Internal electron donor for olefin polymerization, catalyst component, catalyst and application of internal electron donor

Abstract

The invention discloses an internal electron donor for olefin polymerization, a catalyst component, a catalyst and application of the internal electron donor, the internal electron donor for olefin polymerization has a structure as shown in a formula I. In the formula I, R1 and R2 are the same or different and are independently selected from C1-C20 alkyl containing or not containing heteroatoms, and R1 and R2 are independently selected from C1-C20 alkyl containing or not containing heteroatoms. The heteroatom is one or a combination of more than two heteroatoms selected from H, N, O, S, P, Si and halogen; x is CH or N. The internal electron donor adopts a non-plasticizer internal electron donor, the prepared catalyst has high catalytic activity which is generally higher than that of common phthalate and diether internal electron donor catalysts in industry, and the polymer obtained by catalytic polymerization has the advantages of regular particle size, high bulk density, high isotacticity, small temperature fluctuation in a kettle during polymerization, and good stability. The reaction is stable and industrial production is facilitated.

Description

Technical Field

[0001] This invention belongs to the field of polyolefin catalyst technology, specifically relating to an internal electron donor for olefin polymerization, catalyst components, catalysts and their applications. Background Technology

[0002] Currently, Ziegler-Natta catalysts (ZN catalysts) still dominate the production of polyolefins. Most ZN catalyst development focuses on developing highly active and stereoregularly oriented catalysts and improving their copolymerization capabilities. Traditional ZN catalysts (transition metal compounds such as titanium chemically bonded to a magnesium support) offer high catalytic efficiency, produce polymers with good overall performance, and are low-cost. Therefore, the vast majority of catalysts used in polypropylene production worldwide are still based on ZN catalytic systems, characterized by high activity, high stereoregularity, long lifespan, and customizable product structures. The development of ZN catalysts shows that, as early as the advent of the first generation of catalysts, it was discovered that adding a third component (mostly an electron donor, also known as a Lewis base; those added during catalyst preparation are called internal electron donors, while those added during polymerization are called external electron donors) significantly impacts olefin polymerization behavior and polymer properties. Changing the internal electron donor in the catalyst can maximally alter the properties of the catalyst's active center, thereby maximizing the change in catalyst performance. Therefore, the development of novel electron donors has always been a hot topic in ZN polypropylene catalyst research and development.

[0003] The high-performance internal electron donor compounds with distinctive features in the prior art mainly include: (1) fatty acid esters and aromatic esters, mainly phthalate esters; (2) diethers (e.g., compounds disclosed in EP0361493 and EP0728724); (3) succinates (e.g., compounds disclosed in WO9856834, WO0063261 and WO03022894); (4) glycol esters (e.g., compounds disclosed in WO9856834, WO0063261 and WO03022894); and (5) compounds with other functional groups (compounds disclosed in CN1105671, CN1242780 and US20060128558), etc. However, in practical applications, the aforementioned compounds all have certain problems as internal electron donors in olefin polymerization catalysts. Phthalate esters, as commonly used plasticizers, pose significant risks to human reproductive health and the environment, creating a strong demand for alternatives, and the use of most phthalate esters has already been restricted. While catalysts using 1,3-diethers as internal electron donors exhibit high activity and good hydrogen-modulated sensitivity, the resulting PP has a narrow molecular weight distribution, hindering the development of different grades of PP. Succinate esters, as internal electron donors, have the advantage of producing PP with a wider molecular weight distribution, but their stereoregularity and hydrogen-modulated sensitivity need improvement. The overall activity of glycol ester catalytic systems is not as ideal as that of diether systems.

[0004] In the production of polyolefins, low catalyst activity increases production costs, increases product ash content, affects product quality, and reduces the competitiveness of polyolefin products. Therefore, it is necessary to improve catalyst activity to meet production requirements. However, when highly active catalysts operate in polyolefin plants, the polymerization temperature often fluctuates greatly due to uneven active centers, excessively high initial reaction rates, and large activity fluctuations, affecting stable production and product quality. Therefore, catalysts with high activity and small temperature fluctuations within the polymerization reactor have greater potential for industrial application. Summary of the Invention

[0005] The purpose of this invention is to provide an internal electron donor for olefin polymerization, a catalyst component, a catalyst, and its application. The internal electron donor of this invention is a non-plasticizer type, and the resulting catalyst has high catalytic activity, generally higher than that of phthalate and diether type internal electron donor catalysts commonly used in industry. Moreover, the polymer obtained by catalytic polymerization has regular particle size, high bulk density, high isotacticity, small temperature fluctuation in the reactor during polymerization, and stable reaction, which is beneficial to industrial production.

[0006] To achieve the above objectives, the present invention provides an internal electron donor for olefin polymerization, having the structure shown in Formula I:

[0007]

[0008] Among them, R 1 and R 2 Whether the two are the same or different, they are each independently selected from C1-C, with or without heteroatoms. 20 The hydrocarbon group, wherein the heteroatom is selected from one or more heteroatoms selected from H, N, O, S, P, Si, and halogens; X is CH or N.

[0009] The internal electron donor for olefin polymerization of the present invention, wherein the C1-C 20 The hydrocarbon group is a straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, alkyl containing heteroatoms, halocycloalkyl, cycloalkyl containing heteroatoms, halophenyl, phenyl containing heteroatoms, haloalkylphenyl, alkylphenyl containing heteroatoms, halophenylalkyl, phenylalkyl containing heteroatoms, halofused-ring aryl, fused-ring aryl containing heteroatoms, halobenzyl, benzyl containing heteroatoms, or heterocyclic aryl substituent; the heteroatoms include one or more combinations of N, O, S, P, and Si.

[0010] The internal electron donor for olefin polymerization of the present invention, wherein the C1-C 20 The hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, either straight-chain or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, fused-ring aryl; preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

[0011] The internal electron donor for olefin polymerization described in this invention, when X is CH, is a pyridine dicarboxylate, including ethyl 2,3-pyridine dicarboxylate, propyl 2,3-pyridine dicarboxylate, butyl 2,3-pyridine dicarboxylate, pentyl 2,3-pyridine dicarboxylate, hexyl 2,3-pyridine dicarboxylate, heptyl 2,3-pyridine dicarboxylate, octyl 2,3-pyridine dicarboxylate, nonyl 2,3-pyridine dicarboxylate, decyl 2,3-pyridine dicarboxylate, dodecyl 2,3-pyridine dicarboxylate, tetradecyl 2,3-pyridine dicarboxylate, hexadecyl 2,3-pyridine dicarboxylate, octadecyl 2,3-pyridine dicarboxylate, phenyl 2,3-pyridine dicarboxylate, and 2,3-pyridine dicarboxylic acid. Benzyl ester, m-chlorophenyl 2,3-pyridinedicarboxylate, o-chlorophenyl 2,3-pyridinedicarboxylate, p-chlorophenyl 2,3-pyridinedicarboxylate, p-methoxyphenyl 2,3-pyridinedicarboxylate, p-methylphenyl 2,3-pyridinedicarboxylate, p-nitrophenyl 2,3-pyridinedicarboxylate, furan methyl 2,3-pyridinedicarboxylate, pentenyl 2,3-pyridinedicarboxylate, phenethyl 2,3-pyridinedicarboxylate, naphthyl 2,3-pyridinedicarboxylate, propylene 2,3-pyridinedicarboxylate, ethyl 2-carboxylate-3-propenyl 2-carboxylate, ethyl 2-carboxylate-3-carboxylate, butyl 2-carboxylate-3-phenyl 2-carboxylate, methyl 2-carboxylate-3-carboxylate, ethyl 2-carboxylate-3-carboxylate.

[0012] The internal electron donor for olefin polymerization described in this invention, when X is N, is a pyrazine dicarboxylate, including ethyl 2,3-pyrazine dicarboxylate, propyl 2,3-pyrazine dicarboxylate, butyl 2,3-pyrazine dicarboxylate, pentyl 2,3-pyrazine dicarboxylate, hexyl 2,3-pyrazine dicarboxylate, heptyl 2,3-pyrazine dicarboxylate, octyl 2,3-pyrazine dicarboxylate, nonyl 2,3-pyrazine dicarboxylate, decyl 2,3-pyrazine dicarboxylate, dodecyl 2,3-pyrazine dicarboxylate, tetradecyl 2,3-pyrazine dicarboxylate, hexadecyl 2,3-pyrazine dicarboxylate, octadecyl 2,3-pyrazine dicarboxylate, phenyl 2,3-pyrazine dicarboxylate, and 2,3-pyrazine dicarboxylic acid. Benzyl ester, m-chlorophenyl 2,3-pyrazinedicarboxylate, o-chlorophenyl 2,3-pyrazinedicarboxylate, p-chlorophenyl 2,3-pyrazinedicarboxylate, p-methoxyphenyl 2,3-pyrazinedicarboxylate, p-methylphenyl 2,3-pyrazinedicarboxylate, p-nitrophenyl 2,3-pyrazinedicarboxylate, furan methyl 2,3-pyrazinedicarboxylate, pentenyl 2,3-pyrazinedicarboxylate, phenethyl 2,3-pyrazinedicarboxylate, naphthyl 2,3-pyrazinedicarboxylate, propylene 2,3-pyrazinedicarboxylate, ethyl 2-carboxylate-3-propenyl 2-carboxylate pyrazine, ethyl 2-carboxylate-3-carboxylate pyrazine, butyl 2-carboxylate-3-phenyl 2-carboxylate pyrazine, methyl 2-carboxylate-3-ethyl 2-carboxylate pyrazine.

[0013] The pyridine dicarboxylate or pyrazine dicarboxylate compound shown in Formula I can be synthesized by methods including but not limited to the following: esterification reaction of pyridine-2,3-dicarboxylic acid or pyrazine-2,3-dicarboxylic acid with an alcohol of a total equivalent of 2 to 4 equivalents (when R1 = R2, a single alcohol is selected as the starting material) to obtain pyridine-2,3-dicarboxylate or pyrazine-2,3-dicarboxylate.

[0014]

[0015] To achieve the above objectives, the present invention also provides a catalyst component for olefin polymerization, comprising Mg, Ti, halogens, and the aforementioned internal electron donor.

[0016] In this invention, Mg is provided by a magnesium compound, and Ti is provided by a titanium compound, wherein the precursor of the magnesium compound is selected from X. n Mg(OR a ) 2-n MgCl2·mR a OH, R a 2-n MgX n One or more combinations of MgCl2 / SiO2, MgCl2 / Al2O3, magnesium halides, and titanium alkoxides, wherein m is 0.1-6, 0≤n≤2, X is a halogen, and R a For C1-C 20 The hydrocarbon group; the general formula of the titanium compound is TiX. n’ (OR b ) 4-n’ In the formula, R b For C1-C 20 The hydrocarbon group, where X is a halogen and n' is 1-4.

[0017] Preferably, the magnesium compound is an alkoxide of magnesium dihalide; or, the magnesium compound is a liquid magnesium compound (a magnesium compound dissolved in a liquid); or, the magnesium compound is a derivative in which at least one halogen atom in a magnesium dihalide molecule is replaced by an alkyl group or a haloalkyl group; preferably, it is an alkyloxy magnesium compound; more preferably, it is an alkoxy magnesium and / or an aryloxy magnesium compound.

[0018] Preferably, the titanium compound includes one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium alkoxyhalides, more preferably titanium tetrachloride.

[0019] Preferably, the alkoxy titanium halide comprises one or a combination of two or more of the following: titanium methoxytrichloride, titanium ethoxytrichloride, titanium propoxytrichloride, titanium n-butoxytrichloride, titanium dimethoxydichloride, titanium diethoxydichloride, titanium dipropoxydichloride, titanium di n-butoxydichloride, titanium trimethoxytrichloride, titanium triethoxytrichloride, titanium tripropoxytrichloride, and titanium tri n-butoxytrichloride.

[0020] The catalyst component for olefin polymerization of the present invention contains, in which the internal electron donor simultaneously comprises a pyridine dicarboxylate ester with X being CH and a pyrazine dicarboxylate ester with X being N.

[0021] The catalyst component for olefin polymerization of the present invention has a molar ratio of pyridine dicarboxylate and pyrazine dicarboxylate of ≥1:9, preferably ≥3:7, further preferably ≥5:5, more preferably ≥7:3, and most preferably ≥9:1.

[0022] In the catalyst component for olefin polymerization of the present invention, the molar ratio of the internal electron donor to magnesium is 0.01-5.0, preferably 0.05-3.0.

[0023] In this invention, the preparation method of the catalyst component for olefin polymerization is not particularly limited, and it can be carried out according to the following listed methods:

[0024] Method 1: A magnesium alkoxide or magnesium chloroalkoxide, excess TiCl4, and an internal electron donor compound are reacted at a temperature of 80℃-135℃; preferably, a compound of the general formula TiX can be used. n’ (OR b ) 4-n’ Titanium compounds (where R) b For C1-C 20 The hydrocarbon group, where X is a halogen, n' = 1-4; preferably TiCl4) and the general formula MgCl2·mR a The adduct of OH (where m is a number from 0.1 to 6, preferably 2 to 4, and R) a For C1-C 20 Solid catalyst components are prepared by reacting hydrocarbon groups (or internal electron donors); wherein the general formula is MgCl2·mR aOH adducts can be suitably prepared into spherical form by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, followed by rapid quenching of the emulsion, thereby solidifying the adduct into spherical particles (see disclosures in US4399054 and US4469648). The spherical adducts obtained by this method can react directly with titanium compounds, or they can be pre-treated with a thermally controlled dealcoholization process (80°C–130°C) to obtain a dealcoholization adduct (wherein the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.5), before proceeding with subsequent reactions.

[0025] For example, the adduct or dealcohol adduct is suspended in cold TiCl4 (typically -25°C to 0°C) to react with a titanium compound, and the mixture is heated to 80°C to 130°C and held at this temperature for 0.5 to 2 hours. The treatment with TiCl4 can be performed once or multiple times, and an internal electron donor compound can be added during the TiCl4 treatment. This treatment can be repeated once or multiple times.

[0026] Method 2: A magnesium compound is dissolved in a solvent system consisting of an organic epoxy compound, an organophosphorus compound, and an inert diluent to form a homogeneous solution. This solution is then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid. This solid is treated with an internal electron-donating compound to load the compound onto the solid. If necessary, further treatment with titanium tetrahalide and an inert diluent is performed. The precipitation aid is one of organic anhydrides, organic acids, ethers, or ketones. The components, per mole of magnesium halide, are: organic epoxy compound 0.2-10 mol, organophosphorus compound 0.1-3 mol, precipitation aid 0-1.0 mol, and Ti compound 0.5-150 mol (based on moles of titanium).

[0027] Method 3: React a TiCl4 or hydroxyl-titanium aromatic hydrocarbon solution (e.g., toluene, xylene, etc.) with a dialkoxymagnesium compound such as magnesium (preferably diethoxymagnesium) or diaryloxymagnesium at -25-0°C, and halogenate at 80-130°C. This treatment with the TiCl4 aromatic hydrocarbon solution can be repeated once or multiple times, and an internal electron donor compound can be added once or in batches during multiple such treatments. For example, the preparation method of the titanium-containing solid catalyst component disclosed in US5077357 can be used as follows: Add magnesium ethoxy, tetraethoxytitanium, o-cresol, ethanol, and chlorobenzene sequentially, and stir; quickly add a TiCl4 / chlorobenzene solution to the above liquid, heat until completely dissolved, and continue heating to a specific temperature; use N2 to bubble away the ethanol reactants, continue stirring for a certain period of time, then wash once with hot chlorobenzene, wash twice with isooctane, and then dry with N2 to obtain the support. Alternatively, as in another example: TiCl4, tetraethoxytitanium, ethoxymagnesium and o-cresol are added to chlorobenzene in sequence and stirred; ethanol is added, and after the ethoxymagnesium dissolves at high temperature, stirring is continued for 3 hours; the mixture is filtered while hot, then washed once with warm chlorobenzene, once with isooctane, and finally dried with N2.

[0028] Method 4: Magnesium dichloride is pre-activated using existing methods, and then treated with excess TiCl4 at approximately 80°C-135°C, wherein the solution contains an internal electron-donating compound. The solid is treated with TiCl4 multiple times and washed with hexane to remove any unreacted TiCl4.

[0029] Method 5: Prepare the titanium-containing solid catalyst component according to the preparation method disclosed in CN1208045: First, contact the liquid magnesium compound and the liquid titanium compound at low temperature in the presence of a compound selected from alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and esters to precipitate a solid. The contact temperature is generally -70°C to 200°C, preferably -30°C to 130°C. During the contact process, treat with an internal electron donor compound.

[0030] Method Six: Anhydrous magnesium chloride and an internal electron donor compound are co-milled under conditions where magnesium dichloride is activated. The resulting product can be treated once or multiple times with excess TiCl4 at a temperature of 80°C-130°C, followed by washing with a hydrocarbon solvent until chloride ions are removed. A more detailed method is as follows: The product obtained by co-milling anhydrous magnesium dichloride, a titanium compound, and an internal electron donor compound is treated with a haloalkane such as 1,2-dichloroethane, chlorobenzene, or dichloromethane. This treatment is carried out at a temperature between 40°C and the boiling point of the haloalkane for 1-4 hours, followed by washing with an inert hydrocarbon solvent such as hexane.

[0031] Method 7: Magnesium compounds supported on inorganic oxides such as SiO2, alumina, or porous silica gel are used as supports for preparation. The mixture is then activated using well-known methods and treated with an excess of TiCl4 at a temperature of approximately 80℃-135℃. During the treatment process, an internal electron donor compound is added.

[0032] The reaction of the above-mentioned catalyst components leads to the formation of magnesium halides in an active form. Typical crystalline magnesium halides have a regular structure and can support very little Ti, resulting in low catalytic activity. To prepare highly active supported catalysts, magnesium halides must undergo activation treatment. Activation methods include using physical and / or chemical methods to prepare them into microcrystals so that active centers are supported on the surface, edges, and defects of the magnesium halide. These treated magnesium halide microcrystals suitable for supporting Ti are called "activated magnesium halides." Besides these reactions, other methods are known in the literature to form magnesium halides in an active form from starting materials different from magnesium halides.

[0033] In any method for preparing the catalyst component, the aforementioned internal electron donor compound can be added directly or optionally, for example, in situ prepared using a suitable precursor that can be converted in the desired internal electron donor compound via known chemical reactions such as esterification or transesterification. Typically, the aforementioned internal electron donor compound is used at a molar ratio of 0.01-5, preferably 0.05-3.0, relative to the molar number of MgCl2. Furthermore, the internal electron donor compound can be added simultaneously or separately during the preparation process, either in batches or in any order and combination.

[0034] To achieve the above objectives, the present invention also provides a catalyst for olefin polymerization, comprising the catalyst components described above and an organoaluminum compound.

[0035] In this invention, the organoaluminum compound has the general formula AlR. c p X (3-p) , where R c It is hydrogen or C1-C 20 The hydrocarbon group, X is a halogen, and p is an integer 0 ≤ p ≤ 3.

[0036] Preferably, the organoaluminum compound comprises one or more of trialkylaluminum compounds, alkylaluminum halides, alkylaluminum hydrides, alkylaluminum sesquichlorides, and alkylaluminoxanes. The trialkylaluminum compound comprises one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and trioctylaluminum; the alkylaluminum halide comprises AlEt2Cl; the alkylaluminum sesquichloride comprises Al2Et3Cl3; more preferably, the organoaluminum compound is a mixture of AlEt2Cl and Al2Et3Cl3.

[0037] The catalyst for olefin polymerization of the present invention has a molar ratio of organoaluminum compound to titanium atoms in the catalyst component of 1-1000:1, more preferably 50-800.

[0038] The catalyst for olefin polymerization described in this invention further includes an external electron donor.

[0039] The catalyst for olefin polymerization described in this invention uses a siloxane compound as the external electron donor.

[0040] In this invention, the general formula of the siloxane compound is R' t Si(OR”) 4-t In this context, R' and R” are each independently selected from C1-C 18 The hydrocarbon group, where t is an integer 0 ≤ t ≤ 3.

[0041] Preferably, R' and R” each contain heteroatoms, and preferably, the heteroatoms include one or more combinations of N, O, S, P, and Si.

[0042] More preferably, the siloxane compound includes trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-n-butyldiethoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldiethoxysilane, di-n-butyldiethoxysilane, and n-butylmethyl Dimethoxysilane, di(2-ethylhexyl)dimethoxysilane, di(2-ethylhexyl)diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane oxysilanes, pentylethyl dimethoxysilane, pentylethyl diethoxysilane, cyclohexyl dimethylmethoxysilane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylmethoxysilane, cyclohexyl diethylethoxysilane, 2-ethylhexyl trimethoxysilane, cyclohexyl dimethoxysilane, cyclohexyl diethoxysilane, 2-ethylhexyl triethoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane, n-propyl trimethoxysilane, n-propyl triethoxysilane, isopropyl trimethoxysilane, isopropyl triethoxysilane, n-butyl trimethoxysilane, isobutyl trimethoxysilane, tert-butyl trimethoxysilane, n-butyl triethoxysilane, cyclohexyl trimethoxysilane, cyclohexyl triethoxysilane, cyclopentyl trimethoxysilane, cyclohexyl trimethoxysilane, cyclohexyl trieth ... Pentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, di(3-methylcyclohexyl)dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, di(4-methylcyclohexyl)dimethoxysilane, 3,One or more combinations of 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis(3,5-dimethylcyclohexyl)dimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.

[0043] Preferably, the siloxane compound comprises one or more combinations of di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyl trimethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclohexylethyl dimethoxysilane, cyclohexylethyl diethoxysilane, cyclopentylmethyl dimethoxysilane, cyclopentylmethyl diethoxysilane, cyclopentylethyl dimethoxysilane, cyclohexylcyclopentyl dimethoxysilane, cyclohexylcyclopentyl diethoxysilane, 3-methylcyclohexylcyclopentyl dimethoxysilane, 4-methylcyclohexylcyclopentyl dimethoxysilane, and 3,5-dimethylcyclopentyl dimethoxysilane.

[0044] Preferably, the siloxane compound comprises one or more of the following: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane, and tert-hexyltrimethoxysilane.

[0045] The catalyst for olefin polymerization of the present invention has a molar ratio of silicon in the external electron donor to titanium atoms in the catalyst component of 0.002-100, more preferably 0.01-20, and even more preferably 0.01-5.

[0046] The catalyst for olefin polymerization described in this invention further includes an activity modifier.

[0047] The catalyst for olefin polymerization described in this invention comprises an activity modifier being a piperate ester of Formula II:

[0048]

[0049] Among them, R 3 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 ester group, R 3 It may or may not contain heteroatoms, which include one or more combinations of N, O, S, P, and Si.

[0050] The catalyst for olefin polymerization described in this invention, R 3 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, and fused-ring aryl.

[0051] The catalyst for olefin polymerization of the present invention comprises one or more of the following: methyl piperate, ethyl piperate, n-propyl piperate, isopropyl piperate, n-butyl piperate, isobutyl piperate, n-pentyl piperate, isopentyl piperate, n-octyl piperate, isooctyl piperate, cyclohexyl piperate, and phenyl piperate.

[0052] In another technical solution of this invention, the activity regulator is a paeonol derivative represented by Formula III:

[0053]

[0054] Among them, R 4 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 ester group, R 4 It may or may not contain heteroatoms, which include one or more combinations of N, O, S, P, and Si.

[0055] The catalyst for olefin polymerization described in this invention, R 4 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, and fused-ring aryl.

[0056] The catalyst for olefin polymerization described in this invention, R 4 Selected from carbonyl alkyl and carbonyl aryl groups with up to 20 carbon atoms.

[0057] The catalyst for olefin polymerization described in this invention includes paeonol derivatives comprising 2-methyl ether-4-methoxyacetophenone, 2-ethyl ether-4-methoxyacetophenone, 2-propyl ether-4-methoxyacetophenone, 2-butyl ether-4-methoxyacetophenone, 2-anisole-4-methoxyacetophenone, 2-acetylphenol ester-4-methoxyacetophenone, 2-propanoylphenol ester-4-methoxyacetophenone, 2-butanoylphenol ester-4-methoxyacetophenone, and 2-pentanoylphenol. One or more of the following: ester-4-methoxyacetophenone, 2-hexanoylphenol ester-4-methoxyacetophenone, 2-benzoylphenol ester-4-methoxyacetophenone, 2-phenylacetylphenol ester-4-methoxyacetophenone, 2-m-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-methoxybenzoylphenol ester-4-methoxyacetophenone, and 2-p-nitrobenzoylphenol ester-4-methoxyacetophenone.

[0058] The catalyst for olefin polymerization described in this invention, when the activity modifier is selected from piperate ester and paeonol derivative, has a feed ratio of piperate ester and paeonol derivative of 50:1-1:50, preferably 20:1-1:20, and more preferably 10:1-1:10.

[0059] The catalyst for olefin polymerization of the present invention has an activity regulator and a siloxane compound in a molar ratio of (0.02-50):1, preferably (0.1-10):1.

[0060] The present invention also provides an application of the catalyst described herein in olefin polymerization.

[0061] The application of the catalyst described in this invention in olefin polymerization, wherein the olefin includes straight-chain or branched olefins, and the olefin includes one or more combinations of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

[0062] The application of the catalyst described in this invention in olefin polymerization, wherein the olefins include ethylene and / or propylene.

[0063] The application of the catalyst described in this invention in olefin polymerization, wherein the polymerization includes homopolymerization or copolymerization.

[0064] During the catalytic process, the order in which the components of the catalyst are added is arbitrary, but it is preferable to add the organoaluminum compound first to the polymerization system, then add the external electron donor, and finally add the catalyst components.

[0065] In the above applications, the polymerization process can be carried out with or without a solvent; the olefin monomer can be in the gas phase or the liquid phase; more preferably, hydrogen can be added as a molecular weight regulator (polymerization can also be carried out without a molecular weight regulator); continuous polymerization or batch polymerization processes can be used, and the polymerization reaction can be carried out in one, two, or multiple steps.

[0066] The application of the catalyst described in this invention in olefin polymerization, wherein the polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; and the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

[0067] Beneficial effects of this invention:

[0068] This invention provides a catalyst component with pyridine diester and / or pyrazine diester as internal electron donors. The catalysts prepared by this series of internal electron donor compounds generally have higher activity than the most commonly used phthalate internal electron donor catalysts in industry, and higher activity than highly active diether catalysts. They also have good stereoselectivity, high isotacticity of the polymer obtained by catalysis, and small temperature fluctuations during operation of the catalyst in the polymerization unit. Detailed Implementation

[0069] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0070] The isotacticity of polymers was determined by the heptane extraction method (boiling heptane extraction for 6 hours): two grams of dry polymer sample were placed in an extractor and extracted with boiling heptane for 6 hours. The residue was then dried to constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotacticity.

[0071] The bulk density of the polymer was determined using the method specified in JB / T 2412-2008.

[0072] Preparation example: Synthesis of the compound shown in Formula I

[0073] In a 500 mL round-bottom flask, 2,3-pyridinedicarboxylic acid (8.4 g), ethanol (13 g), N,N'-dicyclohexylcarbodiimide (DCC) (22.9 g), 4-dimethylaminopyridine (DMAP) (307 mg), and toluene (200 mL) were added sequentially. After reacting at room temperature for 48 hours, the reaction solution was filtered, the filter cake was washed with ethyl acetate, the filtrate was purified by column chromatography after removing the solvent, and the eluent was n-hexane / ethyl acetate to obtain a1.

[0074] a2-a21 was synthesized using the route described above, and the structure and NMR results are shown in Table 1.

[0075]

[0076] The compounds shown in Formula I in Table 1

[0077]

[0078]

[0079]

[0080] Preparation of catalyst components

[0081] Example 1

[0082] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0083] In a 500 mL stirred flask fully purged with nitrogen, 10 g of MgCl2·2.5C2H5OH microspheres and 150 mL of titanium tetrachloride were added to prepare a suspension. The suspension was then maintained at -15 °C for 1 hour, slowly heated to 80 °C, and 10 mmol of ethyl 2,3-pyridinedicarboxylate was added. The temperature was further increased to 110 °C and held constant for 1 hour. The liquid was then filtered off, and the resulting solid was washed three times with 120 mL of titanium tetrachloride at 125 °C. It was then washed four times with 150 mL of hexane at 60 °C. Finally, the liquid was filtered off and dried to obtain solid catalyst component C1. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0084] Example 2-Example 21

[0085] Examples 2-21 each provide a catalyst component C2-C21, the preparation process of which is as shown in Example 1, except that ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 10 mmol of compounds a2-a21 in Table 1 in sequence.

[0086] Example 22

[0087] The catalyst preparation process in this embodiment is the same as in Example 1, except that 10 mmol of ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 1 mmol of ethyl 2,3-pyridinedicarboxylate (a1) and 9 mmol of n-butyl 2,3-pyrazinedicarboxylate (a14).

[0088] Example 23

[0089] The catalyst preparation process in this embodiment is the same as in Example 1, except that 10 mmol of ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 3 mmol of ethyl 2,3-pyridinedicarboxylate (a1) and 7 mmol of n-butyl 2,3-pyrazinedicarboxylate (a14).

[0090] Example 24

[0091] The catalyst preparation process in this embodiment is the same as in Example 1, except that 10 mmol of ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 5 mmol of ethyl 2,3-pyridinedicarboxylate (a1) and 5 mmol of n-butyl 2,3-pyrazinedicarboxylate (a14).

[0092] Example 25

[0093] The catalyst preparation process in this embodiment is the same as in Example 1, except that 10 mmol of ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 7 mmol of ethyl 2,3-pyridinedicarboxylate (a1) and 3 mmol of n-butyl 2,3-pyrazinedicarboxylate (a14).

[0094] Example 26

[0095] The catalyst preparation process in this embodiment is the same as in Example 1, except that 10 mmol of ethyl 2,3-pyridinedicarboxylate (a1) is replaced with 9 mmol of ethyl 2,3-pyridinedicarboxylate (a1) and 1 mmol of n-butyl 2,3-pyrazinedicarboxylate (a14).

[0096] Example 27

[0097] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0098] In a 500 mL stirred flask fully purged with nitrogen, 10 g of anhydrous magnesium chloride, 150 mL of toluene, 17 mL of epichlorohydrin, and 16 mL of tributyl phosphate were added at room temperature. The mixture was heated to 50 °C with stirring and maintained for 2 hours until the solid was completely dissolved. Then, 2.40 g of phthalic anhydride was added, and the mixture was maintained for another hour. The solution was cooled to -25 °C, and 110 mL of titanium tetrachloride was added dropwise over 1 hour. The temperature was slowly raised to 80 °C, and the solid was gradually eluted during the heating process. 10 mmol of titanium tetrachloride was then added. 2,3-Pyridinedicarboxylate (a3) ​​was heated at 80°C for 1 hour; after filtration, it was washed twice with 200 mL of toluene, then 120 mL of toluene and 80 mL of titanium tetrachloride were added, and the temperature was further increased to 110°C and held for 2 hours. The liquid was then filtered clean, and the process was repeated once more. The liquid was filtered off, and the resulting solid was washed once with 100 mL of dichloroethane and four times with hexane. After drying, solid catalyst component C27 was obtained. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0099] Example 28

[0100] This embodiment provides a catalyst component, the preparation method of which is as follows:

[0101] In a 500 mL stirred flask fully purged with nitrogen, 8 g of magnesium diethoxy and 100 mL of toluene were added to prepare a suspension. 25 mL of titanium tetrachloride was added dropwise at -15 °C. After the addition was complete, the temperature was slowly raised to 0 °C, and then 50 mL of titanium tetrachloride was added dropwise. The temperature was then slowly raised to 80 °C, and 2,3-pyridinedicarboxylic acid n-butyl ester (a3) ​​was added. The temperature was further raised to 110 °C and held constant for 2 hours. The liquid was then filtered off. The resulting solid was washed three times with 100 mL of titanium tetrachloride at 125 °C, and then four times with 120 mL of hexane at 60 °C. The liquid was filtered off and dried to obtain solid catalyst component C28. The titanium content, internal electron donor content, and polymerization data of this solid catalyst component are shown in Table 2.

[0102] Comparative Example 1

[0103] This comparative example provides a catalyst component D1, which is prepared in the same way as in Example 1, except that a1 is replaced with 10 mmol of di-n-butyl phthalate (DN).

[0104] Comparative Example 2

[0105] This comparative example provides a catalyst component D2, which is prepared in the same way as in Example 1, except that a1 is replaced with 10 mmol of 9,9-dimethoxyfluorene (FLU).

[0106] Aggregation 1

[0107] The catalyst components obtained above were used as components of olefin polymerization catalysts for polymerization evaluation:

[0108] After purging the 5L stainless steel reactor with nitrogen, 5mL of a 0.5mol / L triethylaluminum hexane solution, 1mL of a 0.1mol / L methylcyclohexyldimethoxysilane hexane solution, and 10mg of the prepared catalyst component were added. Then, 10mL of hexane was added to flush the feed line, followed by 2L (under standard conditions) of hydrogen and 2.5L of purified propylene. The reaction was prepolymerized at 25℃ for 5 minutes, then the temperature was raised to 70℃, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain the polymer. Polymerization data are shown in Table 2.

[0109] Table 2

[0110]

[0111]

[0112] Aggregation 2

[0113] Polymerization evaluation was conducted using catalyst component C3 as a component of the olefin polymerization catalyst.

[0114] After purging the 5L stainless steel reactor with nitrogen, 5 mL of a 0.5 mol / L triethylaluminum hexane solution, 1 mL of a 0.1 mol / L methylcyclohexyldimethoxysilane hexane solution, the activity modifier (0.1 mol / L hexane solution) of the types and amounts described in Table 3, and 10 mg of the prepared catalyst component were added. Then, 10 mL of hexane was added to flush the feed line, followed by 2 L (under standard conditions) of hydrogen and 2.5 L of purified propylene. The reaction was prepolymerized at 25°C for 5 minutes, then the temperature was raised to 70°C, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reactor was cooled and stirring was stopped. The reaction product was discharged and dried to obtain the polymer. The polymerization data are shown in Table 3.

[0115] Table 3

[0116]

[0117] Active modifiers: b1, isopropyl piperate; b2, n-amyl piperate; b3, isooctyl piperate; b4, phenyl piperate; b5, 2-methyl ether-4-methoxyacetophenone; b6, 2-butyrophenol ester-4-methoxyacetophenone; b7, 2-benzoylphenol ester-4-methoxyacetophenone.

[0118] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. An internal electron donor for olefin polymerization, characterized in that, It has the structure shown in Equation I: Among them, R 1 and R 2 Whether the two are the same or different, they are each independently selected from C1-C, with or without heteroatoms. 20 The hydrocarbon group, wherein the heteroatom is selected from one or more heteroatoms selected from H, N, O, S, P, Si, and halogens; X is CH or N.

2. The internal electron donor for olefin polymerization according to claim 1, characterized in that, The C1-C 20 The hydrocarbon group is a straight-chain or branched alkyl, cycloalkyl, alkenyl, ester, phenyl, alkylphenyl, phenylalkyl, fused-ring aryl, benzyl, haloalkyl, alkyl containing heteroatoms, halocycloalkyl, cycloalkyl containing heteroatoms, halophenyl, phenyl containing heteroatoms, haloalkylphenyl, alkylphenyl containing heteroatoms, halophenylalkyl, phenylalkyl containing heteroatoms, halofused-ring aryl, fused-ring aryl containing heteroatoms, halobenzyl, benzyl containing heteroatoms, or heterocyclic aryl substituent; the heteroatoms include one or more combinations of N, O, S, P, and Si.

3. The internal electron donor for olefin polymerization according to claim 1, characterized in that, The C1-C 20 The hydrocarbon groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 The following substituents with 20 or fewer carbon atoms, either straight-chain or branched alkyl groups: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, fused-ring aryl; preferably, the alkenyl group includes propenyl, butenyl, pentenyl, and hexenyl.

4. The internal electron donor for olefin polymerization according to claim 1, characterized in that, When X is CH, the internal electron donor is a pyridine dicarboxylate, including ethyl 2,3-pyridine dicarboxylate, propyl 2,3-pyridine dicarboxylate, butyl 2,3-pyridine dicarboxylate, pentyl 2,3-pyridine dicarboxylate, hexyl 2,3-pyridine dicarboxylate, heptyl 2,3-pyridine dicarboxylate, octyl 2,3-pyridine dicarboxylate, nonyl 2,3-pyridine dicarboxylate, decyl 2,3-pyridine dicarboxylate, dodecyl 2,3-pyridine dicarboxylate, tetradecyl 2,3-pyridine dicarboxylate, hexadecyl 2,3-pyridine dicarboxylate, octadecyl 2,3-pyridine dicarboxylate, phenyl 2,3-pyridine dicarboxylate, benzyl 2,3-pyridine dicarboxylate, etc. m-Chlorophenyl dicarboxylate, o-Chlorophenyl dicarboxylate, p-Chlorophenyl dicarboxylate, p-Methoxyphenyl dicarboxylate, p-Methylphenyl dicarboxylate, p-Nitrophenyl dicarboxylate, furan methyl dicarboxylate, pentenyl dicarboxylate, phenethyl dicarboxylate, naphthyl dicarboxylate, propylene dicarboxylate, ethyl 2-carboxylate-3-propenyl 2-carboxylate, ethyl 2-carboxylate-3-carboxylate, butyl 2-carboxylate-3-carboxylate, phenyl 2-carboxylate-3-carboxylate, methyl 2-carboxylate-3-carboxylate.

5. The internal electron donor for olefin polymerization according to claim 1, characterized in that, When X is N, the internal electron donor is a pyrazine dicarboxylate, including ethyl 2,3-pyrazine dicarboxylate, propyl 2,3-pyrazine dicarboxylate, butyl 2,3-pyrazine dicarboxylate, pentyl 2,3-pyrazine dicarboxylate, hexyl 2,3-pyrazine dicarboxylate, heptyl 2,3-pyrazine dicarboxylate, octyl 2,3-pyrazine dicarboxylate, nonyl 2,3-pyrazine dicarboxylate, decyl 2,3-pyrazine dicarboxylate, dodecyl 2,3-pyrazine dicarboxylate, tetradecyl 2,3-pyrazine dicarboxylate, hexadecyl 2,3-pyrazine dicarboxylate, octadecyl 2,3-pyrazine dicarboxylate, phenyl 2,3-pyrazine dicarboxylate, benzyl 2,3-pyrazine dicarboxylate, and 2,3-pyrazine dicarboxylate. m-chlorophenyl dicarboxylate, o-chlorophenyl 2,3-pyrazinedicarboxylate, p-chlorophenyl 2,3-pyrazinedicarboxylate, p-methoxyphenyl 2,3-pyrazinedicarboxylate, p-methylphenyl 2,3-pyrazinedicarboxylate, p-nitrophenyl 2,3-pyrazinedicarboxylate, furan methyl 2,3-pyrazinedicarboxylate, pentenyl 2,3-pyrazinedicarboxylate, phenethyl 2,3-pyrazinedicarboxylate, naphthyl 2,3-pyrazinedicarboxylate, propylene 2,3-pyrazinedicarboxylate, ethyl 2-carboxylate-3-propenyl 2-carboxylate pyrazine, ethyl 2-carboxylate-3-carboxylate pyrazine, butyl 2-carboxylate-3-phenyl 2-carboxylate pyrazine, methyl 2-carboxylate-3-ethyl 2-carboxylate pyrazine.

6. A catalyst component for olefin polymerization, characterized in that, Including Mg, Ti, halogens, and internal electron donors as described in any one of claims 1-5.

7. The catalyst component for olefin polymerization according to claim 6, characterized in that, The internal electron donor contains both pyridine dicarboxylate (where X is CH) and pyrazine dicarboxylate (where X is N).

8. The catalyst component for olefin polymerization according to claim 7, characterized in that, The molar ratio of pyridine dicarboxylate to pyrazine dicarboxylate is ≥1:9, preferably ≥3:

7.

9. The catalyst component for olefin polymerization according to claim 6, characterized in that, The molar ratio of the internal electron donor to magnesium is 0.01-5.0, preferably 0.05-3.

0.

10. A catalyst for olefin polymerization, characterized in that, It includes the catalyst component and organoaluminum compound as described in any one of claims 6-9.

11. The catalyst for olefin polymerization according to claim 10, characterized in that, The molar ratio of the organoaluminum compound to the titanium atoms in the catalyst component is 1-1000:1, more preferably 50-800.

12. The catalyst for olefin polymerization according to claim 10, characterized in that, The catalyst also includes an external electron donor.

13. The catalyst for olefin polymerization according to claim 12, characterized in that, The external electron donor is a siloxane compound.

14. The catalyst for olefin polymerization according to claim 13, characterized in that, The molar ratio of silicon in the external electron donor to titanium atoms in the catalyst component is 0.002-100, more preferably 0.01-20, and even more preferably 0.01-5.

15. The catalyst for olefin polymerization according to claim 10, characterized in that, The catalyst also includes an activity modifier.

16. The catalyst for olefin polymerization according to claim 15, characterized in that, The activity modifier is the piperate ester shown in Formula II: Among them, R 3 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 ester group, R 3 It may or may not contain heteroatoms, which include one or more combinations of N, O, S, P, and Si.

17. The catalyst for olefin polymerization according to claim 16, characterized in that, R 3 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, and fused-ring aryl.

18. The catalyst for olefin polymerization according to claim 16, characterized in that, The piperate esters include one or more of the following: methyl piperate, ethyl piperate, n-propyl piperate, isopropyl piperate, n-butyl piperate, isobutyl piperate, n-pentyl piperate, isopentyl piperate, n-octyl piperate, isooctyl piperate, cyclohexyl piperate, and phenyl piperate.

19. The catalyst for olefin polymerization according to claim 15, characterized in that, The activity modifier is a paeonol derivative as shown in Formula III: Among them, R 4 Selected from C1-C 20 Straight-chain or branched alkyl groups and their derivatives, C3-C 20 cycloalkyl, C6-C 20 aryl groups and their derivatives, C7-C 20 Araneyl groups and their derivatives, C2-C 10 olefin group, C 10 -C 20 Fused ring aryl, C 10 -C 20 ester group, R 4 It may or may not contain heteroatoms, which include one or more combinations of N, O, S, P, and Si.

20. The catalyst for olefin polymerization according to claim 19, characterized in that, R 4 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, C 11 -C 20 Straight-chain or branched alkyl groups, and the following substituents with 20 or fewer carbon atoms: alkenyl, phenyl, m-chlorophenyl, p-chlorophenyl, o-chlorophenyl, m-methoxyphenyl, p-methoxyphenyl, o-methoxyphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, benzyl and its derivatives, phenethyl and its derivatives, furanyl, pyrroleyl, thiophenyl, and fused-ring aryl.

21. The catalyst for olefin polymerization according to claim 20, characterized in that, R 4 Selected from carbonyl alkyl and carbonyl aryl groups with up to 20 carbon atoms.

22. The catalyst for olefin polymerization according to claim 19, characterized in that, The paeonol derivatives include 2-methyl ether-4-methoxyacetophenone, 2-ethyl ether-4-methoxyacetophenone, 2-propyl ether-4-methoxyacetophenone, 2-butyl ether-4-methoxyacetophenone, 2-anisole-4-methoxyacetophenone, 2-acetylphenol ester-4-methoxyacetophenone, 2-propionylphenol ester-4-methoxyacetophenone, 2-butyrylphenol ester-4-methoxyacetophenone, and 2-pentanoylphenol ester-4-methoxyacetophenone. One or more of the following: ketone, 2-hexanoylphenol ester-4-methoxyacetophenone, 2-benzoylphenol ester-4-methoxyacetophenone, 2-phenylacetylphenol ester-4-methoxyacetophenone, 2-m-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-chlorobenzoylphenol ester-4-methoxyacetophenone, 2-p-methoxybenzoylphenol ester-4-methoxyacetophenone, and 2-p-nitrobenzoylphenol ester-4-methoxyacetophenone.

23. The catalyst for olefin polymerization according to claim 15, characterized in that, When the active modifier is selected from piperate esters and paeonol derivatives, the feed ratio of piperate esters and paeonol derivatives is 50:1-1:50, preferably 20:1-1:20, and more preferably 10:1-1:

10.

24. The catalyst for olefin polymerization according to claim 10, characterized in that, The catalyst comprises a siloxane external electron donor and an activity modifier, wherein the molar ratio of the activity modifier to the siloxane compound is (0.02-50):1, preferably (0.1-10):

1.

25. The use of the catalyst according to any one of claims 10-24 in olefin polymerization.

26. The application of the catalyst according to claim 25 in olefin polymerization, characterized in that, The olefins include straight-chain or branched olefins, and the olefins include one or more combinations of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, butadiene, vinylcyclopentene, and vinylcyclohexene.

27. The application of the catalyst according to claim 25 in olefin polymerization, characterized in that, The olefins include ethylene and / or propylene.

28. The application of the catalyst according to claim 25 in olefin polymerization, characterized in that, The polymerization includes homopolymerization or copolymerization.

29. The application of the catalyst according to claim 25 in olefin polymerization, characterized in that, The polymerization temperature is ≤200℃, more preferably 20-100℃, and even more preferably 40-80℃; the polymerization pressure is ≤10MPa, more preferably 0.3-5MPa.

Images