₆-C₃₀An aryl group;

R⁴⁰to R⁵⁴Each independently selected from hydrogen, C₁-C₃₀Hydrocarbyl or substituted C as hereinbefore described₁-C₃₀A hydrocarbon group in which these groups may be the same as or different from each other, in which adjacent groups may be bonded to each other to form a bond or form a ring, and

the group T is as defined above.

9. The process for preparing ultra-high molecular weight polyethylene according to claim 6, 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 alkoxy halides, preferably selected from TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄Most preferably selected from TiCl₄And ZrCl₄One or more of (a).

10. An ultra-high molecular weight polyethylene characterized in that the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 150-.

11. The ultra-high molecular weight polyethylene of claim 10, wherein the polyethylene has a bulk density of 0.30 to 0.55g/cm³Preferably 0.33 to 0.52g/cm³More preferably 0.40 to 0.50g/cm³The true density is 0.900-0.940g/cm³Preferably 0.905 to 0.935g/cm³More preferably 0.915 to 0.930g/cm³The melting point is 140-152 ℃, preferably 142-150 ℃, and the crystallinity is 40-75%, preferably 45-70%.

12. Ultra-high molecular weight polyethylene according to claim 10 or 11, characterized in that the polyethylene has a titanium content of 0-3ppm, preferably 0-2ppm, a calcium content of 0-5ppm, preferably 0-3ppm, a magnesium content of 0-10ppm, preferably 0-5ppm, an aluminium content of 0-30ppm, preferably 0-20ppm, a silicon content of 0-10ppm, preferably 0-5ppm, a chlorine content of 0-50ppm, preferably 0-30 ppm.

13. Ultra-high molecular weight polyethylene according to any of claims 10 to 12, wherein the polyethylene is of random copolymeric structure with a molar insertion of comonomer of 0.05 to 4.0%, preferably 0.10 to 2.0%, the comonomer being selected from C₃-C₁₀The alpha-olefin of (a) may be selected from propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, preferably from 1-butene and 1-hexene.

14. Ultra-high molecular weight polyethylene according to any of claims 10 to 13, characterized in that the ash content of the polyethylene is less than 200ppm, preferably less than 150 ppm.