Solid catalyst component for olefin polymerization, catalyst and application thereof

Abstract

The invention discloses a solid catalyst component for olefin polymerization, a catalyst and application thereof, the solid catalyst component comprises titanium, magnesium, halogen and an electron donor compound, the electron donor compound is selected from a compound of the following general formula (I): # imgabs0 #, wherein R1 is selected from hydrogen or C1-C18 alkyl; r2 is selected from alkyl groups of C1 to C18; r is selected from C1-C18 alkyl groups, C6-C30 aryl groups containing or not containing substituent groups, C7-C30 aralkyl groups containing or not containing substituent groups, and C5-C30 cycloalkyl groups containing or not containing substituent groups. The novel solid catalyst component and the catalyst and the prepolymerization catalyst prepared by using the solid catalyst component provided by the invention have excellent comprehensive performance, and have higher activity when being used for olefin polymerization, especially propylene polymerization, and the obtained polypropylene has high isotacticity and better application prospect.

Description

Technical Field

[0001] The present invention relates to a solid catalyst component for olefin polymerization, more specifically, the present invention relates to an olefin polymerization solid catalyst component containing an ether ester electron donor compound, the present invention also relates to a catalyst prepared from the solid catalyst component and the application of the catalyst in olefin polymerization. Background Art

[0002] As is well known, titanium-containing solid catalyst components with titanium, magnesium, halogen and electron donor as basic components can be used for the polymerization reaction of olefins (CH2=CHR), particularly in the polymerization of alpha-olefins with 3 or more carbon atoms, can obtain polymers with higher stereoregularity with higher yield, wherein the electron donor compound is one of the indispensable components in the catalyst component, and the discovery of new internal electron donor compounds has led to the continuous renewal of polyolefin catalysts. At present, a large number of multiple electron donor compounds have been disclosed, such as polycarboxylic acids, monocarboxylates or polycarboxylates, anhydrides, monoethers or polyethers, ketones, alcohols, amines and derivatives thereof, wherein aromatic dicarboxylates are more commonly used, such as di-n-butyl phthalate or diisobutyl phthalate, etc. The catalyst activity containing phthalic acid diester compounds is not high, and the molecular weight distribution of the obtained polymer is not wide either. During polymerization, it is necessary to use an external electron donor to achieve high catalytic activity and obtain a polymer with higher isotacticity.

[0003] In the 1990s, Himont Company disclosed a class of 1,3-diether electron donor compounds in Chinese patent CN1041752A. The use of catalysts containing 1,3-diether compounds can obtain highly isotactic polypropylene with high catalytic activity. However, the relative molecular weight distribution of the resulting polymer is relatively narrow, which is not conducive to the processing of the polymer. In addition, 1,3-diether compounds are prepared by O-alkylation of the corresponding 1,3-diols. The synthesis process of the intermediate compound 1,3-diol involved in the preparation process is relatively complicated and has a low yield. The O-alkylation reaction conditions are harsh and require the use of strong base potassium tert-butoxide or sodium hydride for dehydrogenation. At the same time, the O-alkylation agent methyl iodide used is a highly toxic chemical. Summary of the invention

[0004] The present invention provides a solid catalyst component containing a novel ether ester electron donor compound and a catalyst prepared therefrom, which have excellent comprehensive performance; the solid catalyst component and the catalyst are used for olefin polymerization, especially propylene polymerization, have high catalytic activity, good polymer stereoregularity, and have good application prospects.

[0005] The first aspect of the present invention is to provide a solid catalyst component comprising titanium, magnesium, halogen and an electron donor compound, wherein the electron donor compound is selected from at least one of the compounds of the following general formula (I):

[0006]

[0007] In formula (I), R 1 Selected from hydrogen or C1-C 18 Alkyl; R 2 Selected from C1-C 18 R is selected from C1-C 18 Alkyl, C6-C 30 aromatic, C7-C 30 Arylalkyl, C5-C 30 Cycloalkyl, i.e. R is selected from C1-C 18 Alkyl, C6-C 30 aromatic, C7-C 30 Arylalkyl, C5-C 30 A cycloalkyl group.

[0008] According to a preferred embodiment of the present invention, in the compound represented by the general formula (I), R 1 It is selected from hydrogen or C1-C6 alkyl, preferably hydrogen or C1-C4 alkyl, more preferably hydrogen or methyl or ethyl.

[0009] According to a preferred embodiment of the present invention, R 2 The alkyl group is selected from C1-C6, preferably C1-C4, and more preferably methyl or ethyl.

[0010] According to a preferred embodiment of the present invention, R is selected from C1-C6 alkyl, C6-C6 with or without substituents. 20 aromatic, C7-C 20 Arylalkyl, C5-C 20 Cycloalkyl, preferably C1-C4 alkyl, C6-C 10 aromatic, C7-C 10 Arylalkyl, C5-C 10 The cycloalkyl group is more preferably a C1-C3 alkyl group, a phenyl group which may be substituted, a naphthyl group which may be substituted, a benzyl group which may be substituted, a phenethyl group which may be substituted, or a cyclohexyl group which may be substituted.

[0011] In one embodiment of the above solid catalyst component, in the compound represented by the general formula (I), R 1 R is selected from hydrogen or C1-C6 alkyl, preferably hydrogen or C1-C4 alkyl, more preferably hydrogen or methyl or ethyl; 2 is selected from a C1-C6 alkyl group, preferably a C1-C4 alkyl group, more preferably a methyl group or an ethyl group; R is selected from a C1-C6 alkyl group, a C6-C4 alkyl group with or without a substituent group 20 aromatic, C7-C 20 Arylalkyl, C5-C 20 Cycloalkyl, preferably C1-C4 alkyl, C6-C 10 aromatic, C7-C 10 Arylalkyl, C5-C 10 The cycloalkyl group is more preferably a C1-C3 alkyl group, a phenyl group which may be substituted, a naphthyl group which may be substituted, a benzyl group which may be substituted, a phenethyl group which may be substituted, or a cyclohexyl group which may be substituted.

[0012] According to a preferred embodiment of the present invention, the substituent is selected from C1-C 18 Alkyl, C1-C 18 The alkoxy group or halogen group is preferably a C1-C6 alkyl group, a C1-C6 alkoxy group or a halogen group, more preferably a C1-C4 alkyl group, a C1-C4 alkoxy group, chlorine or bromine group, and most preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group or chlorine group.

[0013] In the above-mentioned solid catalyst component, specific examples of the compound represented by the general formula (I) include:

[0014] The electron donor compound is selected from at least one of the following compounds: 2-methoxyphenyl acetate, 2-methoxyphenyl propionate, 2-methoxyphenyl n-butyrate, 2-methoxyphenyl isobutyrate, 2-methoxyphenyl benzoate, 2-methoxyphenyl 2-ethoxybenzoate, 2-methoxyphenyl 2-methoxybenzoate, 2-methoxyphenyl 2-ethylbenzoate, 2-methoxyphenyl 2-methylbenzoate, 2-methoxyphenyl 2-chlorobenzoate, 2-methoxyphenyl 4-ethoxybenzoate, 2-methoxyphenyl 4-methoxybenzoate, 2-methoxyphenyl 4-ethylbenzoate, 2-methoxyphenyl 4-methylbenzoate, 2-methoxyphenyl 4-chlorobenzoate, 2-methoxyphenyl 2,4,6-trimethylbenzoate, 1 2-Methoxyphenyl 2-naphthoate, 2-methoxyphenyl 2-phenylacetate, 2-methoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(2-methoxyphenyl)acetate, 2-methoxyphenyl 2-(2-ethylphenyl)acetate, 2-methoxyphenyl 2-(2-methylphenyl)acetate, 2-methoxyphenyl 2-(2-chlorophenyl)acetate, 2-methoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(4-methoxyphenyl)acetate, 2-methoxyphenyl 2-(4-ethylphenyl)acetate, 2-methoxyphenyl 2-(4-methylphenyl)acetate, 2-methoxyphenyl 2-(4-chlorophenyl)acetate, 2-methoxyphenyl 3-phenylpropanoate, 3-(2-ethoxyphenyl)acetate 2-Methoxyphenyl 3-(2-methoxyphenyl)propionate, 2-methoxyphenyl 3-(2-ethylphenyl)propionate, 2-methoxyphenyl 3-(2-methylphenyl)propionate, 2-methoxyphenyl 3-(2-chlorophenyl)propionate, 2-methoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxyphenyl 3-(4-methoxyphenyl)propionate, 2-methoxyphenyl 3-(4-ethylphenyl)propionate, 2-methoxyphenyl 3-(4-methylphenyl)propionate, 2-methoxyphenyl 3-(4-chlorophenyl)propionate, 2-methoxyphenyl cyclohexanecarboxylate, 2-ethoxyphenyl acetate, 2-ethoxyphenyl propionate, 2-ethoxyphenyl butyrate, 2-ethoxyphenyl isobutyrate, benzoic acid 2-ethoxyphenyl 2-ethoxybenzoate, 2-ethoxyphenyl 2-methoxybenzoate, 2-ethoxyphenyl 2-ethylbenzoate, 2-ethoxyphenyl 2-methylbenzoate, 2-ethoxyphenyl 2-chlorobenzoate, 2-ethoxyphenyl 4-ethoxybenzoate, 2-ethoxyphenyl 4-methoxybenzoate, 2-ethoxyphenyl 4-ethylbenzoate, 2-ethoxyphenyl 4-methylbenzoate, 2-ethoxyphenyl 4-chlorobenzoate, 2-ethoxyphenyl 2,4,6-trimethylbenzoate, 2-ethoxyphenyl 1-naphthoic acid, 2-ethoxyphenyl 2-phenylacetate, 2-ethoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(2-methoxyphenyl)acetate,2-ethoxyphenyl 2-(2-ethylphenyl)acetate, 2-ethoxyphenyl 2-(2-methylphenyl)acetate, 2-ethoxyphenyl 2-(2-chlorophenyl)acetate, 2-ethoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-methoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-ethylphenyl)acetate, 2-ethoxyphenyl 2-(4-methylphenyl)acetate, 2-ethoxyphenyl 2-(4-chlorophenyl)acetate, 2-ethoxyphenyl 3-phenylpropanoate, 2-ethoxyphenyl 3-(2-ethoxyphenyl)propanoate, 2-ethoxyphenyl 3-(2-methoxyphenyl)propanoate, 2-ethoxyphenyl 3-(2-ethylphenyl)propanoate, 2-ethoxyphenyl 3-(2-methylphenyl)propanoate Ethoxyphenyl ester, 2-ethoxyphenyl 3-(2-chlorophenyl) propionate, 2-ethoxyphenyl 3-(4-ethoxyphenyl) propionate, 2-ethoxyphenyl 3-(4-methoxyphenyl) propionate, 2-ethoxyphenyl 3-(4-ethylphenyl) propionate, 2-ethoxyphenyl 3-(4-methylphenyl) propionate, 2-ethoxyphenyl 3-(4-chlorophenyl) propionate, 2-ethoxyphenyl cyclohexanecarboxylate, 2-methoxy-4-methylphenyl acetate, 2-methoxy-4-methylphenyl propionate, 2-methoxy-4-methylphenyl butyrate, 2-methoxy-4-methylphenyl isobutyrate, 2-methoxy-4-methylphenyl benzoate, 2-methoxy-4-methylphenyl 2-ethoxybenzoate, 2-methoxy-4-methylphenyl 2-methoxybenzoate 2-methoxy-4-methylphenyl 2-ethylbenzoate, 2-methoxy-4-methylphenyl 2-methylbenzoate, 2-methoxy-4-methylphenyl 2-chlorobenzoate, 2-methoxy-4-methylphenyl 4-ethoxybenzoate, 2-methoxy-4-methylphenyl 4-methoxybenzoate, 2-methoxy-4-methylphenyl 4-ethylbenzoate, 2-methoxy-4-methylphenyl 4-methylbenzoate, 2-methoxy-4-methylphenyl 4-chlorobenzoate, 2-methoxy-4-methylphenyl 2,4,6-trimethylbenzoate, 2-methoxy-4-methylphenyl 1-naphthoic acid, 2-methoxy-4-methylphenyl 2-phenylacetate, 2-methoxy-4-methylphenyl 2-(2-ethoxyphenyl)acetate 2-methoxy-4-methylphenyl 2-(2-methoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-ethylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-methylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-chlorophenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-ethoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-methoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-ethylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-methylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-chlorophenyl)acetate, 2-methoxy-4-methylphenyl 3-phenylpropanoate,2-Methoxy-4-methylphenyl 3-(2-ethoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-methoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-ethylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-methylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-chlorophenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-methoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-ethylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-methylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl ester, cyclohexanecarboxylic acid 2-methoxy-4-methylphenyl ester, acetic acid 2-ethoxy-4-methylphenyl ester, propionic acid 2-ethoxy-4-methylphenyl ester, butyric acid 2-ethoxy-4-methylphenyl ester, isobutyric acid 2-ethoxy-4-methylphenyl benzoate, 2-ethoxy-4-methylphenyl 2-ethoxybenzoate, 2-methoxy-4-methylphenyl ester, 2-ethoxy-4-methylphenyl 2-ethylbenzoate, 2-ethoxy-4-methylphenyl 2-methylbenzoate, 2-ethoxy-4-methylphenyl 2-chlorobenzoate, 4-ethoxy-4-methylphenyl 2-ethoxybenzoate, 4-methoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 2-Ethoxy-4-methylphenyl ethylbenzoate, 2-Ethoxy-4-methylphenyl 4-methylbenzoate, 2-Ethoxy-4-methylphenyl 4-chlorobenzoate, 2-Ethoxy-4-methylphenyl 2,4,6-trimethylbenzoate, 2-Ethoxy-4-methylphenyl 1-naphthoic acid, 2-Ethoxy-4-methylphenyl 2-phenylacetate, 2-Ethoxy-4-methylphenyl 2-(2-ethoxyphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-methoxyphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-ethylphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-methylphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-chlorophenyl)acetate, 2 2-ethoxy-4-methylphenyl-(4-ethoxyphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-methoxyphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-ethylphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-methylphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-chlorophenyl)acetate, 2-ethoxy-4-methylphenyl-3-phenylpropionate, 2-ethoxy-4-methylphenyl-3-(2-ethoxyphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-methoxyphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-ethylphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-methylphenyl)propionate,2-ethoxy-4-methylphenyl 3-(2-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-ethoxyphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-methoxyphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-ethylphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-methylphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl cyclohexanecarboxylate, 2-methoxy-4-ethylphenyl acetate, 2-methoxy-4-ethylphenyl propionate, 2-methoxy-4-ethylphenyl butyrate, 2-methoxy-4-ethylphenyl isobutyrate, 2-methoxy-4-ethylphenyl benzoate, 2-Methoxy-4-ethylphenyl 2-ethoxybenzoate, 2-methoxy-4-ethylphenyl 2-methoxybenzoate, 2-methoxy-4-ethylphenyl 2-ethylbenzoate, 2-methoxy-4-ethylphenyl 2-methylbenzoate, 2-methoxy-4-ethylphenyl 2-chlorobenzoate, 2-methoxy-4-ethylphenyl 4-ethoxybenzoate, 2-methoxy-4-ethylphenyl 4-methoxybenzoate, 2-methoxy-4-ethylphenyl 4-ethylbenzoate, 2-methoxy-4-ethylphenyl 4-methylbenzoate, 2-methoxy-4-ethylphenyl 4-chlorobenzoate, 2-methoxy-4-ethylphenyl 2,4,6-trimethylbenzoate, 2-methoxy-4-ethylphenyl 1-naphthoate, 2 2-methoxy-4-ethylphenyl-2-phenylacetate, 2-methoxy-4-ethylphenyl-2-(2-ethoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-methoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-ethylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-methylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-chlorophenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-ethoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-methoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-ethylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-methylphenyl)acetate, 2-methoxy-4-ethylphenyl 2-(4-chlorophenyl)acetate, 2-methoxy-4-ethylphenyl 3-phenylpropionate, 2-methoxy-4-ethylphenyl 3-(2-ethoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-methoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-ethylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-methylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-chlorophenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-methoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-ethylphenyl)propionate,2-Methoxy-4-ethylphenyl 3-(4-methylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-chlorophenyl)propionate, 2-methoxy-4-ethylphenyl cyclohexanecarboxylate, 2-ethoxy-4-ethylphenyl acetate, 2-ethoxy-4-ethylphenyl propionate, 2-ethoxy-4-ethylphenyl butyrate, 2-ethoxy-4-ethylphenyl isobutyrate, 2-ethoxy-4-ethylphenyl benzoate, 2-ethoxy-4-ethylphenyl 2-ethoxybenzoate, 2-ethoxy-4-ethylphenyl 2-methoxybenzoate, 2-ethoxy-4-ethylphenyl 2-ethylbenzoate, 2-ethoxy-4-ethylphenyl 2-methylbenzoate, 2-ethoxy-2-chlorobenzoate 4-ethylphenyl ester, 2-ethoxy-4-ethylphenyl 4-ethoxybenzoate, 2-ethoxy-4-ethylphenyl 4-methoxybenzoate, 2-ethoxy-4-ethylphenyl 4-ethylbenzoate, 2-ethoxy-4-ethylphenyl 4-methylbenzoate, 2-ethoxy-4-ethylphenyl 4-chlorobenzoate, 2-ethoxy-4-ethylphenyl 2,4,6-trimethylbenzoate, 2-ethoxy-4-ethylphenyl 1-naphthoic acid, 2-ethoxy-4-ethylphenyl 2-phenylacetate, 2-ethoxy-4-ethylphenyl 2-(2-ethoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-methoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-ethylphenyl)acetate 2-ethoxy-4-ethylphenyl 2-(2-methylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-chlorophenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-ethoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-methoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-ethylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-methylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-chlorophenyl)acetate, 2-ethoxy-4-ethylphenyl 3-phenylpropanoate, 2-ethoxy-4-ethylphenyl 3-(2-ethoxyphenyl)propanoate, 3-(2-methylphenyl)acetate 2-ethoxy-4-ethylphenyl 3-(2-ethylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(2-methylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(2-chlorophenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-ethoxyphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-methoxyphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-ethylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-methylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-chlorophenyl) propionate, 2-ethoxy-4-ethylphenyl cyclohexanecarboxylate. ,

[0015] In the present invention, the preparation method of the ether ester compound comprises:

[0016] The para-substituted or unsubstituted o-alkoxyphenol represented by formula N and the acyl halide represented by formula S are subjected to an esterification reaction in a solvent under the action of an acid binding agent to obtain an ether ester compound represented by formula M;

[0017] In formula S, X is a halogen.

[0018] As an example, the ether ester compound according to the present invention can be obtained by the following preparation method:

[0019] The para-substituted or unsubstituted o-alkoxyphenol (Formula N) and the acyl chloride (Formula S) are subjected to an esterification reaction in a solvent (such as THF) under the action of an acid binding agent (such as Et3N) to obtain an ether ester compound as shown in Formula M:

[0020]

[0021] According to the present invention, X is halogen, preferably, X is Cl.

[0022] In the present invention, the acid binding agent includes but is not limited to triethylamine.

[0023] According to the present invention, the molar ratio of the acid binding agent to the o-alkoxyphenol can be selected within a wide range. In a preferred embodiment of the present invention, the molar ratio of the acid binding agent to the o-alkoxyphenol is (1.3-1.7):1.

[0024] According to the present invention, the solvent includes but is not limited to tetrahydrofuran.

[0025] According to the present invention, the amount of the solvent can be selected within a wide range. In a preferred embodiment of the present invention, the amount of the solvent is 1-5 ml relative to 1 mmol of o-alkoxyphenol.

[0026] According to the present invention, the molar ratio of the o-alkoxyphenol to the acyl halide can be selected within a wide range. In a preferred embodiment of the present invention, the molar ratio of the o-alkoxyphenol to the acyl halide is 1:(0.8-1.2).

[0027] In a preferred embodiment of the present invention, the conditions of the esterification reaction include: reacting at a temperature of 15-80° C. (preferably the reflux temperature of the solvent) for 7-24 hours under a protective atmosphere; preferably, the preparation method includes:

[0028] Under a protective atmosphere (such as nitrogen and / or inert gas), the o-alkoxyphenol, the acid binding agent and the solvent are mixed, the solution containing the acyl halide is added dropwise at 10-20° C., and then refluxed at the reflux temperature of the solvent for 7-24 hours.

[0029] According to a preferred embodiment of the present invention, based on the total weight of the solid catalyst component as 100wt%, the content of the compound represented by the general formula (I) is 3-25wt%, for example 3wt%, 5wt%, 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, and any two values ​​or any interval between any two values; the content of titanium is 1-8wt%, for example 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, and any two values ​​or any interval between any two values; the content of magnesium is 8-30wt%, for example 8wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, and any two values ​​or any interval between any two values.

[0030] More preferably, based on 100 wt% of the total weight of the solid catalyst component, the content of the compound represented by general formula (I) is 5-25 wt%, the content of titanium is 1-6 wt%, and the content of magnesium is 10-25 wt%.

[0031] According to the present invention, preferably, the solid catalyst component comprises a reaction product of a titanium compound, a magnesium compound and a compound selected from the group consisting of compounds represented by general formula (I).

[0032] Preferably, the magnesium compound is selected from magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate of magnesium dihalide and a derivative of magnesium dihalide in which one halogen atom is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group, preferably magnesium dihalide or an alcoholate of magnesium dihalide. Specific examples are magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.

[0033] Preferably, the titanium compound is of the general formula TiX m (OR1) 4-m , wherein R1 is C1~C 20 wherein X is a halogen, 1≤m≤4, and m is preferably an integer. For example: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium triethoxide monochloride, titanium diethoxide dichloride, titanium trichloride monoethoxide, preferably titanium tetrachloride.

[0034] The solid catalyst component of the present invention can be prepared, for example, by the following method: firstly, a magnesium compound is dissolved in a solvent system comprising an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, and then mixed with a titanium compound, and a solid is precipitated in the presence of a precipitation aid; the solid is treated with a compound selected from the general formula (I) so that it is supported on the solid, and if necessary, the solid is treated with titanium tetrahalide and an inert diluent.

[0035] The magnesium compound, titanium compound and compound represented by general formula (I) are as described above. The organic epoxy compound, organic phosphorus compound and precipitation aid are disclosed in Chinese patent CN85100997, and its relevant contents are cited here as reference. For example, the organic epoxy compound can be selected from the oxides, glycidyl ethers and internal ethers of aliphatic olefins, dienes or halogenated aliphatic olefins or dienes with carbon atoms of 2 to 8. Specific compounds include: ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene dioxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran. For example, the organic phosphorus compound may include hydrocarbon esters or halogenated hydrocarbon esters of orthophosphoric acid or phosphorous acid, such as: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenylmethyl phosphite. For example, the precipitation aid can be selected from organic anhydrides, organic acids, ethers, ketones and esters. Specifically include: 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, amyl ether, succinate, malonic acid, glutaric acid, 2,4-pentanediol ester, 3,5-heptanediol ester.

[0036] Preferably, the amount of the organic epoxy compound used in each component is 0.2 to 10 moles per mole of magnesium compound (i.e. relative to each mole of magnesium compound), the amount of the organic phosphorus compound used is 0.1 to 3 moles, the amount of the precipitation aid used is 0 to 1.0 mole, the amount of the titanium compound used is 0.5 to 150 moles, and the amount of the compound represented by the general formula (I) used is 0.01 to 1.0 mole.

[0037] The solid catalyst component in the present invention may also be prepared by other methods, specifically including the methods listed below.

[0038] Method 1: The catalyst component is prepared according to the method disclosed in patent CN1506384. First, a magnesium compound and an organic alcohol compound are mixed with an inert solvent in a molar ratio of 2 to 5, the temperature is raised to 120 to 150°C, and the reaction is carried out for 1 to 5 hours at a magnesium / anhydride molar ratio of 5 to 10. Then, the alcoholate cooled to room temperature is added to a titanium compound solution precooled to -15 to -40°C at a titanium / magnesium molar ratio of 20 to 50, the temperature is raised to 90 to 110°C, and a compound selected from the general formula (I) is added at a magnesium / internal electron donor molar ratio of 2 to 10, and the reaction is carried out at 100 to 130°C for 1 to 3 hours, and solid particles are separated by filtration. Then, the solid particles are added to the titanium compound solution at a titanium / magnesium molar ratio of 20 to 50, stirred and reacted at 100 to 130°C for 1.5 to 3 hours, and the solid particles are separated by filtration. Finally, the solid particles are washed with an inert solvent at 50 to 80°C, and the catalyst component is obtained after drying.

[0039] Method 2: The solid catalyst component is prepared by reacting the titanium compound described in the present invention, specifically TiCl4, with an adduct of the general formula MgCl2·pROH. In MgCl2·pROH, p is a number from 0.1 to 6, preferably from 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms. The adduct can be suitably made into a spherical shape by the following method: in the presence of an inert hydrocarbon that is not miscible with the adduct, alcohol (ROH) and MgCl2 are mixed, and the emulsion is rapidly quenched, so that the adduct solidifies in the form of spherical particles. The adduct thus obtained can be directly reacted with the titanium compound, or it can be subjected to a heat-controlled dealcoholation (80 to 130° C.) before reacting with the titanium compound to obtain an adduct in which the molar number of alcohol is generally less than 3, preferably between 0.1 and 2.7. The reaction with the titanium compound can be carried out by suspending the adduct (de-alcoholated or itself) in cold TiCl4 (generally 0°C) and heating the mixture to 80-130°C and keeping it at this temperature for 0.1-2 hours. The TiCl4 treatment can be carried out once or multiple times. During the treatment with TiCl4, the compound of the general formula (I) of the present invention can be added for treatment, and this treatment can also be repeated once or multiple times.

[0040] Method 3: Prepare the catalyst component according to the method disclosed in patent CN1091748. The magnesium chloride alcoholate melt is dispersed in a dispersant system of white oil and silicone oil by high-speed stirring to form an emulsion, which is then discharged into a coolant and rapidly cooled and shaped to form magnesium chloride alcoholate microspheres. The coolant is an inert hydrocarbon solvent with a low boiling point, such as petroleum ether, pentane, hexane, heptane, etc. The obtained magnesium chloride alcoholate microspheres are washed and dried to form spherical carriers, and the molar ratio of alcohol to magnesium chloride is 2 to 3, preferably 2 to 2.5. The carrier particle size is 10 to 300 microns, preferably 30 to 150 microns.

[0041] The spherical carrier is treated with excess titanium tetrachloride at low temperature, and the temperature is gradually increased. During the treatment, the electron donor represented by the general formula (I) of the present invention is added, and after the treatment, it is washed with an inert solvent for multiple times, and dried to obtain a solid powdery spherical catalyst component. The molar ratio of titanium tetrachloride to magnesium chloride is 20 to 200, preferably 30 to 60; the initial treatment temperature is -30 to 0°C, preferably -25 to -20°C; and the final treatment temperature is 80 to 136°C, preferably 100 to 130°C.

[0042] Method 4: Dialkoxy magnesium can also be added to an aromatic hydrocarbon compound and stirred to form a suspension; the suspension is treated with tetravalent titanium chloride at -20 to 100°C and reacted at 0 to 130°C. During this process, an electron donor of the general formula (I) of the present invention is added at -20 to 130°C for reaction, and the obtained solid is washed with an aromatic hydrocarbon compound; then, it is treated with tetravalent titanium chloride in an aromatic hydrocarbon solvent at 0 to 130°C, and finally washed with an inert solvent and dried to obtain a solid catalyst component. Wherein, 0.5 to 100 mol of tetravalent titanium chloride is used for each mol of dialkyl magnesium, and 0.01 to 10 mol of electron donor is used.

[0043] Method 5: Halogenate a dihydrocarbyloxymagnesium compound such as dialkoxymagnesium or diaryloxymagnesium with TiCl4 or its aromatic hydrocarbon solution at 80-130°C. The treatment with TiCl4 or its aromatic hydrocarbon solution can be repeated one or more times, and the compound of the general formula (I) of the present invention is added in one or more such treatments.

[0044] Method 6: Prepare the catalyst component according to the method disclosed in patent US4540679. First, the magnesium alcohol and carbon dioxide react to obtain a hydrocarbyl magnesium carbonate carrier. Then the transition metal compound (preferably a tetravalent titanium compound) and the hydrocarbyl magnesium carbonate carrier react with the electron donor of the general formula (I) of the present invention in a certain ratio in an inert solvent, wherein the molar ratio of the transition metal element to the magnesium element is at least 0.5:1, and the amount of the electron donor of the general formula (I) of the present invention is at most 1.0 mole per gram of titanium atom. The inert solvent must be purified to remove substances such as water, oxygen, and carbon dioxide that are easy to poison the catalyst. The reaction is carried out at -10 to 170°C, and the reaction time is from a few minutes to a few hours.

[0045] Another method for preparing the solid catalyst component is to form an emulsion of a magnesium compound, an electron donor, etc. in a diluent, add a titanium compound to fix it to obtain a spherical solid, and then treat it to obtain a solid catalyst component.

[0046] In any of the above-mentioned preparation methods, the required electron donor compound (I) can be added in the form of a compound; it can also be added in other ways, such as by obtaining it in situ using a suitable precursor of the electron donor compound (I), which can be converted into the required electron donor compound through, for example, known chemical reactions such as esterification reactions.

[0047] A second aspect of the present invention is to provide a catalyst for olefin polymerization, which comprises the reaction product of the following components:

[0048] a) the solid catalyst component described in the first aspect;

[0049] b) Alkyl aluminum compounds, the general formula is AlR n X 3-n, where R is hydrogen or C1~C 20 A hydrocarbon group, X is a halogen, 1≤n≤3; preferably n is an integer.

[0050] In the above catalysts, specific examples of the alkylaluminum compound include triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrogenate, diisobutylaluminum monohydrogenate, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride, preferably triethylaluminum and triisobutylaluminum.

[0051] For applications requiring high stereoregularity of olefin polymers, it is necessary to add an external electron donor component c) to the catalyst. The external electron donor component c) is selected from the general formula R 2’ k Si(OR 3’ ) 4-k A compound of the formula, wherein 0≤k≤3, preferably k is an integer, R 3’ is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, R 2’ Selected from alkyl, cycloalkyl, aryl, halogenated alkyl, amino, substituted amino, halogen, hydrogen atom. For example: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane.

[0052] According to a preferred embodiment of the present invention, the molar ratio of component a) to component b) is 1:(5-5000), preferably 1:(20-500), calculated as titanium:aluminum; and / or,

[0053] The molar ratio of the component a) to the component c) is 1:(0-500), preferably 1:(3-100), calculated as titanium:silicon.

[0054] The third aspect of the present invention is to provide a prepolymerization catalyst for olefin polymerization, wherein the prepolymerization catalyst comprises a prepolymer obtained by prepolymerizing the catalyst described in the second aspect with an olefin, and the prepolymerization multiple is 0.1 to 1000 based on the mass ratio of the olefin polymer to the solid catalyst component. That is, the prepolymerization catalyst comprises a prepolymer obtained by prepolymerizing the above catalyst with an olefin, and the prepolymerization multiple is 0.1 to 1000g olefin polymer / g solid catalyst component.

[0055] In the present invention, "prepolymerized catalyst" refers to a catalyst that has been subjected to a polymerization step with a relatively low degree of conversion. According to the present invention, the prepolymerization can be carried out with the same alpha-olefin as the olefin used for the polymerization, wherein the olefin to be prepolymerized is preferably ethylene or propylene. Specifically, it is particularly preferred to carry out the prepolymerization with ethylene or a mixture thereof with up to 20 mol% of one or more alpha-olefins. Preferably, the degree of conversion of the prepolymerized catalyst component is about 0.2 to 500 g polymer / g solid catalyst component.

[0056] The prepolymerization process can be carried out at a temperature of -20 to 80°C, preferably 0 to 50°C, in liquid or gas phase. The prepolymerization step can be carried out online as part of a continuous polymerization process, or independently in a batch operation. In order to prepare a polymer in an amount of 0.5 to 20 g / g of catalyst component, batch prepolymerization of the catalyst of the present invention with ethylene is particularly preferred. The polymerization pressure is 0.01 to 10 MPa.

[0057] Preferably, the olefin used in the prepolymerization is ethylene or propylene.

[0058] The fourth aspect of the present invention is to provide a method for olefin polymerization, wherein the olefin is polymerized under the action of the catalyst described in the second aspect or the prepolymerized catalyst described in the third aspect.

[0059] The catalyst of the present invention can be directly added to the reactor for use in the polymerization process, or the catalyst can be prepolymerized with olefins to obtain a prepolymerized catalyst and then added to the reactor.

[0060] The olefin polymerization of the present invention is carried out according to known polymerization methods, and can be carried out in liquid phase or gas phase, or can also be carried out under the operation of a combination of liquid phase and gas phase polymerization stages. Conventional techniques such as slurry process, gas phase fluidized bed, etc. are adopted. Preferably, the following reaction conditions are adopted: polymerization temperature 0 to 150° C., preferably 60 to 90° C. In a specific embodiment, the polymerization is slurry polymerization.

[0061] The general formula of the olefins in the present invention is CH2=CHR, wherein R is hydrogen or C1~C 12 The alkyl or aryl group of the present invention is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. Preferably, the alkyl or propylene group is selected from ethylene or propylene. For example, the homopolymerization of propylene or the copolymerization of propylene and other olefins.

[0062] The process of the present invention is also applicable to the homopolymerization of ethylene and the copolymerization of ethylene with α-olefins such as propylene, butene, pentene, hexene, octene and 4-methyl-1-pentene.

[0063] Through the above technical scheme, the present invention provides a new solid catalyst component and a catalyst and a prepolymerization catalyst prepared using the solid catalyst component by using an ether ester compound as an internal electron donor, which has excellent comprehensive performance, has high activity when used for olefin polymerization, especially propylene polymerization, and has high isotacticity of the obtained polymer, and has good application prospects. The preparation method of the ether ester compound used is simple, the reaction conditions are mild, the operation is simple and safe, and the raw materials are cheap and easy to obtain. DETAILED DESCRIPTION

[0064] The present invention is described in detail below in conjunction with specific embodiments. It is necessary to point out that the following embodiments are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made to the present invention by those skilled in the art based on the contents of the present invention still fall within the scope of protection of the present invention.

[0065] The present invention is further described below in conjunction with specific embodiments, but does not constitute any limitation to the present invention.

[0066] Test Method

[0067] Nuclear magnetic resonance measurement: measured using a Bruker DMX300 nuclear magnetic resonance instrument 1 H-NMR (300 MHz, solvent CDCl3, TMS as internal standard, measurement temperature 300 K).

[0068] Isotactic index of polymer: It is determined by heptane extraction method (extraction with boiling heptane for 6 hours): 2 grams of dry polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The residue is dried to constant weight. The ratio of the obtained polymer weight (g) to 2 is the isotactic index.

[0069] 1. Synthesis of compounds

[0070] Preparation Example 1 Compound (1)

[0071] The synthesized ether ester compound (1) has the following structure:

[0072]

[0073] Under nitrogen protection, add 20 mmol of 2-methoxyphenol, 30 mmol of triethylamine, and 20 ml of tetrahydrofuran (THF) to a 250 ml three-necked flask and stir to mix. Cool to 10°C with an ice bath, and add 20 mmol of acetyl chloride in 10 ml of THF solution at 10-20°C. After the addition is complete, remove the ice bath and naturally warm to room temperature. Heat to the reflux temperature of THF and reflux for 7-24 hours, and monitor the reaction by TLC. After the reaction is complete, cool to room temperature. Add 30 ml of water for washing, separate the liquids, extract the aqueous phase twice with 25 ml*2 ether, and combine the organic phases. Wash with 30 ml of 1N HCl, then wash with 50 ml of saturated NaHCO3 solution, and wash with 50 ml of water. Dry the organic phase with 10 g of anhydrous Na2SO4, concentrate in vacuo to remove the solvent, and purify by column chromatography to obtain the target ether ester compound (1).

[0074] use 1 The structure of the synthesized ether ester compound (1) was confirmed by H NMR.

[0075] 1 H NMR (300 MHz, CDCl3, TMS as internal standard, δ / ppm): 6.91-7.22 (m, 4H), 3.82 (s, 3H), 2.31 (s, 3H).

[0076] Preparation Example 2-11 Compounds (2) to (11)

[0077] According to the synthesis method similar to the above compound (1), different para-substituted or unsubstituted o-alkoxyphenols (II) and different acyl chlorides (RCOCl) are selected as raw materials for esterification reaction to synthesize a series of ether ester compounds (2) to (11) having the general formula (I). 1 The structures of the synthesized compounds were confirmed by H NMR. Para-substituted or unsubstituted o-alkoxyphenol (II) and acyl chloride (RCOCl) and R in the product structure (I) 1 , R 2 and R are shown in Table 1.

[0078]

[0079] Table 1 Ether ester compounds

[0080]

[0081]

[0082] 2. Preparation and application of solid catalyst components

[0083] Example 1

[0084] In a reactor fully replaced with high-purity nitrogen, 4.8 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added in sequence, and the temperature was raised to 50°C under stirring and maintained for 2.5 hours. The solid was completely dissolved, and 1.4 g of phthalic anhydride was added and maintained for another hour. The solution was cooled to below -25°C, and 56 mL of TiCl4 was added dropwise within 1 hour. The temperature was slowly raised to 80°C. Solids were gradually precipitated during the heating process. 6 mmol of the above-prepared compound (1) was added as an internal electron donor, and the temperature was maintained for 1 hour. After filtering, the solid was washed twice with 70 mL of toluene to obtain a solid precipitate. Then 60 mL of toluene and 40 mL of TiCl4 were added, and the temperature was raised to 110°C and maintained for 2 hours. After the filtrate was discharged, the same operation was repeated once, and then 70 mL of toluene was used to wash three times at 110°C, each time for 10 minutes, and then 60 mL of hexane was added and washed twice to obtain a solid catalyst component (containing 3 wt% of Ti element).

[0085] After the dry 250mL three-necked flask was fully replaced with nitrogen and propylene, 100mL of heptane was added, and after heating to 70°C, 2.0mmol AlEt3 and 0.1mmol methylcyclohexyldimethoxysilane (CHMMS) were added under normal pressure to ensure that Al / Si=20 (mol). At this temperature, 10mg of the solid catalyst component prepared above was added, and the reaction was reacted for 2h, and the reaction was terminated with ethanol. The polymer was washed with anhydrous ethanol and vacuum dried to obtain a polymer. The test data is shown in Table 2.

[0086] Example 2

[0087] Same as Example 1, except that the internal electron donor added is compound (2). See Table 2 for data.

[0088] Example 3

[0089] Same as Example 1, except that the internal electron donor added is compound (3). The data are shown in Table 2.

[0090] Example 4

[0091] Same as Example 1, except that the internal electron donor added is compound (4). The data are shown in Table 2.

[0092] Example 5

[0093] Same as Example 1, except that the internal electron donor added is compound (5). The data are shown in Table 2.

[0094] Example 6

[0095] Same as Example 1, except that the internal electron donor added is compound (6). The data are shown in Table 2.

[0096] Example 7

[0097] Same as Example 1, except that the internal electron donor added is compound (7). The data are shown in Table 2.

[0098] Example 8

[0099] Same as Example 1, except that the internal electron donor added is compound (8). The data are shown in Table 2.

[0100] Example 9

[0101] Same as Example 1, except that the internal electron donor added is compound (9). The data are shown in Table 2.

[0102] Example 10

[0103] Same as Example 1, except that the internal electron donor added is compound (10). The data are shown in Table 2.

[0104] Embodiment 11

[0105] Same as Example 1, except that the internal electron donor added is compound (11). The data are shown in Table 2.

[0106] Table 2 Catalyst catalyzed propylene polymerization results

[0107]

[0108] It can be seen from Table 2 that the solid catalyst component and catalyst prepared by using the ether ester compound of the present invention as an electron donor have good activity and high polymer isotacticity when used for olefin polymerization.

[0109] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation to the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein, on the contrary, the present invention can be extended to all other methods and applications with the same functions.

[0110] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definition in this specification shall prevail.

[0111] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0112] The endpoints and any values ​​of the scope disclosed in the present application document are not limited to the precise scope or value, and these scopes or values ​​should be understood to include values ​​close to these scopes or values. For numerical ranges, between the endpoint values ​​of each scope, between the endpoint values ​​of each scope and a separate point value, and between separate point values, one or more new numerical ranges can be combined with each other, and these numerical ranges should be considered as specifically disclosed in this article. Hereinafter, in principle, each technical solution can be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in this article.

[0113] In the context of the present specification, any matters or items not mentioned are directly applicable to those known in the art without any changes except those explicitly stated.

[0114] Moreover, any embodiment described in this document may be freely combined with one or more other embodiments described in this document, and the technical solutions or technical ideas formed thereby are deemed to be part of the original disclosure or original record of the present invention, and should not be regarded as new content that has not been disclosed or anticipated in this document, unless a person skilled in the art considers that the combination is obviously unreasonable.

Claims

1. A solid catalyst component comprising titanium, magnesium, halogen and an electron donor compound, wherein the electron donor compound is selected from at least one of the compounds of the following general formula (I): In formula (I), R 1 Selected from hydrogen or C1-C 18 Alkyl; R 2 Selected from C1-C 18 An alkyl group; R is selected from C1-C 18 Alkyl, C6-C 30 aromatic, C7-C 30 Arylalkyl, C5-C 30 Cycloalkyl.

2. The solid catalyst component according to claim 1, characterized in that In the compound represented by the general formula (I), R 1 is selected from hydrogen or C1-C6 alkyl, preferably hydrogen or C1-C4 alkyl, more preferably hydrogen or methyl or ethyl; and / or, R 2 An alkyl group selected from C1-C6, preferably a C1-C4 alkyl group, more preferably a methyl group or an ethyl group; and / or, R is selected from C1-C6 alkyl, C6-C6 with or without substituents 20 aromatic, C7-C 20 Arylalkyl, C5-C 20 Cycloalkyl, preferably C1-C4 alkyl, C6-C 10 aromatic, C7-C 10 Arylalkyl, C5-C 10 The cycloalkyl group is more preferably a C1-C3 alkyl group, a phenyl group which may be substituted, a naphthyl group which may be substituted, a benzyl group which may be substituted, a phenethyl group which may be substituted, or a cyclohexyl group which may be substituted.

3. The solid catalyst component according to claim 1, characterized in that The substituent is selected from C1-C 18 Alkyl, C1-C 18 The alkoxy group or halogen group is preferably a C1-C6 alkyl group, a C1-C6 alkoxy group or a halogen group, more preferably a C1-C4 alkyl group, a C1-C4 alkoxy group, chlorine or bromine group, and most preferably a methyl group, an ethyl group, a methoxy group, an ethoxy group or chlorine group.

4. The solid catalyst component according to claim 1, characterized in that The electron donor compound is selected from at least one of the following compounds: 2-methoxyphenyl acetate, 2-methoxyphenyl propionate, 2-methoxyphenyl n-butyrate, 2-methoxyphenyl isobutyrate, 2-methoxyphenyl benzoate, 2-methoxyphenyl 2-ethoxybenzoate, 2-methoxyphenyl 2-methoxybenzoate, 2-methoxyphenyl 2-ethylbenzoate, 2-methoxyphenyl 2-methylbenzoate, 2-methoxyphenyl 2-chlorobenzoate, 2-methoxyphenyl 4-ethoxybenzoate, 2-methoxyphenyl 4-methoxybenzoate, 2-methoxyphenyl 4-ethylbenzoate, 2-methoxyphenyl 4-methylbenzoate, 2-methoxyphenyl 4-chlorobenzoate, 2-methoxyphenyl 2,4,6-trimethylbenzoate, 1 2-Methoxyphenyl 2-naphthoate, 2-methoxyphenyl 2-phenylacetate, 2-methoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(2-methoxyphenyl)acetate, 2-methoxyphenyl 2-(2-ethylphenyl)acetate, 2-methoxyphenyl 2-(2-methylphenyl)acetate, 2-methoxyphenyl 2-(2-chlorophenyl)acetate, 2-methoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-methoxyphenyl 2-(4-methoxyphenyl)acetate, 2-methoxyphenyl 2-(4-ethylphenyl)acetate, 2-methoxyphenyl 2-(4-methylphenyl)acetate, 2-methoxyphenyl 2-(4-chlorophenyl)acetate, 2-methoxyphenyl 3-phenylpropanoate, 3-(2-ethoxyphenyl)acetate 2-Methoxyphenyl 3-(2-methoxyphenyl)propionate, 2-methoxyphenyl 3-(2-ethylphenyl)propionate, 2-methoxyphenyl 3-(2-methylphenyl)propionate, 2-methoxyphenyl 3-(2-chlorophenyl)propionate, 2-methoxyphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxyphenyl 3-(4-methoxyphenyl)propionate, 2-methoxyphenyl 3-(4-ethylphenyl)propionate, 2-methoxyphenyl 3-(4-methylphenyl)propionate, 2-methoxyphenyl 3-(4-chlorophenyl)propionate, 2-methoxyphenyl cyclohexanecarboxylate, 2-ethoxyphenyl acetate, 2-ethoxyphenyl propionate, 2-ethoxyphenyl butyrate, 2-ethoxyphenyl isobutyrate, benzoic acid 2-ethoxyphenyl 2-ethoxybenzoate, 2-ethoxyphenyl 2-methoxybenzoate, 2-ethoxyphenyl 2-ethylbenzoate, 2-ethoxyphenyl 2-methylbenzoate, 2-ethoxyphenyl 2-chlorobenzoate, 2-ethoxyphenyl 4-ethoxybenzoate, 2-ethoxyphenyl 4-methoxybenzoate, 2-ethoxyphenyl 4-ethylbenzoate, 2-ethoxyphenyl 4-methylbenzoate, 2-ethoxyphenyl 4-chlorobenzoate, 2-ethoxyphenyl 2,4,6-trimethylbenzoate, 2-ethoxyphenyl 1-naphthoic acid, 2-ethoxyphenyl 2-phenylacetate, 2-ethoxyphenyl 2-(2-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(2-methoxyphenyl)acetate,2-ethoxyphenyl 2-(2-ethylphenyl)acetate, 2-ethoxyphenyl 2-(2-methylphenyl)acetate, 2-ethoxyphenyl 2-(2-chlorophenyl)acetate, 2-ethoxyphenyl 2-(4-ethoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-methoxyphenyl)acetate, 2-ethoxyphenyl 2-(4-ethylphenyl)acetate, 2-ethoxyphenyl 2-(4-methylphenyl)acetate, 2-ethoxyphenyl 2-(4-chlorophenyl)acetate, 2-ethoxyphenyl 3-phenylpropanoate, 2-ethoxyphenyl 3-(2-ethoxyphenyl)propanoate, 2-ethoxyphenyl 3-(2-methoxyphenyl)propanoate, 2-ethoxyphenyl 3-(2-ethylphenyl)propanoate, 2-ethoxyphenyl 3-(2-methylphenyl)propanoate Ethoxyphenyl ester, 2-ethoxyphenyl 3-(2-chlorophenyl) propionate, 2-ethoxyphenyl 3-(4-ethoxyphenyl) propionate, 2-ethoxyphenyl 3-(4-methoxyphenyl) propionate, 2-ethoxyphenyl 3-(4-ethylphenyl) propionate, 2-ethoxyphenyl 3-(4-methylphenyl) propionate, 2-ethoxyphenyl 3-(4-chlorophenyl) propionate, 2-ethoxyphenyl cyclohexanecarboxylate, 2-methoxy-4-methylphenyl acetate, 2-methoxy-4-methylphenyl propionate, 2-methoxy-4-methylphenyl butyrate, 2-methoxy-4-methylphenyl isobutyrate, 2-methoxy-4-methylphenyl benzoate, 2-methoxy-4-methylphenyl 2-ethoxybenzoate, 2-methoxy-4-methylphenyl 2-methoxybenzoate 2-methoxy-4-methylphenyl 2-ethylbenzoate, 2-methoxy-4-methylphenyl 2-methylbenzoate, 2-methoxy-4-methylphenyl 2-chlorobenzoate, 2-methoxy-4-methylphenyl 4-ethoxybenzoate, 2-methoxy-4-methylphenyl 4-methoxybenzoate, 2-methoxy-4-methylphenyl 4-ethylbenzoate, 2-methoxy-4-methylphenyl 4-methylbenzoate, 2-methoxy-4-methylphenyl 4-chlorobenzoate, 2-methoxy-4-methylphenyl 2,4,6-trimethylbenzoate, 2-methoxy-4-methylphenyl 1-naphthoic acid, 2-methoxy-4-methylphenyl 2-phenylacetate, 2-methoxy-4-methylphenyl 2-(2-ethoxyphenyl)acetate 2-methoxy-4-methylphenyl 2-(2-methoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-ethylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-methylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(2-chlorophenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-ethoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-methoxyphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-ethylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-methylphenyl)acetate, 2-methoxy-4-methylphenyl 2-(4-chlorophenyl)acetate, 2-methoxy-4-methylphenyl 3-phenylpropanoate,2-Methoxy-4-methylphenyl 3-(2-ethoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-methoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-ethylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-methylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(2-chlorophenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-methoxyphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-ethylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-methylphenyl)propionate, 2-methoxy-4-methylphenyl 3-(4-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl ester, cyclohexanecarboxylic acid 2-methoxy-4-methylphenyl ester, acetic acid 2-ethoxy-4-methylphenyl ester, propionic acid 2-ethoxy-4-methylphenyl ester, butyric acid 2-ethoxy-4-methylphenyl ester, isobutyric acid 2-ethoxy-4-methylphenyl benzoate, 2-ethoxy-4-methylphenyl 2-ethoxybenzoate, 2-methoxy-4-methylphenyl ester, 2-ethoxy-4-methylphenyl 2-ethylbenzoate, 2-ethoxy-4-methylphenyl 2-methylbenzoate, 2-ethoxy-4-methylphenyl 2-chlorobenzoate, 4-ethoxy-4-methylphenyl 2-ethoxybenzoate, 4-methoxybenzoic acid 2-ethoxy-4-methylphenyl ester, 2-Ethoxy-4-methylphenyl ethylbenzoate, 2-Ethoxy-4-methylphenyl 4-methylbenzoate, 2-Ethoxy-4-methylphenyl 4-chlorobenzoate, 2-Ethoxy-4-methylphenyl 2,4,6-trimethylbenzoate, 2-Ethoxy-4-methylphenyl 1-naphthoic acid, 2-Ethoxy-4-methylphenyl 2-phenylacetate, 2-Ethoxy-4-methylphenyl 2-(2-ethoxyphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-methoxyphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-ethylphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-methylphenyl)acetate, 2-Ethoxy-4-methylphenyl 2-(2-chlorophenyl)acetate, 2 2-ethoxy-4-methylphenyl-(4-ethoxyphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-methoxyphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-ethylphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-methylphenyl)acetate, 2-ethoxy-4-methylphenyl-2-(4-chlorophenyl)acetate, 2-ethoxy-4-methylphenyl-3-phenylpropionate, 2-ethoxy-4-methylphenyl-3-(2-ethoxyphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-methoxyphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-ethylphenyl)propionate, 2-ethoxy-4-methylphenyl-3-(2-methylphenyl)propionate,2-ethoxy-4-methylphenyl 3-(2-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-ethoxyphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-methoxyphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-ethylphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-methylphenyl)propionate, 2-ethoxy-4-methylphenyl 3-(4-chlorophenyl)propionate, 2-ethoxy-4-methylphenyl cyclohexanecarboxylate, 2-methoxy-4-ethylphenyl acetate, 2-methoxy-4-ethylphenyl propionate, 2-methoxy-4-ethylphenyl butyrate, 2-methoxy-4-ethylphenyl isobutyrate, 2-methoxy-4-ethylphenyl benzoate, 2-Methoxy-4-ethylphenyl 2-ethoxybenzoate, 2-methoxy-4-ethylphenyl 2-methoxybenzoate, 2-methoxy-4-ethylphenyl 2-ethylbenzoate, 2-methoxy-4-ethylphenyl 2-methylbenzoate, 2-methoxy-4-ethylphenyl 2-chlorobenzoate, 2-methoxy-4-ethylphenyl 4-ethoxybenzoate, 2-methoxy-4-ethylphenyl 4-methoxybenzoate, 2-methoxy-4-ethylphenyl 4-ethylbenzoate, 2-methoxy-4-ethylphenyl 4-methylbenzoate, 2-methoxy-4-ethylphenyl 4-chlorobenzoate, 2-methoxy-4-ethylphenyl 2,4,6-trimethylbenzoate, 2-methoxy-4-ethylphenyl 1-naphthoate, 2 2-methoxy-4-ethylphenyl-2-phenylacetate, 2-methoxy-4-ethylphenyl-2-(2-ethoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-methoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-ethylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-methylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(2-chlorophenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-ethoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-methoxyphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-ethylphenyl)acetate, 2-methoxy-4-ethylphenyl-2-(4-methylphenyl)acetate, 2-methoxy-4-ethylphenyl 2-(4-chlorophenyl)acetate, 2-methoxy-4-ethylphenyl 3-phenylpropionate, 2-methoxy-4-ethylphenyl 3-(2-ethoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-methoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-ethylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-methylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(2-chlorophenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-ethoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-methoxyphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-ethylphenyl)propionate,2-Methoxy-4-ethylphenyl 3-(4-methylphenyl)propionate, 2-methoxy-4-ethylphenyl 3-(4-chlorophenyl)propionate, 2-methoxy-4-ethylphenyl cyclohexanecarboxylate, 2-ethoxy-4-ethylphenyl acetate, 2-ethoxy-4-ethylphenyl propionate, 2-ethoxy-4-ethylphenyl butyrate, 2-ethoxy-4-ethylphenyl isobutyrate, 2-ethoxy-4-ethylphenyl benzoate, 2-ethoxy-4-ethylphenyl 2-ethoxybenzoate, 2-ethoxy-4-ethylphenyl 2-methoxybenzoate, 2-ethoxy-4-ethylphenyl 2-ethylbenzoate, 2-ethoxy-4-ethylphenyl 2-methylbenzoate, 2-ethoxy-2-chlorobenzoate 4-ethylphenyl ester, 2-ethoxy-4-ethylphenyl 4-ethoxybenzoate, 2-ethoxy-4-ethylphenyl 4-methoxybenzoate, 2-ethoxy-4-ethylphenyl 4-ethylbenzoate, 2-ethoxy-4-ethylphenyl 4-methylbenzoate, 2-ethoxy-4-ethylphenyl 4-chlorobenzoate, 2-ethoxy-4-ethylphenyl 2,4,6-trimethylbenzoate, 2-ethoxy-4-ethylphenyl 1-naphthoic acid, 2-ethoxy-4-ethylphenyl 2-phenylacetate, 2-ethoxy-4-ethylphenyl 2-(2-ethoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-methoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-ethylphenyl)acetate 2-ethoxy-4-ethylphenyl 2-(2-methylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(2-chlorophenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-ethoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-methoxyphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-ethylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-methylphenyl)acetate, 2-ethoxy-4-ethylphenyl 2-(4-chlorophenyl)acetate, 2-ethoxy-4-ethylphenyl 3-phenylpropanoate, 2-ethoxy-4-ethylphenyl 3-(2-ethoxyphenyl)propanoate, 3-(2-methylphenyl)acetate 2-ethoxy-4-ethylphenyl 3-(2-ethylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(2-methylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(2-chlorophenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-ethoxyphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-methoxyphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-ethylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-methylphenyl) propionate, 2-ethoxy-4-ethylphenyl 3-(4-chlorophenyl) propionate, 2-ethoxy-4-ethylphenyl cyclohexanecarboxylate. , 5. The solid catalyst component according to any one of claims 1 to 4, characterized in that Based on the total weight of the solid catalyst component as 100wt%, the content of the compound represented by the general formula (I) is 3-25wt%, the content of the titanium element is 1-8wt%, and the content of the magnesium element is 8-30wt%; preferably, Based on the total weight of the solid catalyst component being 100 wt%, the content of the compound represented by the general formula (I) is 5 to 25 wt%, the content of the titanium element is 1 to 6 wt%, and the content of the magnesium element is 10 to 25 wt%.

6. The solid catalyst component according to any one of claims 1 to 4, comprising a reaction product of a titanium compound, a magnesium compound and a compound selected from the group consisting of the compounds represented by general formula (I); preferably, The magnesium compound is selected from magnesium dihalide, alkoxy magnesium, alkyl magnesium, hydrate or alcoholate of magnesium dihalide and a derivative of magnesium dihalide in which one halogen atom in the molecular formula is replaced by a hydrocarbonoxy group or a halogenated hydrocarbonoxy group; and / or, The titanium compound is of the general formula TiX m (OR1) 4-m The compound, wherein R1 is C1~C 20 A hydrocarbon group, X is a halogen, 1≤m≤4.

7. A catalyst for olefin polymerization, comprising the reaction product of: a) the solid catalyst component according to any one of claims 1 to 6; b) Alkyl aluminum compounds, general formula: AlR n X 3-n , where R is hydrogen or C1~C 20 A hydrocarbon group, X is a halogen, and 1≤n≤3.

8. The catalyst according to claim 7, characterized in that The catalyst is added with an external electron donor component c), which is selected from the general formula R 2’ k Si(OR 3’ ) 4-k The compound, wherein 0≤k≤3, R 3’ is selected from alkyl, cycloalkyl, aryl, halogenated alkyl, R 2’ Selected from alkyl, cycloalkyl, aryl, halogenated alkyl, amino, substituted amino, halogen, and hydrogen atom.

9. The catalyst according to claim 7 or 8, characterized in that The molar ratio of the component a) to the component b) is 1:(5-5000), preferably 1:(20-500), calculated as titanium:aluminum; and / or, The molar ratio of the component a) to the component c) is 1:(0-500), preferably 1:(3-100), calculated as titanium:silicon.

10. A prepolymerization catalyst for olefin polymerization, the prepolymerization catalyst comprising a prepolymer obtained by prepolymerizing the catalyst according to any one of claims 7 to 9 with an olefin, wherein the prepolymerization multiple is 0.1 to 1000 based on the mass ratio of the olefin polymer to the solid catalyst component; Preferably, the olefin used in the prepolymerization is ethylene or propylene.

11. A method for olefin polymerization, wherein the olefin is polymerized under the action of the catalyst according to any one of claims 7 to 9 or the prepolymerized catalyst according to claim 10.

12. The method according to claim 11, characterized in that The general formula of the olefin is CH2=CHR, wherein R is hydrogen or C1~C 12 The alkyl or aryl group is preferably selected from ethylene or propylene.

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