CN109485762B

CN109485762B - Supported non-metallocene catalyst, preparation method and application thereof

Info

Publication number: CN109485762B
Application number: CN201710814595.8A
Authority: CN
Inventors: 李传峰; 任鸿平; 汪文睿; 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: 2017-09-11
Filing date: 2017-09-11
Publication date: 2023-05-26
Anticipated expiration: 2037-09-11
Also published as: CN109485762A

Abstract

The invention relates to a supported non-metallocene catalyst, a preparation method and application thereof. The preparation method of the supported non-metallocene catalyst comprises the following steps: a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent in the presence of an alcohol to obtain a magnesium compound solution; a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry; drying the mixed slurry, or adding a precipitant into the mixed slurry to obtain a composite carrier, wherein the content of the alcohol in the composite carrier is 0.5-2.5wt%; and a step of treating the composite carrier with a chemical treatment agent selected from group IVB metal compounds to obtain the supported non-metallocene catalyst. The supported non-metallocene catalyst has the characteristics of simple and feasible preparation method, flexible and adjustable polymerization activity and the like.

Description

Supported non-metallocene catalyst, preparation method and application thereof

Technical Field

The present invention relates to a non-metallocene catalyst. In particular, the invention relates to a supported non-metallocene catalyst, a preparation method thereof and application thereof in olefin homo/copolymerization.

Background

The non-metallocene catalysts, also known as post-metallocene catalysts, which occur in the middle and late 90 s of the 20 th century, the central atoms of the main catalyst include almost all transition metal elements, and are fourth generation olefin polymerization catalysts subsequent to Ziegler, ziegler-Natta and metallocene catalysts, which have achieved or even exceeded the metallocene catalysts in some properties. The non-metallocene catalyst does not contain cyclopentadienyl, and the coordination atoms are oxygen, nitrogen, sulfur and phosphorus, and is characterized in that the central ion has stronger electrophilicity, and has a cis-alkyl or halogen metal central structure, so that olefin insertion and sigma-bond transfer are easy to carry out, the central metal is easy to alkylate, and the generation of a cation active center is facilitated; the complexes formed have defined geometric configurations, stereoselectivity, electronegativity and chiral adjustability. In addition, the formed metal-carbon bond is easily polarized, which is beneficial to the polymerization of olefin. Thus, an olefin polymer having a higher molecular weight can be obtained even at a higher polymerization temperature.

However, homogeneous olefin polymerization catalysts have been demonstrated to have short duration of activity, easy pot sticking, high methylaluminoxane usage, and too low or too high molecular weight of the resulting polymer in olefin polymerization, which severely limits industrial applications.

The olefin homo/copolymerization catalyst or the catalyst system prepared by the patents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 has wide olefin homo/copolymerization performance, is suitable for various polymerization processes, but the catalyst or the catalyst system disclosed in the patent needs higher cocatalyst dosage during olefin polymerization to obtain proper olefin polymerization activity, and has a kettle sticking phenomenon in the polymerization process.

It is common practice to make non-metallocene catalysts into supported catalysts by certain supporting techniques, thereby improving the polymerization properties of the olefins and the particle morphology of the resulting polymers. The catalyst has the advantages of properly reducing the initial activity of the catalyst to a certain extent, prolonging the service life of the polymerization activity of the catalyst, reducing or even avoiding the agglomeration or polymerization explosion phenomenon in the polymerization process, improving the morphology of the polymer, improving the apparent density of the polymer, and being capable of meeting more polymerization processes, such as gas phase polymerization or slurry polymerization, and the like.

The non-metallocene catalysts disclosed in patents ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 are supported in various ways to obtain supported non-metallocene catalysts, such as patent CN1539855A, CN 1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/06501, 200510119401.X, but all of the patents relate to the loading of non-metallocene organic compounds (or called non-metallocene catalysts or non-metallocene complexes) containing transition metals on a treated carrier, or the loading of the non-metallocene catalysts is lower or the combination of the non-metallocene catalysts and the carrier is not very tight.

The existing olefin polymerization catalysts are mostly based on metallocene catalysts, such as US 4808561, US 5240894, CN 1049439, CN 1136239, CN 1344749, CN 1126480, CN1053673, CN 1307594, CN 1130932, CN 1103069, CN1363537, CN1060179, US574417, EP685494, US4871705 and EP0206794 etc., but these patents also relate to the loading of a transition metal containing metallocene catalyst on a treated support.

Patent EP708116 discloses that gasified zirconium tetrachloride is contacted with a carrier at a temperature of 160 to 450 ℃ and supported, and then the supported zirconium tetrachloride is reacted with a lithium salt of a ligand to obtain a supported metallocene catalyst, which is then used for the polymerization of olefins by co-catalyst. The catalyst has the problems that the loading process requires high temperature and high vacuum, and is not suitable for industrial production.

There are literature reports on the treatment of MgCl with ethylaluminum chloride ₂ (THF) ₂ And supporting zirconocene dichloride, thereby preparing the supported metallocene catalyst. The process is as follows: magnesium chloride was dissolved in tetrahydrofuran, washed with hexane precipitate, treated with ethylaluminum chloride, and finally loaded with zirconocene dichloride (EUROPEAN POLYMER JOURNAL,2005, 41, 941-947).

Sun Min et al disclose in the paper "in situ reaction method for preparing CpTi (dbm) Cl ₂ /MgCl ₂ Carrier-type catalyst for catalyzing ethylene polymerization research "(high molecular report, 2004, (1): 138) prepared by Grignard reagent method and adding CpTi (dbm) Cl ₂ Thus preparing CpTi (dbm) Cl ₂ /MgCl ₂ A supported catalyst. Thus, the alkylation and the loading of the catalyst are completed in one step, and the preparation procedures of the catalyst are greatly reduced.

Patent CN200510080210.7 discloses a supported vanadium non-metallocene polyolefin catalyst synthesized in situ, a preparation method and application thereof, wherein dialkyl magnesium is reacted with acyl naphthol or beta-diketone to form acyl naphthol magnesium or beta-diketone magnesium compound, and then reacted with tetravalent vanadium chloride to form carrier and active catalytic component.

Patent CN200610026765.8 discloses a single site ziegler-natta olefin polymerization catalyst. The catalyst takes salicylaldehyde or substituted salicylaldehyde derivative containing coordination groups as an electron donor, and is obtained by adding a pretreated carrier (such as silica gel), a metal compound (such as titanium tetrachloride) and the electron donor into a magnesium compound (such as magnesium chloride)/tetrahydrofuran solution, and treating.

Patent CN200610026766.2, similarly, discloses a class of heteroatom-containing organic compounds and their use in ziegler-natta catalysts.

The patent CN200710162676.0 discloses a magnesium compound supported non-metallocene catalyst and a preparation method thereof, wherein the non-metallocene catalyst is obtained by directly contacting a non-metallocene ligand with a magnesium compound containing a catalytic active metal by an in-situ supporting method. However, the contact between the catalytic active metal and the magnesium compound means that the IV B group metal compound is added into the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), so that the contact cannot fully react between the catalytic active metal and the magnesium compound, and the obtained magnesium compound carrier containing the catalytic active metal is heterogeneous and not fully contacted and reacted among molecules, thereby limiting the full play of the action of the non-metallocene ligand added subsequently.

Similarly, patent CN200710162667.1 discloses a magnesium compound supported non-metallocene catalyst and a preparation method thereof, which have similar problems. Which is obtained by directly contacting a catalytically active metal compound with a magnesium compound containing a non-metallocene ligand by an in situ supporting method. However, the contact means that the non-metallocene ligand solution is added to the formed magnesium compound solid (such as the magnesium compound solid or the modified magnesium compound solid), and such contact cannot achieve sufficient reaction of the non-metallocene ligand with the magnesium compound, and the obtained magnesium compound carrier containing the non-metallocene ligand is necessarily heterogeneous and is not sufficiently contacted and reacted between molecules, thereby limiting the full play of the effect of the non-metallocene ligand.

The above problems still exist in PCT patent PCT/CN2008/001739, which is filed based on the above two patents.

The catalyst using anhydrous magnesium chloride as a carrier shows higher catalytic activity in the olefin polymerization process, but the catalyst is very brittle and is easy to break in a polymerization reactor, so that the polymer morphology is poor. The silica supported catalyst has good flowability and can be used for gas-phase fluidized bed polymerization, but the silica supported metallocene and non-metallocene catalysts show lower catalytic activity. Therefore, if magnesium chloride and silicon dioxide are organically combined well, it is possible to prepare a catalyst with high catalytic activity, controllable particle size and good abrasion resistance.

Patent ZL01131136.3 discloses a method for synthesizing a supported metallocene catalyst. Wherein silica gel and IV B group transition metal halide are mixed in a solvent under normal pressure and then directly react with ligand anions, thereby realizing the synthesis and the loading of the metallocene catalyst in one step. However, this method requires a molar ratio of transition metal to ligand of 1:1 and the addition of proton donors such as butyllithium and the like, and the ligand employed is a bridged or unbridged cyclopentadienyl-containing metallocene ligand.

Xiao Yizhi et al disclose "novel Ni (acac) ₂ /TiCl ₄ Research on the preparation of branched polyethylene by polymerization of ethylene catalyzed by a ligand-L composite catalyst (university of Zhongshan university: nature science edition, 2003, 42 (3): 28) which will be anhydrous MgCl ₂ 、Ni(acac) ₂ And L, after dissolving in tetrahydrofuran-ethanol mixed solvent, adding silica gel, stirring to react, adding a certain amount of titanium tetrachloride to continue the reaction, and then adding a certain amount of Et ₂ AlCl reaction, and suction drying to obtain catalyst, so that the Ni (acac) 2/TiCl4 composite catalyst using magnesium chloride-silica gel as carrier and using alpha-diimine ligand L modification is prepared. The catalyst is used for catalyzing the polymerization of mono-ethylene to obtain branched polyethylene, wherein the ligand L2 is used for preparing the branched polyethylene with the branching degree of 4-12 branched chains per 1000 ℃.

Patent CN200910210991.5 discloses a preparation method of a supported non-metallocene catalyst, which comprises the following steps: a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent in the presence of an alcohol to obtain a magnesium compound solution; a step of mixing the porous support, which is optionally subjected to the heat activation treatment, with the magnesium compound solution to obtain a mixed slurry; adding a precipitant into the mixed slurry to obtain a composite carrier; and a step of treating the composite carrier with a chemical treatment agent selected from group IV B metal compounds to obtain the supported non-metallocene catalyst. It can be seen from the disclosure that the alcohol introduced acts only as a co-solvent for the magnesium compound and the non-metallocene ligand and is then removed by drying during the drying process.

From the above, it can be seen that the supported non-metallocene catalysts of the prior art have the general problem that heterogeneous composition and distribution formed during the preparation of the catalyst limit the catalyst polymerization product properties and its particle morphology.

Thus, there is still a need for a supported non-metallocene catalyst which is simple in preparation process, suitable for industrial production, and which can overcome those problems existing in the prior art supported non-metallocene catalysts.

Disclosure of Invention

The present inventors have made intensive studies on the basis of the prior art, and have found that the aforementioned problems can be solved by using a specific preparation method for producing the supported non-metallocene catalyst, particularly by controlling the concentration of alcohol in a composite carrier, thereby exerting its effect in improving the catalyst activity, the morphology of polymer particles, and the like, and have completed the present invention.

In the preparation of the supported non-metallocene catalysts of the present invention, no proton donor (such as those conventionally used in the art) is added. In addition, in the preparation method of the supported non-metallocene catalyst of the present invention, no electron donor (such as monoester, diester, diether, diketone, glycol ester, etc. compounds conventionally used for this purpose in the art) is added. Furthermore, in the preparation method of the supported non-metallocene catalyst of the present invention, the strict reaction requirements and reaction conditions are not required. Therefore, the preparation method of the supported catalyst is simple and is very suitable for industrial production.

Specifically, the invention relates to a preparation method of a supported non-metallocene catalyst, which comprises the following steps:

a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent in the presence of an alcohol to obtain a magnesium compound solution;

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

drying the mixed slurry or adding a precipitant to the mixed slurry to obtain a composite carrier, wherein the content of the alcohol in the composite carrier is 0.5-2.5wt%, preferably 1.0-2.0wt%; and

and a step of treating the composite carrier with a chemical treatment agent selected from group IV B metal compounds to obtain the supported non-metallocene catalyst.

The invention also relates to a supported non-metallocene catalyst prepared by the preparation method and application thereof in olefin homo/copolymerization.

Technical effects

The in-situ preparation method of the supported non-metallocene catalyst has simple and feasible process, the non-metallocene ligand is uniformly distributed in the magnesium compound, and the loading capacity of the non-metallocene ligand is adjustable.

By adopting the preparation method of the catalyst provided by the invention, surprisingly, the catalyst activity and the polymer bulk density are obviously improved and the cocatalyst amount required in the polymerization process is lower because a certain alcohol content is strictly controlled and reserved in the drying process of the composite carrier.

The supported non-metallocene catalyst prepared by the invention has remarkable copolymerization effect, namely the copolymerization activity of the catalyst is higher than that of homopolymerization, and the copolymerization reaction can improve the bulk density of the polymer, namely the particle morphology of the polymer.

The supported non-metallocene catalyst provided by the invention can polymerize to obtain the ultra-high molecular weight polyethylene with higher molecular weight under the condition of no hydrogen participating in the homopolymerization reaction.

Detailed Description

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

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

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

According to the invention, a preparation method of a supported non-metallocene catalyst is provided, which comprises the following steps: a step of dissolving a magnesium compound and a non-metallocene ligand in a solvent in the presence of an alcohol to obtain a magnesium compound solution; a step of mixing a porous support, which is optionally subjected to a heat activation treatment and/or a chemical activation treatment, with the magnesium compound solution to obtain a mixed slurry; drying the mixed slurry, or adding a precipitant into the mixed slurry to obtain a composite carrier, wherein the content of the alcohol in the composite carrier is 0.5-2.5wt%; and a step of treating the composite carrier with a chemical treatment agent selected from group IV B metal compounds to obtain the supported non-metallocene catalyst.

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

According to this step, the magnesium compound and the non-metallocene ligand are dissolved in an appropriate solvent (i.e., a solvent for dissolving the magnesium compound) in the presence of an alcohol, thereby obtaining the magnesium compound solution.

Examples of the solvent include C _6-12 Aromatic hydrocarbons, halogenated C _6-12 Solvents such as aromatic hydrocarbons, esters and ethers. Specific examples thereof include toluene, xylene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloroethylbenzene, bromotoluene, bromoethylbenzene, ethyl acetate, tetrahydrofuran, and the like. Of these, C is preferred _6-12 Aromatic hydrocarbons and tetrahydrofuran, most preferably tetrahydrofuran.

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

According to the invention, the term "alcohol" refers to a hydrocarbon chain (such as C _1-30 Hydrocarbon) in which at least one hydrogen atom is substituted with a hydroxyl group.

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

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

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

As said C _4-30 Examples of alicyclic alcohols include cyclohexanol, cyclopentanol, cyclooctanol, methylcyclopentanol, ethylcyclopentanol, propylcyclopentanol, methylcyclohexanol, ethylcyclopentanol Hexanol, propylcyclohexanol, methylcyclooctanol, ethylcyclooctanol, propylcyclooctanol and the like, with cyclohexanol and methylcyclohexanol being preferred.

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

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

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

In order to prepare the magnesium compound solution, the magnesium compound and the non-metallocene ligand may be added to a mixed solvent formed of the solvent and the alcohol to be dissolved, or the magnesium compound and the non-metallocene ligand may be added to the solvent and simultaneously or subsequently added to the alcohol to be dissolved, but not limited thereto.

In preparing the magnesium compound solution, the molar ratio of the magnesium compound (solid) to the alcohol is 1:0.02 to 4.00, preferably 1:0.05 to 3.00, more preferably 1:0.10 to 2.50 in terms of magnesium element, and the ratio of the magnesium compound (solid) to the solvent is generally 1 mol:75 to 400ml, preferably 1 mol:150 to 300ml, more preferably 1 mol:200 to 250ml in terms of magnesium element.

According to the invention, the non-metallocene ligand is used in such an amount that the molar ratio of the magnesium compound (solid) to the non-metallocene ligand in terms of Mg element is 1:0.0001 to 1, preferably 1:0.0002 to 0.4, more preferably 1:0.0008 to 0.2, still more preferably 1:0.001 to 0.1.

The preparation time of the magnesium compound solution (i.e., the dissolution time of the magnesium compound and the non-metallocene ligand) 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 dissolution of the magnesium compound and the non-metallocene ligand. The stirring may take any form, such as a stirring paddle (typically at a speed of 10 to 1000 rpm), or the like. Dissolution may be promoted by appropriate heating, as needed.

The magnesium compound is specifically described below.

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

According to the present invention, examples of the magnesium compound include magnesium halide, alkoxymagnesium, alkylmagnesium halide and alkylalkoxymagnesium.

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

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

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

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

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

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

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

When used in a plurality of mixed forms, the molar ratio between any 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.

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

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

according to the present invention, the group A, D and E (coordinating group) in the compound form a coordination bond by the coordination reaction of the coordinating atom (e.g., N, O, S, se and P, etc. hetero atom) contained therein and the group IV B metal atom contained in the group IV B metal compound used as the chemical treating agent in the present invention, thereby forming a complex having the group IV B metal atom as the central metal atom M (i.e., the non-metallocene complex of the present invention).

In a more specific embodiment, the non-metallocene ligand is selected from the group consisting of compounds (a) and (B) having the following chemical formulas:

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

/>

/>

in all of the above chemical structural formulas,

q is 0 or 1;

d is 0 or 1;

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

-NR ²³ R ²⁴ 、-N(O)R ²⁵ R ²⁶ 、/>

-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ OR ³¹ Of sulfone, sulfoxide or-Se (O) R ³⁹ Wherein N, O, S, se and P are each an atom for coordination;

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

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

e is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, a phosphorus-containing group, or a cyano group (-CN), wherein N, O, S, se and P are each a coordinating atom;

f is selected from a nitrogen atom, a nitrogen-containing group, an oxygen-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;

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

y is selected from a nitrogen-containing group, an oxygen-containing group, a sulfur-containing group, a selenium-containing group, or a phosphorus-containing group, wherein N, O, S, se and P are each an atom for coordination;

z is selected from nitrogen-containing groups, oxygen-containing groups, sulfur-containing groups, selenium-containing groups, phosphorus-containing groups or cyano groups (-CN), for example, -NR ²³ R ²⁴ 、-N(O)R ²⁵ R ²⁶ 、-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ R ³¹ 、-OR ³⁴ 、-SR ³⁵ 、-S(O)R ³⁶ 、-SeR ³⁸ or-Se (O) R ³⁹ Wherein N, O, S, se and P are each an atom for coordination;

-represents a single bond or a double bond;

-represents a covalent bond or an ionic bond.

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

R ⁸ Selected from lone pair electrons on nitrogen, hydrogen, C ₁ -C ₃₀ Hydrocarbyl, substituted C ₁ -C ₃₀ Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, selenium-containing groups, or phosphorus-containing groups. When R is ⁵ R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group ⁵ The N, O, S, P and Se of (a) may be used as the coordinating atom (coordinating with the central metal atom M).

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

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

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

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

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

In the context of the present invention,

the halogen is selected from F, cl, br or I. The nitrogen-containing group is selected from

-NR ²³ R ²⁴ 、 -T-NR ²³ R ²⁴ or-N (O) R ²⁵ R ²⁶ . The phosphorus-containing group is selected from->

-PR ²⁸ R ²⁹ 、 -P(O)R ³⁰ R ³¹ or-P (O) R ³² (OR ³³ ). The oxygen-containing group is selected from the group consisting of hydroxy, -OR ³⁴ and-T-OR ³⁴ . The sulfur-containing group is selected from the group consisting of-SR ³⁵ 、-T-SR ³⁵ 、-S(O)R ³⁶ or-T-SO ₂ R ³⁷ . The selenium-containing group is selected from the group consisting of-Ser ³⁸ 、-T-SeR ³⁸ 、-Se(O)R ³⁹ or-T-Se (O) R ³⁹ . The radicals T being selected from C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group. The R is ³⁷ Selected from hydrogen, C ₁ -C ₃₀ Hydrocarbyl or substituted C ₁ -C ₃₀ A hydrocarbon group.

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

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

In the context of the present invention, the substituted C ₁ -C ₃₀ Hydrocarbyl refers to C bearing one or more inert substituents ₁ -C ₃₀ A hydrocarbon group. By inert substituents is meant that these substituents are substituted for the aforementioned coordinating groups (meaning the aforementioned groups A, D, E, F, Y and Z, or optionally also including R ⁵ ) The coordination process with the central metal atom M (i.e., the aforementioned group IV B metal atom) is not substantially disturbed; in other words, these substituents have no ability or opportunity (e.g., affected by steric hindrance, etc.) to undergo a coordination reaction with the group IV B metal atom to form a coordination bond, as limited by the chemical structure of the ligands of the present invention. In general, the inert substituents are selected from halogen or C ₁ -C ₃₀ Alkyl (preferably C ₁ -C ₆ Alkyl groups such as isobutyl).

In the context of the present invention, the silicon-containing group is selected from the group consisting of-SiR ⁴² R ⁴³ R ⁴⁴ or-T-SiR ⁴⁵ The method comprises the steps of carrying out a first treatment on the surface of the The germanium-containing group is selected from-GeR ⁴⁶ R ⁴⁷ R ⁴⁸ or-T-GeR ⁴⁹ The method comprises the steps of carrying out a first treatment on the surface of the The tin-containing group is selected from-SnR ⁵⁰ R ⁵¹ R ⁵² 、-T-SnR ⁵³ or-T-Sn (O) R ⁵⁴ The method comprises the steps of carrying out a first treatment on the surface of the And said R is ⁴² To R ⁵⁴ Each independently selected from hydrogen, C as described above ₁ -C ₃₀ Hydrocarbyl or substituted C as previously described ₁ -C ₃₀ Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or a ring. Wherein the radicals T are as defined above.

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

/>

/>

/>

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

/>

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

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

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

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

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

A mixed slurry is obtained by mixing a porous support with the magnesium compound solution.

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

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

According to the invention, the mixed slurry is a semi-dry system, in which no free liquid is present. Although not necessary, in order to ensure uniformity of the system, the mixed slurry is preferably subjected to closed standing for a certain period of time (2 to 48 hours, preferably 4 to 24 hours, and most preferably 6 to 18 hours) after the preparation.

The porous support is specifically described below.

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

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

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

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

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

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

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

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

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

Suitable silicas according to the invention can be produced by conventional methods or can be any commercially available product, such as Grace 955, grace 948, grace SP9-351, grace SP9-485, grace SP9-10046, davision Syloid 245 and Aerosi1812 from Ineos, ES70X, ES, 70Y, ES, 70W, ES757, EP10X and EP11 from Grace, and CS-2133 and MS-3040 from PQ.

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

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

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

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

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

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

The chemical activator will be specifically described below.

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

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

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

M(OR ¹ ) _m X _n R ² _4-m-n

wherein:

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

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

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

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

R ¹ And R is ² Each independently selected from C _1-10 Alkyl groups such as methyl, ethyl, propyl, n-butyl, isobutyl, etc., R ¹ And R is ² May be the same or different.

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

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

Hafnium tetrafluoride (HfF) ₄ ) Hafnium tetrachloride (HfCl) ₄ ) Hafnium tetrabromide (HfBr) ₄ ) Hafnium tetraiodide (HfI) ₄ )。

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Specifically, C may be mentioned _5-12 Alkanes, C _5-12 Cycloalkane, halogenated C _5-12 Alkanes, halogenated C _5-12 Cycloalkane, C _6-12 Aromatic hydrocarbons or halogenated C _6-12 Aromatic hydrocarbons and the like are exemplified by pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, toluene, ethylbenzene, xylene, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane, chlorotoluene, chloroethylbenzene, chloroxylenes and the like, and among them, pentane, hexane, decane, cyclohexane, toluene and the like are preferable, and hexane and toluene are most preferable.

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

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

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

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

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

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

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

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

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

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

The composite carrier is obtained by metering a precipitant into the mixed slurry to precipitate solid matter from the mixed slurry. Alternatively, the composite carrier is obtained by directly drying the mixed slurry.

The precipitant is specifically described below.

According to the present invention, the term "precipitant" is used in the general sense of the art to refer to a chemically inert liquid phase which is capable of reducing the solubility of a solute (such as the magnesium compound) in its solution and thus allowing it to precipitate out of the solution in solid form.

According to the present invention, examples of the precipitant include solvents that are poor solvents for the magnesium compound and good solvents for the solvent for dissolving the magnesium compound, and examples of the precipitant include alkanes, cycloalkanes, haloalkanes, and halocycloalkanes.

Examples of the alkane include pentane, hexane, heptane, octane, nonane, decane, and the like, and among them, hexane, heptane, decane are preferable, and hexane is most preferable.

Examples of the cycloalkane include cyclohexane, cyclopentane, cycloheptane, cyclodecane, and cyclononane, and cyclohexane is most preferable.

Examples of the halogenated alkane include methylene chloride, dichlorohexane, dichloroheptane, chloroform, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, and tribromobutane.

Examples of the halogenated cycloalkanes include chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane, and bromocyclodecane.

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

The precipitant may be added in one-time or dropwise, preferably in one-time. During this precipitation process, agitation may be used to facilitate the dispersion of the precipitant in the mixed slurry and to facilitate the final precipitation of the solid product. The stirring may take any form, such as a stirring paddle (typically at a speed of 10 to 1000 rpm), or the like.

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

The temperature of the precipitating agent is not particularly limited, but is generally preferably at ordinary temperature. Moreover, the precipitation process is also generally preferably carried out at normal temperature.

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

The washing is generally carried out 1 to 6 times, preferably 2 to 3 times, as required. Among them, the same solvent as the precipitant is preferably used for the washing solvent, but may be different.

According to the invention, the alcohol content of the composite carrier is controlled to be 0.5-2.5wt%, preferably 1.0-2.0wt%, by drying the mixed slurry or by drying the solid product (optionally after washing).

According to the present invention, the drying may be performed by a conventional method such as an inert gas drying method, a vacuum drying method or a vacuum heating drying method, preferably an inert gas drying method or a vacuum heating drying method, and most preferably a vacuum heating drying method.

According to the present invention, the drying mode (including drying temperature, drying vacuum degree and drying time) is limited by the fact that the alcohol content in the composite carrier meets the requirements of the present invention. For example, the mixed slurry is dried under vacuum of 2 to 100mBar, preferably 5 to 50mBar, absolute pressure, at a temperature of 5 to 40 ℃ lower than the boiling point of the solvent, preferably 10 to 30 ℃ lower than the boiling point of the solvent, for 2 to 48 hours, preferably 4 to 24 hours, and then dried under vacuum of 2 to 100mBar, preferably 5 to 50mBar, absolute pressure, for 1 to 24 hours, preferably 2 to 12 hours, at a temperature of 50 ℃ higher than the boiling point of the solvent, preferably from the boiling point of the solvent to a temperature of 40 ℃ higher than the boiling point of the solvent, thereby obtaining the composite carrier. Alternatively, a precipitant is added to the mixed slurry, and the obtained precipitate (optionally after washing) is dried under vacuum of 2 to 100mBar absolute pressure, preferably 5 to 50mBar, preferably 4 to 24 hours at a temperature of 5 to 40 ℃ lower than the boiling point of the solvent, preferably 5 to 50mBar absolute pressure, preferably 4 to 12 hours, and then dried under vacuum of 2 to 100mBar absolute pressure, preferably 5 to 50mBar, preferably 2 to 12 hours at a temperature of 50 ℃ higher than the boiling point of the solvent, preferably from the boiling point of the solvent to a temperature of 40 ℃ higher than the boiling point of the solvent, thereby obtaining the composite carrier.

Next, the composite support is treated with a chemical treatment agent selected from group IV B metal compounds, thereby obtaining the supported non-metallocene catalyst of the present invention.

According to the present invention, the supported non-metallocene catalyst of the present invention can be obtained by chemically treating the composite support with the chemical treatment agent, and reacting the chemical treatment agent with a non-metallocene ligand contained in the composite support, thereby generating a non-metallocene complex in situ on the support (in situ supporting reaction).

The chemical treatment agent is specifically described below.

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

Examples of the group IV B metal compound include group IV B metal halides, group IV B metal alkyls, group IV B metal alkoxides, group IV B metal alkyl halides, and group IV B metal alkoxy halides.

Examples of the group IV B metal halide, the group IV B metal alkyl compound, the group IV B metal alkoxy compound, the group IV B metal alkyl halide, and the group IV B metal alkoxy halide include compounds having the structure of the following general formula (IV):

M(OR ¹ ) _m X _n R ² _4-m-n (IV)

Wherein:

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

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

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

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

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

Hafnium tetrafluoride (HfF) ₄ ) Hafnium tetrachloride (Hf)Cl ₄ ) Hafnium tetrabromide (HfBr) ₄ ) Hafnium tetraiodide (HfI) ₄ )。

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

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

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

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

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

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

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

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

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

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

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

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

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

Specifically, C may be mentioned _5-12 Alkanes, C _5-12 Cycloalkane, halogenated C _5-12 Alkanes and halogenated C _5-12 Examples of cycloalkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, and chlorocyclohexane, and among these, pentane, hexane, decane, and cyclohexane are preferable, and hexane is most preferable.

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

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

As a method for performing the chemical treatment, for example, in the case of using a solid chemical treatment agent (such as zirconium tetrachloride), a solution of the chemical treatment agent is first prepared, and then a predetermined amount of the chemical treatment agent is added (preferably dropwise) to the composite support to be treated; in the case of using a liquid chemical treatment agent such as titanium tetrachloride, a predetermined amount of the chemical treatment agent may be directly (but may also be after preparation into a solution) added (preferably dropwise) to the composite carrier to be treated, and the chemical treatment reaction (with stirring if necessary) may be 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, followed by filtration, washing and drying.

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

According to the present invention, the chemical treatment agent is used in such an amount that the molar ratio of the magnesium compound (solid) in terms of Mg element to the chemical treatment agent in terms of group IV B metal (such as Ti element) is 1:0.01 to 1, preferably 1:0.01 to 0.50, more preferably 1:0.10 to 0.30.

According to a particular embodiment of the present invention, the process for the preparation of a supported non-metallocene catalyst according to the present invention further comprises a step of pre-treating the composite support with a co-chemical treatment agent selected from aluminoxane, alkyl aluminium or any combination thereof, before treating the composite support with the chemical treatment agent (pre-treatment step). Then, the chemical treatment is performed with the chemical treatment agent in exactly the same manner as described above, except that the composite carrier is replaced with the pretreated composite carrier.

The chemical assistant is specifically described below.

According to the present invention, examples of the auxiliary chemical agent include aluminoxane and aluminum alkyl.

Examples of the aluminoxane include linear aluminoxanes represented by the following general formula (I): (R) (R) Al- (Al (R) -O) _n -O-Al (R), and a cyclic aluminoxane represented by the following general formula (II): - (Al (R) -O-) _n+2 -。

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

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

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

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

Al(R) ₃ (III)

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

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

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

According to the present invention, the auxiliary chemical agent may be the aluminoxane alone or the aluminum alkyl alone, but may be any mixture of the aluminoxane and the aluminum alkyl. The proportions of the components in the mixture are not particularly limited, and may be arbitrarily selected as needed.

According to the invention, the chemical-assisted treatment agent is generally used in the form of a solution. In preparing the solution of the co-chemical treatment agent, the solvent used at this time is not particularly limited as long as it can dissolve the co-chemical treatment agent and does not destroy (e.g., dissolve) the existing carrier structure of the carrier.

Specifically, examples of the solvent include C _5-12 Alkanes and halogenated C _5-12 Examples of alkanes include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, chloropentane, chlorohexane, chloroheptane, chlorooctane, chlorononane, chlorodecane, chloroundecane, chlorododecane, chlorocyclohexane and the like, and among these, pentane, hexane, decane and cyclohexane are preferable, and hexane is most preferable.

The concentration of the auxiliary chemical treatment agent in the solution is not particularly limited, and may be appropriately selected as required, as long as it can perform the pretreatment with a predetermined amount of the auxiliary chemical treatment agent.

As a method for carrying out the pretreatment, for example, there may be mentioned a method in which a solution of the co-chemical treatment agent is first prepared, then the co-chemical treatment agent solution (containing a predetermined amount of the co-chemical treatment agent) is metered (preferably dropwise) into a composite carrier to be pretreated with the co-chemical treatment agent at a temperature of-30 to 60 ℃ (preferably-20 to 30 ℃), or the composite carrier is metered into the co-chemical treatment agent solution, thereby forming a reaction mixture, and the reaction mixture is allowed to react for 1 to 8 hours, preferably 2 to 6 hours, and most preferably 3 to 4 hours (with stirring as necessary). The pretreated product obtained is then isolated from the reaction mixture by filtration, washing (1 to 6 times, preferably 1 to 3 times) and optionally drying, or alternatively, it may be used directly in the form of a mixture without such isolation for the subsequent reaction step (i.e. the aforementioned chemical treatment step). At this time, since a certain amount of solvent is already contained in the mixed solution, the amount of solvent involved in the subsequent reaction step can be reduced accordingly.

According to the invention, the co-chemical treatment agent is used in such an amount that the molar ratio of the magnesium compound (solid) in terms of Mg element to the co-chemical treatment agent in terms of Al element is 1:0 to 1.0, preferably 1:0 to 0.5, more preferably 1:0.1 to 0.5.

It is known to those skilled in the art that all of the process steps described above are preferably carried out under substantially anhydrous and oxygen-free conditions. As used herein, substantially anhydrous and oxygen-free means that the water and oxygen content of the system is continuously less than 10ppm. Moreover, the supported non-metallocene catalyst of the present invention is usually required to be preserved under a micro positive pressure under a closed condition for standby after preparation.

According to the invention, the molar ratio of the magnesium compound to the non-metallocene ligand in terms of Mg element is 1:0.0001-1, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2, further preferably 1:0.001-0.1, the ratio of the magnesium compound to the solvent is 1:75-400 ml, preferably 1:150-300 ml, more preferably 1:200-250 ml, the molar ratio of the magnesium compound to the alcohol in terms of Mg element is 1:0.02-4.00, preferably 1:0.05-3.00, more preferably 1:0.10-2.50, the mass ratio of the magnesium compound to the porous carrier in terms of magnesium compound solid is 1:0.1-20, preferably 1:0.5-10, more preferably 1:1-5, the volume ratio of the precipitant to the solvent is 1:0.2-5, preferably 1:0.5, more preferably 1:0.5, and the ratio of the metal in terms of the group IV is 1:0.02-4.00, preferably 1:0.05-3.50, more preferably 1:0.50, the mass ratio of the magnesium compound to the porous carrier in terms of magnesium compound solid is 1:0.1-20, more preferably 1:1:1-5, more preferably 1:1-5, the volume ratio of the precipitant to the solvent is 1:1:0.5 to the solvent is 1:0.0.0-0.0.

In one embodiment, the present invention also relates to a supported non-metallocene catalyst (sometimes also referred to as a supported non-metallocene olefin polymerization catalyst) made by the aforementioned process for the preparation of a supported non-metallocene catalyst.

In a further embodiment, the present invention relates to a process for homo/co-polymerizing olefins, wherein the supported non-metallocene catalyst of the present invention is used as catalyst for olefin polymerization to homo or co-polymerize olefins.

The olefin homo/copolymerization method according to the present invention is not particularly limited, and other matters (such as a polymerization reactor, an olefin amount, a catalyst, an addition mode of olefin, etc.) which are not explicitly described below may be directly applied to those conventionally known in the art, and the descriptions thereof are omitted here.

According to the homo/copolymerization method of the invention, the supported non-metallocene catalyst of the invention is used as a main catalyst, and one or more selected from aluminoxane, alkyl aluminum, halogenated alkyl aluminum, boron fluorine, alkyl boron and alkyl boron ammonium salt are used as cocatalysts to homo or copolymerize olefin.

The main catalyst and the cocatalyst can be added into the polymerization reaction system by adding the main catalyst, then adding the cocatalyst, or adding the cocatalyst, then adding the main catalyst, or adding the main catalyst and the cocatalyst after contact and mixing, or adding the main catalyst and the cocatalyst simultaneously. When the main catalyst and the cocatalyst are added respectively, the main catalyst and the cocatalyst can be added in the same feeding pipeline in sequence or in multiple feeding pipelines in sequence, and when the main catalyst and the cocatalyst are added respectively and simultaneously, multiple feeding pipelines are selected. For continuous polymerization, it is preferable that the multiple feed lines are fed simultaneously and continuously, while for batch polymerization, it is preferable that the two are mixed first and then fed together in the same feed line, or that the cocatalyst is fed first and then the main catalyst is fed in the same feed line.

The reaction mode of the olefin homo/copolymerization process according to the present invention is not particularly limited, and those known in the art can be employed, and examples thereof include a slurry process, an emulsion process, a solution process, a bulk process, and a gas phase process, and among them, a slurry process and a gas phase process are preferable.

According to the present invention, examples of the olefin include C ₂ ～C ₁₀ Mono-olefins, di-olefins, cyclic olefins and other ethylenically unsaturated compounds.

Specifically, as the C ₂ ～C ₁₀ Examples of the mono-olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-undecene, 1-dodecene, and styrene; examples of the cyclic olefin include 1-cyclopentene and norbornene; examples of the diolefin include 1, 4-butadiene, 2, 5-pentadiene, 1, 6-hexadiene, norbornadiene, and 1, 7-octadiene; examples of the other ethylenically unsaturated compound include vinyl acetate and (meth) acrylate. Among them, homopolymerization of ethylene or copolymerization of ethylene with propylene, 1-butene or 1-hexene is preferable.

According to the invention, homopolymerization refers to the polymerization of only one of said olefins, whereas copolymerization refers to the polymerization between two or more of said olefins.

According to the invention, the cocatalyst is selected from the group consisting of alumoxanes, alkyl aluminums, haloalkylaluminum, boroalkanes, alkyl boron and alkyl boron ammonium salts, of which alumoxanes and alkyl aluminums are preferred.

Examples of the aluminoxane include linear aluminoxanes represented by the following general formula (I-1): (R) (R) Al- (Al (R) -O) _n -O-Al (R) (R), and a cyclic aluminoxane represented by the following general formula (II-1): - (Al (R) -O-) _n+2 -。

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

Examples of the aluminum alkyl include compounds represented by the following general formula (III-1):

Al(R) ₃ (III-1)

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

As the haloalkylaluminum, the borane, the alkylboron and the alkylboron ammonium salt, those conventionally used in the art may be directly used without particular limitation.

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

According to the present invention, depending on the reaction mode of the olefin homo/copolymerization method, a solvent for polymerization may be used.

As the solvent for polymerization, those conventionally used in the art for homo/copolymerization of olefins can be used, and there is no particular limitation.

Examples of the solvent for polymerization include C _4-10 Alkanes (such as butane, pentane, hexane, heptane, octane, nonane, decane, etc.), halogenated C' s _1-10 Alkanes (such as methylene chloride), aromatic hydrocarbon solvents (such as toluene and xylene), ether solvents (such as diethyl ether or tetrahydrofuran), ester solvents (such as ethyl acetate), and ketone solvents (such as acetone), and the like. Among them, hexane is preferably used as the solvent for polymerization.

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

According to the present invention, the polymerization pressure of the olefin homo/copolymerization method is generally 0.1 to 10MPa, preferably 0.1 to 4MPa, more preferably 1 to 3MPa, but is not limited thereto in some cases. According to the present invention, the polymerization temperature is generally-40 to 200 ℃, preferably 10 to 100 ℃, more preferably 40 to 90 ℃, but is not limited thereto in some cases.

In addition, according to the present invention, the olefin homo/copolymerization process may be performed in the presence of hydrogen or in the absence of hydrogen. The partial pressure of hydrogen, when present, may be 0.01% to 99%, preferably 0.01% to 50%, of the polymerization pressure, but is sometimes not limited thereto.

In carrying out the olefin homo/copolymerization process according to the present invention, the molar ratio of the cocatalyst in terms of aluminum or boron to the supported non-metallocene catalyst in terms of group IV B metal is generally from 1:1 to 1000, preferably from 1:1 to 500, more preferably from 1:10 to 500, but is not limited thereto in some cases.

Examples

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

Polymer bulk Density (in g/cm) ³ ) The measurement of (C) is performed by referring to the national standard GB 1636-79.

The content of IV B group metal (such as Ti) and Mg element in the supported non-metallocene catalyst is determined by adopting an ICP-AES method, and the content of the non-metallocene ligand is determined by adopting an elemental analysis method.

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

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

Mv＝5.37×10 ⁴ ×[η] ^1.37

Wherein η is the intrinsic viscosity.

The alcohol content in the carrier is determined according to the following method: quantitative analysis is carried out by capillary gas chromatography, an Agilent 6890N-type gas chromatograph is adopted as an instrument, and an automatic sampler and a hydrogen Flame Ionization Detector (FID) are arranged; the column was DB-1 (30 m. Times.0.32 mm. Times.0.25 μm), gas chromatography operating conditions: temperature: the gasification chamber is 250 ℃, the column temperature is 60 ℃, and the detector is 250 ℃; the carrier gas is high-purity nitrogen; the flow rate of the carrier gas is 1.4ml/min; the split ratio is 70:1; the sample injection amount is 0.2ml; the test reagent is chromatographic pure ethanol or n-butanol, wherein the content of the ethanol is determined by n-butanol, the content of the n-butanol is determined by ethanol, and the content of other alcohols is determined by ethanol or n-butanol. The relative retention times were determined to be 2.426min for ethanol and 3.151min for n-butanol. And accurately preparing ten solutions of alcohol to be detected with different concentrations in reagent alcohol as standard samples, calculating correction factors of all components by an area normalization method under the condition of gas chromatography, and obtaining a relation diagram of alcohol concentration index and actual concentration. Accurately weighing 1.00g of carrier, adding 10ml of alcohol reagent, stirring and dissolving for 20min at normal temperature, filtering, and collecting filtrate for later use. Under the gas chromatographic condition, adding quantitative filtrate into an automatic sampler, automatically performing program sample injection measurement, dividing the area of the peak of the alcohol to be detected by the normalized total area to calculate the filtrate alcohol concentration index, substituting the index into a relation diagram to obtain the actual alcohol concentration, and finally obtaining the alcohol content in the carrier after conversion.

Example 1

The magnesium compound adopts anhydrous magnesium chloride, the porous carrier adopts silicon dioxide, namely silica gel, and the model is ES757 of Ineos company. The silica gel was first heat activated by continuous calcination at 600℃under nitrogen atmosphere for 4 hours. The alcohol adopts butanol, the solvent for dissolving magnesium compound adopts tetrahydrofuran (boiling point 65.4 ℃) and the non-metallocene ligand adopts structural formula as follows

The precipitant is hexane, and the chemical treating agent is titanium tetrachloride.

2.5g of anhydrous magnesium chloride (MgCl) of magnesium compound was weighed out ₂ ) Adding a certain amount of butanol and tetrahydrofuran, heating to 60deg.C for dissolving, adding a certain amount of non-metallocene ligand, stirring at 60deg.C to dissolve completely, adding silica gel to form mixed slurry, stirring for 2 hr, adding precipitant hexane to precipitate, filtering, washing for 2 times, adding precipitant in the same amount as before,

the obtained precipitate was dried at a temperature of 50℃below the boiling point of the solvent at 15.4℃under vacuum at an absolute pressure of 5mBar for 12 hours, and then at a temperature of 90℃above the boiling point of 24.6℃under vacuum at an absolute pressure of 5mBar for 8 hours to prepare a composite carrier, wherein the alcohol content was 1.7% by weight.

25ml of hexane solvent was weighed and added to the composite carrier, and titanium tetrachloride (TiCl) was added dropwise with stirring for 15 minutes ₄ ) Chemical treating agent at 30 DEG CAfter the reaction for 4 hours, filtering, washing with hexane for 3 times, 25ml each time, and finally vacuumizing and drying to obtain the supported non-metallocene catalyst.

The mixture ratio is as follows: the molar ratio of the magnesium compound to butanol is 1:0.5; the ratio of the magnesium compound to the tetrahydrofuran solvent for dissolving the magnesium compound is 1 mol:200 ml; the molar ratio of the magnesium compound to the non-metallocene ligand is 1:0.004; the mass ratio of the magnesium compound to the porous carrier silica gel is 1:2; the volume ratio of the precipitator hexane to the tetrahydrofuran solvent for dissolving the magnesium compound is 1:1; the molar ratio of the magnesium compound to the chemical treatment agent titanium tetrachloride is 1:0.20.

The catalyst was designated CAT-1.

Example 2

Substantially the same as in example 1, but with the following modifications:

the mixed slurry was dried under vacuum of 5mBar absolute pressure at a temperature 25.4 ℃ lower than the boiling point of the solvent for 16 hours, and then dried under vacuum of 5mBar absolute pressure at a temperature 34.6 ℃ higher than the boiling point of the solvent for 10 hours to produce a composite carrier, wherein the alcohol content was 1.5wt%.

The catalyst was designated CAT-2.

Example 3

Substantially the same as in example 1, but with the following modifications:

25ml of hexane solvent was weighed and added to the composite carrier obtained in example 1, and the auxiliary chemical treatment agent triethylaluminum (Al (C) was added dropwise over 15 minutes with stirring ₂ H ₅ ) ₃ ) After stirring and reacting for 1h, filtering, washing with hexane for 2 times, 25ml each time, and vacuumizing and drying to obtain the pretreated composite carrier.

Wherein the molar ratio of the magnesium compound to the auxiliary chemical treatment agent is 1:0.35.

The catalyst was designated CAT-3.

Example 4

Substantially the same as in example 3, but with the following modifications:

the auxiliary chemical treating agent is changed into Methylaluminoxane (MAO).

Wherein: the molar ratio of the magnesium compound to the co-chemical treatment agent was 1:0.5.

The catalyst was designated CAT-4.

Comparative example A

Substantially the same as in example 1, but with the following modifications:

adding the mixed slurry into precipitator hexane to precipitate, filtering, washing for 2 times, wherein the dosage of the precipitator is the same as the previous dosage, uniformly heating the obtained precipitate to 120 ℃ (higher than the boiling point of the solvent by 54.6 ℃) and drying for 24 hours under vacuum of absolute pressure of 5mBar to obtain the composite carrier, wherein the alcohol content is 0.03 weight percent.

The catalyst was designated CAT-A.

Comparative example B

Substantially the same as in example 1, but with the following modifications:

the obtained precipitate was dried at a temperature of 20 ℃ (45.4 ℃ below the boiling point of the solvent) under vacuum at an absolute pressure of 5mBar for 12 hours to obtain a composite carrier, wherein the alcohol content was 3.6wt%.

The catalyst was designated CAT-B.

Example 3 (application example)

The supported non-metallocene catalysts CAT-1 to 4 and CAT-A to B were weighed respectively, and homo-polymerization and copolymerization of ethylene with a cocatalyst (methylaluminoxane or triethylaluminum) were carried out under the following conditions, respectively, to prepare ultra-high molecular weight polyethylene.

The homopolymerization is as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85 ℃, hydrogen partial pressure 0.2MPa, reaction time 2h. Firstly, 2.5L of hexane is added into a polymerization autoclave, stirring is started, then 20mg of a supported non-metallocene catalyst and cocatalyst mixture is added, then hydrogen is added to 0.2MPa, and finally ethylene is continuously introduced to ensure that the total polymerization pressure is constant at 0.8MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 1.

The copolymerization is as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.8MPa, polymerization temperature 85 ℃, hydrogen partial pressure 0.2MPa, reaction time 2h. Firstly, 2.5L of hexane is added into a polymerization autoclave, stirring is started, then 20mg of a supported non-metallocene catalyst and cocatalyst mixture is added, 50g of hexene-1 comonomer is added at one time, then hydrogen is added to 0.2MPa, and finally ethylene is continuously introduced to ensure that the total polymerization pressure is constant at 0.8MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 1.

The preparation of the ultra-high molecular weight polyethylene is polymerized as follows: 5L polymerization autoclave, slurry polymerization process, 2.5L hexane solvent, total polymerization pressure 0.5MPa, polymerization temperature 70℃and reaction time 6h. Firstly, 2.5L of hexane is added into a polymerization autoclave, stirring is started, then 20mg of supported non-metallocene catalyst and cocatalyst mixture are added, the molar ratio of the cocatalyst to the catalyst active metal is 100, and finally ethylene is continuously introduced to ensure that the total polymerization pressure is constant at 0.5MPa. And after the reaction is finished, the gas in the kettle is exhausted, the polymer in the kettle is discharged, and the mass is weighed after the drying. The specific cases of the polymerization reaction and the polymerization evaluation results are shown in table 2.

TABLE 1 Supported non-metallocene catalyst used for olefin polymerization effect list

TABLE 2 polymerization effect schedule for Supported non-metallocene catalysts for the preparation of ultra-high molecular weight polyethylene

As is evident from the comparison of the effects obtained by the numbers 1 and 3 in Table 1, the copolymerization effect of the catalyst is remarkable, that is, the copolymerization activity of the catalyst is higher than that of the homopolymerization activity, and the copolymerization reaction can increase the bulk density of the polymer, that is, improve the particle morphology of the polymer.

As can be seen from the comparison of the effects obtained by the numbers 1 and 2 in Table 1, the polymerization performance obtained at the conditions of the molar ratio of the cocatalyst required for the polymerization process to the catalyst active metal of 50 and 100 is equivalent, thereby indicating that the catalyst provided by the present invention requires a smaller amount of cocatalyst for olefin polymerization.

As can be seen from the comparison of the numbers 1, 2, 7 and 8 in Table 1 and the numbers 1, 2, 3 and 4 in Table 2, the catalyst obtained by controlling the alcohol content in the composite carrier in the preparation process of the catalyst of the invention has better catalytic activity, polymer bulk density, ultra-high molecular weight polyethylene viscosity average molecular weight and other properties than the catalyst obtained by completely drying the composite carrier or having higher alcohol content.

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

Claims

1. A method for preparing a supported non-metallocene catalyst, comprising the following steps:

mixing the porous carrier subjected to the heat activation treatment with the magnesium compound solution to obtain a mixed slurry;

Adding a precipitant into the mixed slurry to obtain a composite carrier, wherein the content of the alcohol in the composite carrier is 1.0-2.0wt%; and

a step of treating the composite support with a chemical treatment agent selected from group IVB metal compounds to obtain the supported non-metallocene catalyst,

the porous carrier is one or more of refractory oxide or refractory composite oxide of metals of IIA, IIIA, IVA or IVB groups of periodic table, clay, molecular sieve, mica, montmorillonite, bentonite and diatomite,

the alcohol is selected from one or more of ethanol and butanol,

the step of obtaining the composite carrier is carried out in the following manner: adding a precipitant to the mixed slurry, drying the obtained precipitate at a temperature lower than the boiling point of the solvent by 10-30 ℃ under vacuum of 5-50mBar absolute pressure for 4-24 hours, and then drying at a temperature from the boiling point of the solvent to 40 ℃ higher than the boiling point of the solvent under vacuum of 5-50mBar absolute pressure for 2-12 hours to obtain the composite carrier.

2. The method of preparing according to claim 1, further comprising the step of pre-treating the composite support with a co-chemical treatment agent selected from the group consisting of alumoxane, aluminum alkyls, or any combination thereof, prior to treating the composite support with the chemical treatment agent.

3. The method of claim 1, wherein the porous support is selected from one or more of silica, alumina, magnesia, silica alumina, magnesia alumina, titania, molecular sieves, and montmorillonite.

4. The method according to claim 1, wherein the magnesium compound is selected from one or more of magnesium halide, alkoxymagnesium, alkylmagnesium halide and alkylalkoxymagnesium.

5. The process according to claim 1, wherein the solvent is selected from the group consisting of C _6-12 Aromatic hydrocarbons, halogenated C _6-12 One or more of aromatic hydrocarbons, esters and ethers.

6. The process according to claim 1, wherein the non-metallocene ligand is selected from one or more of the compounds (A-1) to (A-4) and the compounds (B-1) to (B-4) having the following chemical structural formula:

/>

in all of the above chemical formulas,

q is 0 or 1;

d is 0 or 1;

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

-NR ²³ R ²⁴ 、-N(O)R ²⁵ R ²⁶ 、/>

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

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

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

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 bond or an ionic bond;

R ¹ to R ⁴ 、R ⁶ To R ²¹ Each independently selected from hydrogen, C ₁ －C ₃₀ Hydrocarbyl, substituted C ₁ －C ₃₀ Hydrocarbyl or inert functional group, R ²² To R ³⁶ 、R ³⁸ And R is ³⁹ Each independently selected from hydrogen, C ₁ －C ₃₀ Hydrocarbyl or substituted C ₁ －C ₃₀ Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form an aromatic ring;

The 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, C ₁ －C ₁₀ Ester groups and nitro groups;

R ⁵ selected from lone pair electrons on nitrogen, hydrogen, C ₁ －C ₃₀ Hydrocarbyl, substituted C ₁ －C ₃₀ Hydrocarbon groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, selenium-containing groups, or phosphorus-containing groups; when R is ⁵ R in the case of an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a selenium-containing group or a phosphorus-containing group ⁵ N, O, S, P and Se in (3) may be used as the coordinating atoms;

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

7. A process according to claim 6, wherein,

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

the nitrogen-containing group is selected from

-NR ²³ R ²⁴ 、-T-NR ²³ R ²⁴ or-N (O) R ²⁵ R ²⁶ ；

The phosphorus-containing groups are selected from

-PR ²⁸ R ²⁹ 、-P(O)R ³⁰ R ³¹ or-P (O) R ³² (OR ³³ )；

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

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

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

The radicals T being selected from C ₁ －C ₃₀ Hydrocarbyl or substituted C ₁ －C ₃₀ A hydrocarbon group;

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

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

the silicon-containing group is selected from-SiR ⁴² R ⁴³ R ⁴⁴ or-T-SiR ⁴⁵ ；

The germanium-containing group is selected from-GeR ⁴⁶ R ⁴⁷ R ⁴⁸ or-T-GeR ⁴⁹ ；

The tin-containing group is selected from-SnR ⁵⁰ R ⁵¹ R ⁵² 、-T-SnR ⁵³ or-T-Sn (O) R ⁵⁴ ；

The R is ⁴² To R ⁵⁴ Each independently selected from hydrogen, the foregoing C ₁ －C ₃₀ Hydrocarbyl or substituted C as previously described ₁ －C ₃₀ Hydrocarbyl groups, which may be the same or different from each other, wherein adjacent groups may be bonded to each other to form a bond or a ring.

8. The method of claim 1, wherein the non-metallocene ligand is selected from one or more of the compounds having the following chemical formulas:

9. the process according to claim 1, wherein the molar ratio of said magnesium compound to said non-metallocene ligand, calculated as Mg element, is 1:0.0001-1, wherein the ratio of the magnesium compound to the solvent is 1mol: 75-400 ml, the molar ratio of the magnesium compound to the alcohol calculated as Mg element is 1: 0.02-4.00, wherein the mass ratio of the magnesium compound to the porous carrier calculated by the solid of the magnesium compound is 1:0.1-20, wherein the volume ratio of the precipitant to the solvent is 1:0.2 to 5, and the molar ratio of the magnesium compound calculated as Mg element to the chemical treatment agent calculated as group ivb metal element is 1:0.01-1.

10. The method of claim 1, wherein the group ivb metal compound is selected from one or more of group ivb metal halides, group ivb metal alkyls, group ivb metal alkoxides, group ivb metal alkyl halides, and group ivb metal alkoxy halides.

11. The process according to claim 1, wherein the IVB-group metal compound is selected from TiCl ₄ 、TiBr ₄ 、ZrCl ₄ 、ZrBr ₄ 、HfCl ₄ And HfBr ₄ One or more of the following.

12. The process according to claim 2, wherein the aluminoxane is one or more selected from the group consisting of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and n-butylaluminoxane, and the alkylaluminum is one or more selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, triisopentylaluminum, tri-n-pentylaluminum, trihexylaluminum, triisohexylaluminum, diethylmethylaluminum and dimethylethylaluminum.

13. The process according to claim 2, wherein the aluminoxane is one or more selected from the group consisting of methylaluminoxane and isobutylaluminoxane; the alkyl aluminum is selected from one or more of trimethyl aluminum, triethyl aluminum, tripropyl aluminum and triisobutyl aluminum.

14. The method according to claim 2, wherein the molar ratio of the magnesium compound in terms of Mg element to the co-chemical treatment agent in terms of Al element is 1:0-1.0.

15. The process according to claim 1, wherein the precipitating agent is one or more selected from the group consisting of alkanes, cycloalkanes, haloalkanes and halocycloalkanes.

16. The process according to claim 1, wherein the precipitant is one or more selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cycloheptane, cyclodecane, cyclononane, dichloromethane, dichlorohexane, dichloroheptane, trichloromethane, trichloroethane, trichlorobutane, dibromomethane, dibromoethane, dibromoheptane, tribromomethane, tribromoethane, chlorobutane, chlorocyclopentane, chlorocyclohexane, chlorocycloheptane, chlorocyclooctane, chlorocyclononane, chlorocyclodecane, bromocyclopentane, bromocyclohexane, bromocycloheptane, bromocyclooctane, bromocyclononane and bromocyclodecane.

17. A supported non-metallocene catalyst produced by the production method according to any one of claims 1 to 16.

18. An olefin polymerization process comprising the step of homo-or copolymerizing an olefin with the supported non-metallocene catalyst according to claim 17 as a main catalyst and one or more selected from the group consisting of aluminoxane, alkylaluminum, haloalkylaluminum, borane, alkylboron and alkylammonium salts as a cocatalyst.