Catalyst for olefin polymerization and olefin polymerization method

Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and relates to a catalyst for olefin polymerization and an olefin polymerization method. The catalyst comprises reaction products of the following components: 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor compound comprises a polyol ester compound; 2) an aluminum alkyl compound; 3) a compound of an external electron donor, wherein the compound of the external electron donor comprises an ester compound and alkyl dialkoxy silane; the ester compound is selected from at least one of compounds shown in a formula (I); in the # imgabs0 # formula (I), R1 and R2 are respectively and independently selected from linear alkyl, branched alkyl, cycloalkyl, alkaryl, aralkyl, condensed ring aryl or alkylene; r3 is selected from linear alkyl, branched alkyl or alkyl; and R4 is selected from linear alkyl, branched alkyl, cycloalkyl, alkaryl, aralkyl or fused ring aryl. The polymerization activity of the catalyst is improved, and the hydrogen regulation sensitivity is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of olefin polymerization catalysts, and more specifically, relates to a catalyst for olefin polymerization and an olefin polymerization method. Background Art

[0002] The catalyst system used in the homopolymerization or copolymerization of α-olefins generally consists of three parts: (1) a main catalyst (a solid catalyst component containing titanium and magnesium or a catalyst suspension), (2) a co-catalyst (usually an alkyl aluminum compound) and (3) an external electron donor compound added during the polymerization.

[0003] It is well known to those skilled in the art that one or more external electron donor compounds are used to control the stereoregularity and morphology of polymers during polymerization. In addition to affecting the stereoregularity of polymers, external electron donors often affect other aspects of the catalyst performance to varying degrees. Although a variety of compounds are known to be external electron donors, different external electron donor compounds may produce different polymer properties for a specific catalyst. Selecting a suitable external electron donor can be particularly compatible with a specific catalyst system, that is, finding a suitable external electron donor can significantly improve certain aspects of the performance of the polymer product, so it is very advantageous to find a group of external electron donors that can be used for a specific catalyst to give the polymer outstanding performance in certain aspects.

[0004] CN1169845C and CN1213080C describe the use of polyol ester compounds as catalyst components of internal electron donors, and also use different external electron donors commonly used in industry. For example, in addition to methylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, dicyclopentyldimethoxysilane, etc. are also used. The catalyst system exhibits high activity, high directional ability and a wide molecular weight distribution of the prepared polymer.

[0005] Patent documents CN02100896.5, CN02100900.7, CN03109781.2, CN03140565.7, CN200410073623.8, and CN200410073621.9 respectively describe catalyst components using polyol ester compounds and phthalic acid ester compounds as internal electron donors. When the catalyst component is used for propylene polymerization, the external electron donor hydrocarbyl dihydrocarbyloxy silane used is an external electron donor commonly used in industry, such as methylcyclohexyldimethoxysilane (CHMMS) and the like.

[0006] CN101724102B, CN102234339B, CN1121368C, CN100348624C, CN101560273A, CN1743348A, US9133286 and the like describe catalyst components using a diether compound alone or a diether compounded with a polyol ester compound as an internal electron donor. When the catalyst component is used for propylene polymerization, the external electron donor hydrocarbyl dihydrocarbyloxysilane used is an external electron donor commonly used in industry, such as methylcyclohexyldimethoxysilane (CHMMS) and the like.

[0007] The research of existing olefin polymerization catalysts mainly focuses on improving the performance of olefin polymerization activity and stereoregularity of polymers, and has achieved the above-mentioned purpose. However, these catalysts are difficult to control the performance of polymers (such as isotactic index, melt index) by adjusting the amount of external electron donor to a certain extent when the type of external electron donor remains unchanged, resulting in the application of olefin polymerization catalysts being limited. Therefore, it is necessary to develop a new catalyst to solve this problem. Summary of the invention

[0008] The inventors unexpectedly discovered during their research that when a catalyst component containing titanium, magnesium, halogen and a specific internal electron donor compound is added with a composite external electron donor containing a specific structural ester compound during olefin polymerization, a polymer with excellent comprehensive performance can be obtained in combination with a specific catalyst component under the same polymerization conditions. By adjusting the polymerization conditions and the composition of the external electron donor, the obtained catalyst has improved polymerization activity and hydrogen sensitivity while maintaining high directional ability. Based on this discovery, the present invention is proposed.

[0009] In order to achieve the object of the present invention, the first aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the reaction product of the following components:

[0010] 1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor compound is a polyol ester compound;

[0011] 2) Alkyl aluminum compounds;

[0012] 3) a composite external electron donor compound, wherein the composite external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane;

[0013] The ester compound is selected from at least one of the compounds represented by formula (I);

[0014]

[0015] In formula (I), R 1 , R 2 Each independently selected from C1-C20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Arylalkyl or C 10 -C 20 A fused ring aromatic group.

[0016] The second aspect of the present invention provides an olefin polymerization method, which comprises: contacting one or more olefins with the catalyst for olefin polymerization under olefin polymerization reaction conditions.

[0017] Compared with conventional external electron donors such as C-donor and D-donor, the composite external electron donor compound in the catalyst system of the present invention is combined with a solid catalyst component. By adjusting the polymerization conditions and the composition of the composite external electron donor while maintaining good comprehensive performance of the catalyst, the obtained catalyst has improved polymerization activity and hydrogen regulation sensitivity while maintaining high directional ability.

[0018] Other features and advantages of the present invention will be described in detail in the following detailed description. DETAILED DESCRIPTION

[0019] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0020] In order to achieve the object of the present invention, the first aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising the reaction product of the following components:

[0021] 1) A solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor compound is a polyol ester compound;

[0022] 2) Alkyl aluminum compounds;

[0023] 3) a composite external electron donor compound, wherein the composite external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane;

[0024] The ester compound is selected from at least one of the compounds represented by formula (I);

[0025]

[0026] In formula (I), R 1 , R 2 Each independently selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl or C 10 -C 20 A fused ring aromatic group.

[0027] According to the present invention, preferably, the ester compound is selected from the group consisting of 2-methoxybenzylidene dimethyl malonate, 3-methoxybenzylidene dimethyl malonate, 4-methoxybenzylidene dimethyl malonate, 2-ethoxybenzylidene dimethyl malonate, 3-ethoxybenzylidene dimethyl malonate, 4-ethoxybenzylidene dimethyl malonate, 2-propoxybenzylidene dimethyl malonate, 3-propoxybenzylidene dimethyl malonate, 4-propoxybenzylidene dimethyl malonate, 2-isopropoxybenzylidene dimethyl malonate, 3-isopropoxybenzylidene dimethyl malonate, 4-isopropoxybenzylidene dimethyl malonate, 2-butoxybenzylidene dimethyl malonate, 3-butoxybenzylidene dimethyl malonate, 4-butoxybenzylidene dimethyl malonate. dimethyl 2-isobutoxybenzylidene malonate, dimethyl 3-isobutoxybenzylidene malonate, dimethyl 4-isobutoxybenzylidene malonate, diethyl 2-methoxybenzylidene malonate, diethyl 3-methoxybenzylidene malonate, diethyl 4-methoxybenzylidene malonate, diethyl 2-ethoxybenzylidene malonate, diethyl 3-ethoxybenzylidene malonate, diethyl 4-ethoxybenzylidene malonate, diethyl 2-propoxybenzylidene malonate, diethyl 3-propoxybenzylidene malonate, diethyl 4-propoxybenzylidene malonate, diethyl 2-isopropoxybenzylidene malonate, diethyl 3-isopropoxybenzylidene malonate, diethyl 4-isopropoxybenzylidene malonate Diethyl methylmalonate, diethyl 2-butoxybenzylidenemalonate, diethyl 3-butoxybenzylidenemalonate, diethyl 4-butoxybenzylidenemalonate, diethyl 2-isobutoxybenzylidenemalonate, diethyl 3-isobutoxybenzylidenemalonate, diethyl 4-isobutoxybenzylidenemalonate, dipropyl 2-methoxybenzylidenemalonate, dipropyl 3-methoxybenzylidenemalonate, dipropyl 4-methoxybenzylidenemalonate, dipropyl 2-ethoxybenzylidenemalonate, dipropyl 3-ethoxybenzylidenemalonate, dipropyl 4-ethoxybenzylidenemalonate, dipropyl 2-propoxybenzylidenemalonate, dipropyl 3-propoxybenzylidenemalonate, dipropyl 4-propoxybenzylidenemalonate propyl ester, 2-isopropoxybenzylidene malonate dipropyl ester, 3-isopropoxybenzylidene malonate dipropyl ester, 4-isopropoxybenzylidene malonate dipropyl ester, 2-butoxybenzylidene malonate dipropyl ester, 3-butoxybenzylidene malonate dipropyl ester, 4-butoxybenzylidene malonate dipropyl ester, 2-isobutoxybenzylidene malonate dipropyl ester, 3-isobutoxybenzylidene malonate dipropyl ester, 4-isobutoxybenzylidene malonate dipropyl ester, 2-methoxybenzylidene succinate dimethyl ester, 3-methoxybenzylidene succinate dimethyl ester, 4-methoxybenzylidene succinate dimethyl ester, 2-ethoxybenzylidene succinate dimethyl ester, 3-ethoxybenzylidene succinate dimethyl ester,2-propoxybenzylidene succinate dimethyl ester, 3-propoxybenzylidene succinate dimethyl ester, 4-propoxybenzylidene succinate dimethyl ester, 2-isopropoxybenzylidene succinate dimethyl ester, 3-isopropoxybenzylidene succinate dimethyl ester, 4-isopropoxybenzylidene succinate dimethyl ester, 2-butoxybenzylidene succinate dimethyl ester, 3-butoxybenzylidene succinate dimethyl ester, 4-butoxybenzylidene succinate dimethyl ester, 2-isobutoxybenzylidene succinate dimethyl ester, 3-isobutoxybenzylidene succinate dimethyl ester, 4-isobutoxybenzylidene succinate dimethyl ester, 2-methoxybenzylidene succinate diethyl ester, 3-methoxybenzylidene succinate diethyl ester, 4-methoxybenzylidene succinate diethyl ester, 2-ethoxybenzylidene succinate diethyl ester, 3-ethoxybenzylidene succinate diethyl ester, 4-ethoxybenzylidene succinate diethyl ester, 2-propoxybenzylidene succinate diethyl ester, 3-propoxybenzylidene succinate diethyl ester, 4-propoxybenzylidene succinate diethyl ester, 2-isopropoxybenzylidene succinate diethyl ester, 3-isopropoxybenzylidene succinate diethyl ester, 4-isopropoxybenzylidene succinate diethyl ester, 2-butoxybenzylidene succinate diethyl ester 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-meth ... At least one of dipropyl methylene succinate, dipropyl 3-propoxybenzylidene succinate, dipropyl 4-propoxybenzylidene succinate, dipropyl 2-isopropoxybenzylidene succinate, dipropyl 3-isopropoxybenzylidene succinate, dipropyl 4-isopropoxybenzylidene succinate, dipropyl 2-butoxybenzylidene succinate, dipropyl 3-butoxybenzylidene succinate, dipropyl 4-butoxybenzylidene succinate, dipropyl 2-isobutoxybenzylidene succinate, dipropyl 3-isobutoxybenzylidene succinate and dipropyl 4-isobutoxybenzylidene succinate.

[0028] In the present invention, the ester compound can be prepared by conventional synthesis methods, or purchased by the general chemical product procurement method.

[0029] According to the present invention, preferably, the hydrocarbyldihydrocarbyloxysilane is selected from at least one of the compounds represented by formula (II);

[0030]

[0031] In formula (II), R1, R2, R3, and R4 are the same or different and are independently selected from C 1～ C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 of a cycloalkyl group.

[0032] Preferably, the hydrocarbyl dihydrocarbyloxysilane is selected from at least one of methylcyclohexyl dimethoxysilane, diisopropyl dimethoxysilane, diisobutyl dimethoxysilane, dicyclohexyl dimethoxysilane, dicyclopentyl dimethoxysilane, methylcyclohexyl diethoxysilane, diisopropyl diethoxysilane, diisobutyl diethoxysilane, dicyclohexyl diethoxysilane, dicyclopentyl diethoxysilane, methylcyclohexyl dipropoxysilane, diisopropyl dipropoxysilane, diisobutyl dipropoxysilane, dicyclohexyl dipropoxysilane, dicyclopentyl dipropoxysilane, methylcyclohexyl dibutoxysilane, diisopropyl dibutoxysilane, diisobutyl dibutoxysilane, dicyclohexyl dibutoxysilane and dicyclopentyl dibutoxysilane.

[0033] More preferably, the hydrocarbyldihydrocarbyloxysilane is methylcyclohexyldimethoxysilane and / or dicyclopentyldimethoxysilane.

[0034] In the present invention, the hydrocarbyldihydrocarbyloxysilane can be prepared in a laboratory by a common synthesis method, or can be purchased on the market by a general chemical product procurement method.

[0035] According to the present invention, preferably, the amount of the ester compound is 0.001-1.0 mole, and the amount of the hydrocarbyldihydrocarbyloxysilane is 0.001-1.0 mole, calculated per mole of aluminum in the alkyl aluminum compound; the two can be added after mixing, or can be added separately; and the molar ratio of the ester compound to the hydrocarbyldihydrocarbyloxysilane is 1:100 to 100:1, preferably 1:50-50:1.

[0036] During the polymerization process, the external electron donor compound can be pre-contacted with the solid catalyst component for a period of time before being added, or can be mixed with the solid catalyst component for a short time before being added, or can be added at different stages of the polymerization.

[0037] The solid catalyst component of the present invention can be prepared according to conventional methods in the prior art. The solid catalyst component can be prepared by the following method:

[0038] Method 1: In an inert diluent, a magnesium compound and an organic epoxy compound are contacted to form a uniform solution, and then in the presence of a precipitation aid, the uniform solution is contacted with a titanium compound and an internal electron donor compound to react to obtain a solid catalyst component.

[0039] Method 2: contacting and reacting a titanium compound and a magnesium compound with an internal electron donor compound to obtain a solid catalyst component;

[0040] Preferably, the steps include:

[0041] 1) mixing a titanium compound with a spherical magnesium halide alcoholate carrier at a temperature of -30°C to 0°C to obtain a carrier suspension;

[0042] 2) heating the carrier suspension to 80-130° C., adding an internal electron donor compound during the heating process, and reacting at a constant temperature for 0.2-2 hours to obtain a solid precipitate;

[0043] 3) washing and drying the solid precipitate to obtain the solid catalyst component.

[0044] Optionally, in step 3), the solid precipitate is treated with a titanium compound before washing. The treatment may be performed once or multiple times. The inert solvent used for washing may be selected from one or more of hexane, heptane, octane, decane and toluene.

[0045] In addition, in step 1), the mixing is optionally performed in the presence of an inert solvent.

[0046] According to the present invention, preferably, the polyol ester compound is a glycol ester compound. When the internal electron donor compound is a glycol ester compound, in a preferred case, non-limiting examples of the internal electron donor compound include: 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 9,9-bis(benzylcarboxymethyl)fluorene, etc.

[0047] According to the present invention, preferably, in the solid catalyst component, the content of the internal electron donor compound is 0.01-5 moles per mole of magnesium.

[0048] According to the present invention, preferably, the internal electron donor compound further comprises a carboxylate compound and / or an ether compound.

[0049] According to the present invention, preferably, the carboxylate compound is a monovalent or polyvalent aliphatic carboxylate and / or an aromatic carboxylate compound.

[0050] Preferably, the carboxylate compound is selected from at least one of benzoate, phthalate, malonate, succinate and glutarate.

[0051] More preferably, the carboxylate compound is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, 2,2-dimethylsuccinate, dimethyl 2,3-diisopropylsuccinate, dimethyl 2,2-dimethylsuccinate, diethyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, diethyl ...butyl 2,2-dimethylsuccinate, diethyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-dimethylsuccinate, dibutyl 2,2-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-dimethylsuccinate, dibutyl 2,2-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,3-diisopropylsuccinate, dibutyl 2,2-di At least one of diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate.

[0052] More preferably, the carboxylate compound is dibutyl phthalate or diisobutyl phthalate.

[0053] According to the present invention, preferably, the ether compound is a diether compound, preferably selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxy Propane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexyl)-1,3-dimethoxypropane 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxypropane The present invention is preferably selected from the group consisting of 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene; more preferably 2-isopropyl-2-isopentyl-1,3-dimethoxypropane.

[0054] Preferably, the molar ratio of the polyol ester compound to the carboxylic acid ester compound and / or the ether compound is 1:10-10:1.

[0055] In the preparation process of the solid catalyst component of the present invention, if two or more internal electron donors are contained, the internal electron donor compounds used can be used together in a variety of ways, can be used in different steps and under different conditions, can also be added simultaneously, and the internal electron donor compounds used are added in no particular order.

[0056] The specific operation of method 1 can be carried out according to the preparation method of the solid catalyst disclosed in patent documents CN102464746A and CN1258684A, and all the relevant contents disclosed therein are incorporated into the present invention as a reference.

[0057] Specifically, the magnesium compound is selected from magnesium halides, preferably magnesium chloride.

[0058] Preferably, the organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes having 2 to 8 carbon atoms, preferably selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran.

[0059] Preferably, the precipitation aid is selected from at least one of organic anhydrides, organic acids, ethers and ketones, preferably selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether.

[0060] Preferably, the amount of the organic epoxy compound used is 0.2-10 moles, and the amount of the precipitation aid used is 0.03-1 mole per mole of magnesium element.

[0061] In method 2, the spherical magnesium halide alcoholate carrier can be obtained by referring to the preparation methods of CN1091748A, CN1330086A, CN101050245A, US6020279A, CN1580136A and CN1463990A, and all the relevant contents disclosed therein are incorporated herein by reference.

[0062] Specifically, the preparation method of the spherical magnesium halide alcoholate carrier may include: mixing magnesium halide and low-carbon alcohol, heating reaction to generate magnesium halide alcoholate melt, the reaction temperature is 90-140°C, and placing in a cooling inert medium after high shearing in a dispersion medium to form spherical magnesium halide alcoholate particles, and washing and drying to obtain a spherical carrier. High shearing can be obtained by conventional methods, such as high-speed stirring method (e.g., CN00109216.2), spray method (e.g., US6020279A), high-gravity rotating bed (e.g., CN1580136A), and emulsifier method (e.g., CN1463990A). The dispersant system can use hydrocarbon inert solvents, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The cooling inert medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.

[0063] According to the present invention, preferably, the general formula of the titanium compound is Ti(OR w ) 4-k X' k , where R w C1-C 20 alkyl, X' is Cl, Br or I, k is an integer of 0-4; preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, triethoxytitanium monochloride, diethoxytitanium dichloride, triethoxytitanium trichloride and titanium trichloride, more preferably titanium tetrachloride.

[0064] Preferably, in the solid catalyst component, the content of the titanium compound is 0.5-150 moles per mole of magnesium.

[0065] According to the present invention, preferably, the general formula of the alkyl aluminum compound is AlR"' d X 1 3-d , where R'' is C l -C8 alkyl, X 1 is halogen, 0<d≤3, when containing two or three R'', each R''' is the same or different.

[0066] Preferably, the alkyl aluminum compound is triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, Al(n-C6H 13 )3. Al(n-C8H 17 )3 and at least one of AlEt2Cl.

[0067] Preferably, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is 1-1000:1, preferably 1-500:1.

[0068] In the present invention, the alkyl aluminum compound and the external electron donor compound may be contacted with the solid catalyst component alone or as a mixture of the two components.

[0069] According to different requirements on polymer properties, the catalyst of the present invention can be directly used in the polymerization reaction of olefins; or it can be prepolymerized with prepolymerized olefins to generate prepolymerized catalysts, and then polymerized with olefins.

[0070] The second aspect of the present invention provides an olefin polymerization method, which comprises: contacting one or more olefins with the catalyst for olefin polymerization under olefin polymerization reaction conditions.

[0071] In the present invention, the general formula of the olefin can be CH2=CH-R V , where R V It is hydrogen or C1~C6 alkyl.

[0072] Non-limiting examples of the olefin include: ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene. Preferably, the olefin is propylene and / or ethylene; more preferably, the olefin is propylene.

[0073] In addition, according to specific use requirements, the olefin can be polymerized in the presence of a small amount of diene.

[0074] In the present invention, the olefin polymerization reaction can be carried out in liquid phase (liquid phase monomer or monomer is dissolved in an inert solvent) or gas phase, or can be carried out under the operation of liquid phase and gas phase polymerization stage combination. Olefin polymerization reaction can be carried out according to known polymerization techniques, for example, adopt conventional technology such as slurry process, gas phase fluidized bed etc.

[0075] The olefin polymerization conditions include: a polymerization temperature of 0 to 150° C., preferably 60 to 90° C., and a polymerization pressure of normal pressure or higher.

[0076] The present invention will be further described below in conjunction with embodiments, but the scope of the present invention is not limited to these embodiments.

[0077] In the following examples and comparative examples,

[0078] 1) The isotactic index of a polymer is determined by the n-heptane extraction method. According to GB / T 2412-2008, 2 g of a dried polymer sample is placed in an extractor and extracted with boiling n-heptane for 6 hours. The residue is dried to a constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotactic index.

[0079] 2) Polymer melt index: measured according to GB3682-2000 at 230°C and 2.16 kg load.

[0080] Preparation Example 1

[0081] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0082] In a 300mL stirred glass reaction bottle fully replaced with high-purity nitrogen, add 90mL titanium tetrachloride and 10mL hexane, cool to -20°C, add 8g of spherical magnesium chloride alcoholate (prepared according to the method of Example 1 of CN1330086A, the molar ratio of ethanol to magnesium chloride in the carrier is 2.62). Then, under stirring, slowly heat up in stages, and when the temperature reaches 40°C, add 4.9mmol of 2,4-pentanediol dibenzoate and 4.5mmol of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. Continue to heat up to 110°C and keep the temperature constant for 0.5h to obtain a solid precipitate, filter out the liquid, add 100mL of titanium tetrachloride to the solid each time, treat at 110°C for 1 hour, repeat this treatment step 3 times; then wash with hexane 5 times, and finally vacuum dry to obtain a solid catalyst component A.

[0083] Preparation Example 2

[0084] This preparation example is used to illustrate the preparation of a solid catalyst component.

[0085] In a 300mL stirred glass reaction bottle fully replaced with high-purity nitrogen, add 100mL titanium tetrachloride, cool to -20°C, add 8g spherical magnesium chloride alcoholate (prepared according to the method of Example 1 of CN1330086A, the molar ratio of ethanol to magnesium chloride in the carrier is 2.62). Slowly heat to 110°C in stages, add 2.5mmol of 2,4-pentanediol dibenzoate prepared in Preparation Example 1 and 3.9mmol of dibutyl phthalate during the heating process, keep constant temperature at 110°C for 0.5h, obtain solid precipitate, filter out liquid, add 100mL titanium tetrachloride for treatment twice, then wash five times with hexane, and obtain solid catalyst component B after vacuum drying.

[0086] Preparation Example 3

[0087] This preparation example is used to illustrate the preparation of the solid catalyst component of the present invention.

[0088] In a reactor fully replaced with high-purity nitrogen, 4.8g of magnesium chloride, 95mL of toluene, 4mL of epichlorohydrin, and 12.5mL of tributyl phosphate (TBP) were added in sequence, and the temperature was raised to 50°C under stirring, and maintained for 2.5 hours to completely dissolve the solid, and 1.4g of phthalic anhydride was added and maintained for another hour. The solution was cooled to below -25°C, 56mL of TiCl4 was added dropwise within 1 hour, and the temperature was slowly raised to 80°C. Solids gradually precipitated during the heating process, 6mmol of 2,4-pentanediol dibenzoate was added, and the temperature was maintained for 1 hour. After filtering, 70mL of toluene was added, and the solid was washed twice to obtain a solid precipitate. Then 60mL of toluene and 40mL of TiCl4 were added to the solid, the temperature was raised to 100°C, and the solution was treated for 2 hours. After the filtrate was removed, the treatment steps were repeated again. 60mL of toluene was added, and the solution was washed three times in a boiling state, and then 60mL of hexane was added. After washing twice in a boiling state, a solid catalyst component C was obtained.

[0089] Examples 1 to 30 are used to illustrate the catalyst and olefin polymerization method of the present invention.

[0090] Examples 1 to 8

[0091] In a 5-liter autoclave, nitrogen gas was used to purge at 70°C for 1 hour, and then the polymerization autoclave was replaced with gaseous propylene for 3 times. Under nitrogen protection, 5 mL of triethylaluminum (TEAL) hexane solution (the concentration of triethylaluminum was 0.5 mmol / mL), a hexane solution of a composite external electron donor (the concentration of the external electron donor was 0.1 mmol / mL), 10 mL of anhydrous hexane and 4 to 12 mg of solid catalyst component A were introduced. The autoclave was closed, and a set amount of hydrogen and 1.0 to 1.2 kg of liquid propylene were introduced; the temperature in the autoclave was quickly raised to 70°C under stirring. After the polymerization reaction was carried out at 70°C for 1 hour (see the remarks for the polymerization time test), stirring was stopped, unpolymerized propylene monomer was removed, the polymer was collected, and vacuum dried at 70°C for 2 hours to obtain polypropylene. The added external electron donors are 4-methoxybenzylidenemalonic acid dimethyl ester (DMPMBM) and 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester (MPMPDE). The composition and ratio of the external electron donors, the amount of hydrogenation, and the polymerization performance of the catalyst are shown in Table 1.

[0092] Examples 9 to 22

[0093] Propylene polymerization was carried out according to the methods of Examples 1 to 8, except that catalyst B was used as the main catalyst during the polymerization. The composition and ratio of the external electron donor, the amount of hydrogenation, and the polymerization performance of the catalyst are shown in Table 1.

[0094] Embodiments 23 to 30

[0095] Propylene polymerization was carried out according to the methods of Examples 1 to 8, except that catalyst C was used as the main catalyst during the polymerization. The composition and ratio of the external electron donor, the amount of hydrogenation, and the polymerization performance of the catalyst are shown in Table 1.

[0096] Comparative Examples 1-2

[0097] The polymerization method is the same as that of Examples 1 to 8, except that during the polymerization, Catalyst A is used as the main catalyst, and the added external electron donor is changed to a hexane solution of methylcyclohexyldimethoxysilane (C-donor) (the concentration of C-donor is 0.1 mmol / mL), thereby preparing polypropylene. The amount of hydrogenation and the polymerization performance of the catalyst are shown in Table 1.

[0098] Comparative Examples 3 to 6

[0099] The polymerization method is the same as that of Examples 1 to 8, except that during the polymerization, Catalyst B is used as the main catalyst, and the added external electron donor is changed to a hexane solution of methylcyclohexyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor) (the concentration of C-donor is 0.1 mmol / mL), thereby preparing polypropylene. The amount of hydrogenation and the polymerization performance of the catalyst are shown in Table 1.

[0100] Comparative Examples 7 to 10

[0101] The polymerization method is the same as that of Examples 1 to 8, except that during the polymerization, Catalyst C is used as the main catalyst, and the added external electron donor is changed to a hexane solution of methylcyclohexyldimethoxysilane (C-donor) or dicyclopentyldimethoxysilane (D-donor) (the concentration of C-donor and D-donor is 0.1 mmol / mL), thereby preparing polypropylene. The amount of hydrogenation and the polymerization performance of the catalyst are shown in Table 1.

[0102] Table 1

[0103]

[0104]

[0105] in:

[0106] DMPMBM, dimethyl 4-methoxybenzylidenemalonate;

[0107] MPMPDE, 2-[(3-methoxyphenyl)methylene]-malonic acid 1,3-diethyl ester;

[0108] C-donor, cyclohexylmethyldimethoxysilane;

[0109] D-donor, dicyclopentyldimethoxysilane.

[0110] It can be seen from Table 1 that the composite external electron donor of the present invention combined with different main catalysts can obtain polymers with better performance. Specifically, the catalyst of the present invention has improved polymerization activity and hydrogen regulation sensitivity while maintaining high directional ability.

[0111] The embodiments of the present invention have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0112] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

Claims

1. A catalyst for olefin polymerization, characterized in that The catalyst comprises the reaction product of: 1) a solid catalyst component comprising titanium, magnesium, halogen and an internal electron donor compound; the internal electron donor compound comprises a polyol ester compound; 2) Alkyl aluminum compounds; 3) a composite external electron donor compound, wherein the composite external electron donor comprises an ester compound and a hydrocarbyldihydrocarbyloxysilane; The ester compound is selected from at least one of the compounds represented by formula (I); In formula (I), R 1 , R 2 Each independently selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl, C 10 -C 20 A fused aromatic group or a C2-C 20 The olefin group; R 3 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 Cycloalkyl; R 4 Selected from C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C7-C 20 Alkyl, C7-C 20 Aralkyl or C 10 -C 20 A fused ring aromatic group.

2. The catalyst for olefin polymerization according to claim 1, wherein The ester compound is selected from the group consisting of 2-methoxybenzylidene dimethyl malonate, 3-methoxybenzylidene dimethyl malonate, 4-methoxybenzylidene dimethyl malonate, 2-ethoxybenzylidene dimethyl malonate, 3-ethoxybenzylidene dimethyl malonate, 4-ethoxybenzylidene dimethyl malonate, 2-propoxybenzylidene dimethyl malonate, 3-propoxybenzylidene dimethyl malonate, 4-propoxybenzylidene dimethyl malonate, 2-isopropoxybenzylidene dimethyl malonate, 3-isopropoxybenzylidene dimethyl malonate, 4-isopropoxybenzylidene dimethyl malonate, 2-butoxybenzylidene dimethyl malonate, 3-butoxybenzylidene dimethyl malonate, 4-butoxybenzylidene dimethyl malonate dimethyl 2-isobutoxybenzylidene malonate, dimethyl 3-isobutoxybenzylidene malonate, dimethyl 4-isobutoxybenzylidene malonate, diethyl 2-methoxybenzylidene malonate, diethyl 3-methoxybenzylidene malonate, diethyl 4-methoxybenzylidene malonate, diethyl 2-ethoxybenzylidene malonate, diethyl 3-ethoxybenzylidene malonate, diethyl 4-ethoxybenzylidene malonate, diethyl 2-propoxybenzylidene malonate, diethyl 3-propoxybenzylidene malonate, diethyl 4-propoxybenzylidene malonate, diethyl 2-isopropoxybenzylidene malonate, diethyl 3-isopropoxybenzylidene malonate, diethyl 4-isopropoxybenzylidene malonate diethyl ester, diethyl 2-butoxybenzylidene malonate, diethyl 3-butoxybenzylidene malonate, diethyl 4-butoxybenzylidene malonate, diethyl 2-isobutoxybenzylidene malonate, diethyl 3-isobutoxybenzylidene malonate, diethyl 4-isobutoxybenzylidene malonate, dipropyl 2-methoxybenzylidene malonate, dipropyl 3-methoxybenzylidene malonate, dipropyl 4-methoxybenzylidene malonate, dipropyl 2-ethoxybenzylidene malonate, dipropyl 3-ethoxybenzylidene malonate, dipropyl 4-ethoxybenzylidene malonate, dipropyl 2-propoxybenzylidene malonate, dipropyl 3-propoxybenzylidene malonate, dipropyl 4-propoxybenzylidene malonate , 2-isopropoxybenzylidene dipropyl malonate, 3-isopropoxybenzylidene dipropyl malonate, 4-isopropoxybenzylidene dipropyl malonate, 2-butoxybenzylidene dipropyl malonate, 3-butoxybenzylidene dipropyl malonate, 4-butoxybenzylidene dipropyl malonate, 2-isobutoxybenzylidene dipropyl malonate, 3-isobutoxybenzylidene dipropyl malonate, 4-isobutoxybenzylidene dipropyl malonate, 2-methoxybenzylidene dimethyl succinate, 3-methoxybenzylidene dimethyl succinate, 4-methoxybenzylidene dimethyl succinate, 2-ethoxybenzylidene dimethyl succinate, 3-ethoxybenzylidene dimethyl succinate, 4-ethoxybenzylidene dimethyl succinate,2-propoxybenzylidene succinate dimethyl ester, 3-propoxybenzylidene succinate dimethyl ester, 4-propoxybenzylidene succinate dimethyl ester, 2-isopropoxybenzylidene succinate dimethyl ester, 3-isopropoxybenzylidene succinate dimethyl ester, 4-isopropoxybenzylidene succinate dimethyl ester, 2-butoxybenzylidene succinate dimethyl ester, 3-butoxybenzylidene succinate dimethyl ester, 4-butoxybenzylidene succinate dimethyl ester, 2-isobutoxybenzylidene succinate dimethyl ester, 3-isobutoxybenzylidene succinate dimethyl ester, 4-isobutoxybenzylidene succinate dimethyl ester, 2-methoxybenzylidene succinate diethyl ester, 3-methoxybenzylidene succinate diethyl ester, 4-methoxybenzylidene succinate diethyl ester, 2-ethoxybenzylidene succinate diethyl ester, 3-ethoxybenzylidene succinate diethyl ester, 4-ethoxybenzylidene succinate diethyl ester, 2-propoxybenzylidene succinate diethyl ester, 3-propoxybenzylidene succinate diethyl ester, 4-propoxybenzylidene succinate diethyl ester, 2-isopropoxybenzylidene succinate diethyl ester, 3-isopropoxybenzylidene succinate diethyl ester, 4-isopropoxybenzylidene succinate diethyl ester, 2-butoxybenzylidene succinate diethyl ester 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-methoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-ethoxybenzylidene)succinate, 2-(2-(2-meth ... At least one of dipropyl methylene succinate, dipropyl 3-propoxybenzylidene succinate, dipropyl 4-propoxybenzylidene succinate, dipropyl 2-isopropoxybenzylidene succinate, dipropyl 3-isopropoxybenzylidene succinate, dipropyl 4-isopropoxybenzylidene succinate, dipropyl 2-butoxybenzylidene succinate, dipropyl 3-butoxybenzylidene succinate, dipropyl 4-butoxybenzylidene succinate, dipropyl 2-isobutoxybenzylidene succinate, dipropyl 3-isobutoxybenzylidene succinate and dipropyl 4-isobutoxybenzylidene succinate.

3. The catalyst for olefin polymerization according to claim 1, wherein The hydrocarbyldihydrocarbyloxysilane is selected from at least one of the compounds represented by formula (II); In formula (II), R1, R2, R3, and R4 are the same or different and are independently selected from C 1～ C 20 Straight chain alkyl, C3-C 20 Branched alkyl or C3-C 20 of a cycloalkyl group; Preferably, the hydrocarbyldihydrocarbyloxysilane is selected from at least one of methylcyclohexyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, dicyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, methylcyclohexyldiethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldiethoxysilane, methylcyclohexyldipropoxysilane, diisopropyldipropoxysilane, diisobutyldipropoxysilane, dicyclohexyldipropoxysilane, dicyclopentyldipropoxysilane, methylcyclohexyldibutoxysilane, diisopropyldibutoxysilane, diisobutyldibutoxysilane, dicyclohexyldibutoxysilane and dicyclopentyldibutoxysilane; More preferably, the hydrocarbyldihydrocarbyloxysilane is methylcyclohexyldimethoxysilane and / or dicyclopentyldimethoxysilane.

4. The catalyst for olefin polymerization according to claim 1, wherein The amount of the ester compound is 0.001-1.0 mole per mole of aluminum in the alkyl aluminum compound, the amount of the hydrocarbyl dihydrocarbyloxy silane is 0.001-1.0 mole, and the molar ratio of the ester compound to the hydrocarbyl dihydrocarbyloxy silane is 1:100 to 100:1, preferably 1:50-50:

1.

5. The catalyst for olefin polymerization according to claim 1, wherein The solid catalyst component is prepared by the following method 1 or method 2: Method 1: In an inert diluent, a magnesium compound and an organic epoxy compound are contacted to form a uniform solution, and then in the presence of a precipitation aid, the uniform solution is contacted with a titanium compound and an internal electron donor compound to react to obtain a solid catalyst component; Method 2: contacting and reacting a titanium compound and a magnesium compound with an internal electron donor compound to obtain a solid catalyst component; Preferably, the steps include: 1) mixing a titanium compound with a spherical magnesium halide alcoholate carrier at a temperature of -30°C to 0°C to obtain a carrier suspension; 2) heating the carrier suspension to 80-130° C., adding an internal electron donor compound during the heating process, and reacting at a constant temperature for 0.2-2 hours to obtain a solid precipitate; 3) washing and drying the solid precipitate to obtain the solid catalyst component.

6. The catalyst for olefin polymerization according to claim 1 or 5, wherein The polyol ester compound is a diol ester compound, preferably at least one selected from 2-isopropyl-2-isopentyl-1,3-propanediol dibenzoate, 2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate and 9,9-bis(benzylcarboxymethyl)fluorene; In the solid catalyst component, the content of the internal electron donor compound is 0.01-5 moles per mole of magnesium.

7. The catalyst for olefin polymerization according to claim 6, wherein The internal electron donor compound further comprises a carboxylate compound and / or an ether compound; The carboxylate compound is a monobasic or polybasic aliphatic carboxylate and / or an aromatic carboxylate compound, preferably at least one of benzoate, phthalate, malonate, succinate and glutarate, more preferably ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, ... At least one of dimethyl succinate, diisobutyl 2,2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, tributyl trimellitate, triethyl trimellitate, tributyl trimellitate, tetraethyl pyromellitate and tetrabutyl pyromellitate, more preferably dibutyl phthalate and / or diisobutyl phthalate; The ether compound is a diether compound, preferably selected from 2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dimethoxypropane, Cyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)- 1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-phenyl-2-isopropyl-1,3-dimethoxy at least one of propane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane and 9,9-dimethoxymethylfluorene, more preferably 2-isopropyl-2-isopentyl-1,3-dimethoxypropane; Preferably, the molar ratio of the polyol ester compound to the carboxylic acid ester compound and / or the ether compound is 1:10-10:

1.

8. The catalyst for olefin polymerization according to claim 5, wherein In method 1, the magnesium compound is selected from magnesium halides, preferably magnesium chloride; The organic epoxy compound is selected from at least one of oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes having 2 to 8 carbon atoms, preferably at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran; The precipitation aid is selected from at least one of organic anhydrides, organic acids, ethers and ketones, preferably selected from at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and pentyl ether; The amount of the organic epoxy compound used is 0.2-10 moles, and the amount of the precipitation aid used is 0.03-1 mole per mole of magnesium element.

9. The catalyst for olefin polymerization according to claim 5, wherein In method 2, the structural formula of the magnesium halide alcoholate carrier is MgX2·p(ROH), wherein X is Cl, Br or I, preferably Cl; R is C1-C 18 Alkyl, preferably a C2-C4 straight chain alkyl; p is 0.1-6.

10. The catalyst for olefin polymerization according to claim 1, wherein The general formula of the titanium compound is Ti(OR w ) 4-k X' k , where R w C1-C 20 alkyl, X' is Cl, Br or I, k is an integer of 0-4; preferably, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium triethoxide, titanium trichloride, titanium diethoxide, titanium trichloride and titanium trichloride, more preferably titanium tetrachloride; In the solid catalyst component, the content of the titanium compound is 0.5-150 moles per mole of magnesium.

11. The catalyst for olefin polymerization according to claim 1, wherein The general formula of the alkyl aluminum compound is AlR"' d X 1 3-d , where R'' is C l -C8 alkyl, X 1 is a halogen, 0<d≤3, when containing two or three R"'s, each R"' is the same or different; Preferably, the alkyl aluminum compound is triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, Al(n-C6H 13 )3. Al(n-C8H 17 )3 and AlEt2Cl at least one; The molar ratio of aluminum in the alkyl aluminum compound to titanium in the solid catalyst component is 1-1000:1, preferably 1-500:

1.

12. An olefin polymerization method, characterized in that: The method comprises: under olefin polymerization reaction conditions, contacting one or more olefins with the catalyst for olefin polymerization described in any one of claims 1 to 11; the general formula of the olefins is CH2=CH-R V , where R V is hydrogen or C1-C6 alkyl; the olefin is preferably propylene and / or ethylene, more preferably propylene; The olefin polymerization reaction conditions include: a polymerization temperature of 0-150° C., preferably 60-90° C., and a polymerization pressure of normal pressure or higher.

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