Solid catalyst components for the polymerization of olefins, process for their preparation and catalysts containing them

Abstract

This invention discloses a solid catalyst component for olefin polymerization, its preparation method, and a catalyst containing the same component. The solid catalyst component for olefin polymerization includes a support, a titanium-containing compound, and an internal electron donor. The internal electron donor has the following structure: where R1, R2, R3, and R4 may be the same or different, and are selected from hydrogen atoms, C1 to C4 atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7~C 20 Aryl groups and C7-C 20 The alkoxyaryl group. The solid catalyst component for olefin polymerization of the present invention uses a bisphosphine compound containing a thiophene structure as an internal electron donor. The lone pair electrons of the phosphorus and sulfur atoms in the internal electron donor can stabilize the central metallic titanium, thereby giving the catalyst high activity during olefin polymerization.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of olefin polymerization catalysts, and particularly relates to a solid catalyst component for olefin polymerization, a preparation method thereof and a catalyst containing the same. BACKGROUND

[0002] The internal electron donor compound, as one of the important components of the Ziegler-Natta catalyst, plays a crucial role in improving the performance of the catalyst, which can not only improve the orientation ability of the catalyst, but also improve the activity of the catalyst.

[0003] Chinese patent CN101787088A provides a phosphorus-substituted sulfonyl compound as an internal electron donor, the general formula of the internal electron donor is (I),

[0004]

[0005] wherein, R 1 , R 2 are the same or different chain alkyl or aryl, and the hydrogen atoms on the substituents can be replaced by optional halogen atoms. The internal electron donor is used in a propylene polymerization catalyst, and the obtained catalyst has low activity.

[0006] CN105985469A discloses a polypropylene catalyst, and the internal electron donor compound is a double phosphine compound containing a biphenyl structure represented by general formula (I):

[0007]

[0008] In the formula, the substituents R1-R6 are the same or different, and are selected from C1-C20 straight chain alkyl or C3-C20 branched chain alkyl, C6-C20 aryl or C7-C20 alkoxy aryl. The internal electron donor is used in a polypropylene catalyst, and the obtained catalyst has low activity.

[0009] CN101560272A discloses an olefin polymerization catalyst containing A, B and C components: A is a solid catalyst component containing titanium, magnesium, chlorine elements and an internal electron donor, B is a cocatalyst, and C is an external electron donor. The heterocyclic aromatic acid of the internal electron donor 2,4-pentanediol ester in component A is furan carboxylic acid, 1-3 alkyl-substituted furan carboxylic acid, thiophene carboxylic acid or 1-3 alkyl-substituted thiophene carboxylic acid. The internal electron donor is used in a polypropylene catalyst, and the obtained catalyst has low activity.

[0010] Therefore, further research is needed on the internal electron donor for the olefin polymerization catalyst to improve the catalytic activity of the olefin polymerization catalyst. SUMMARY

[0011] The main objective of this invention is to provide a solid catalyst component for olefin polymerization, its preparation method, and a catalyst containing the component, so as to overcome the defects of low catalytic activity of existing catalysts for olefin polymerization, while also having considerable isotacticity and good molecular weight distribution.

[0012] To achieve the above objectives, the present invention provides a solid catalyst component for olefin polymerization, comprising a support, a titanium-containing compound, and an internal electron donor, wherein the internal electron donor has the following structure:

[0013]

[0014] Among them, R1, R2, R3, and R4 may be the same or different, and are selected from hydrogen atoms, C1 to C4 atoms. 20 Straight-chain or branched alkyl groups, C3-C4 20 cycloalkyl, C6-C 20 aryl, C7~C 20 Aryl groups and C7-C 20 alkoxyaryl.

[0015] The solid catalyst component for olefin polymerization of the present invention comprises, based on the total weight of the solid catalyst component for olefin polymerization, 1-20 wt% internal electron donor, 0.5-8 wt% titanium-containing compound (calculated as titanium), and 10-25 wt% support, wherein the support is magnesium halide, as known in the art, and more preferably an alcoholysis of magnesium halide. The catalyst disclosed in this invention also includes halogen atoms, the content of which is affected by the magnesium halide, titanium-containing compound, etc., and is generally 40-70 wt% halogen atoms.

[0016] The solid catalyst component for olefin polymerization of the present invention, wherein the magnesium halide in the alkoxide is selected from at least one of magnesium chloride, magnesium bromide, magnesium chloromethoxy, and magnesium chloroethoxy, and the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.

[0017] The solid catalyst component for olefin polymerization described in this invention, wherein the titanium-containing compound has the general formula Ti(OR'). n X (4-n) Where R' is C1 to C 20 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, X is a halogen, and n is an integer 0 ≤ n < 4.

[0018] The solid catalyst component for olefin polymerization of the present invention, wherein the internal electron donor is selected from at least one of the following compounds: 3,4-di(dimethylphosphino)-thiophene, 3,4-di(diethylphosphino)-thiophene, 3,4-di(di-n-propylphosphino)-thiophene, 3,4-di(diisopropylphosphino)-thiophene, 3,4-di(di-n-butylphosphino)-thiophene, 3,4-di(diisobutylphosphino)-thiophene, 3,4-di(di-n-pentylphosphino)-thiophene, 3,4-di(dicyclopentylphosphino)-thiophene, 3,4-di(di-n-hexylphosphino)-thiophene, 3,4-di(dicyclohexylphosphino)-thiophene, 3,4-di(diphenylphosphino)-thiophene, 3,4-di(di-p-tolylphosphino)-thiophene, 3,4- 3,4-Di(di-p-methoxyphenylphosphino)-thiophene, 3,4-Di(di-m-methoxyphenylphosphino)-thiophene, 3,4-Di(di-o-methoxyphenylphosphino)-thiophene, 3,4-Di(dimethylphosphino)-2-methylthiophene, 3,4-Di(diethylphosphino)-2-methylthiophene, 3,4-Di(di-n-propylphosphino)-2-methylthiophene, 3,4-Di(diisopropylphosphino)-2-methylthiophene, 3,4-Di(di-n-butylphosphino)-2-methylthiophene, 3,4-Di(diisobutylphosphino)-2-methylthiophene, 3,4-Di(di-n-pentylphosphino)-2-methylthiophene, 3,4-Di(dicyclopentylphosphino)-2-methylthiophene, 3,4-di(di-) (n-hexylphosphino)-2-methylthiophene, 3,4-di(dicyclohexylphosphino)-2-methylthiophene, 3,4-di(diphenylphosphino)-2-methylthiophene, 3,4-di(di-p-tolylphosphino)-2-methylthiophene, 3,4-di(di-m-tolylphosphino)-2-methylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(di-m-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(di-o-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(dimethylphosphino)-2-ethylthiophene, 3,4-di(diethylphosphino)-2-ethylthiophene, 3,4-di(di-n-propylphosphino)-2-ethylthiophene, 3,4-di(diisobutylphosphino)- 2-Ethiothiophene, 3,4-Di(dicyclopentylphosphino)-2-ethylthiophene, 3,4-Di(dicyclohexylphosphino)-2-ethylthiophene, 3,4-Di(diphenylphosphino)-2-ethylthiophene, 3,4-Di(di-p-tolylphosphino)-2-ethylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2-ethylthiophene, 3,4-Di(dimethylphosphino)-2-isopropylthiophene, 3,4-Di(diethylphosphino)-2-isopropylthiophene, 3,4-Di(di-n-propylphosphino)-2-isopropylthiophene, 3,4-Di(diisobutylphosphino)-2-isopropylthiophene, 3,4-Di(dicyclopentylphosphino)-2-isopropylthiophene, 3,4-di(2-methoxyphenylphosphino)-2-ethylthiophene, 3,4-di(2-methoxyphenylphosphino)-2- ethylthiophene, 3,4-di(2-methoxyphenylphosphino)-2-iso-propylthiophene, 3,4- di(2-methoxyphenylphosphino)-2-cyclopentylthiophene, 3,4-di(2-methoxyphenylphosphino)- 2-phenylthiophene, 3,4-di(2-methoxyphenylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4- di(2-methoxyphenylphosphino)-2,5-dimethylthiophene, 3,4-di(2-methoxyphenylphosphino)- 2,5-diethylthiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di-n-propylthiophene, 3,4- di(2-methoxyphenylphosphino)-2,5-diisobutylthiophene, 3,4-di(2-methoxyphenylphosphino)- 2,5-dicyclopentylthiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-diphenylthiophene, 3,4-di(2-methoxyphenylphosphino)- 2,5-di-p-tolylthiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di-p-methoxyphenylthiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di(2-methoxyphenyl)thiophene, 3,4- di(2-methoxyphenylphosphino)-2,5-di(3-methoxyphenyl)thiophene, 3,4-di(2- methoxyphenylphosphino)-2,5-di(4-methoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)- 2,5-di(2-ethoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di(3- ethoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di(4-ethoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di(2-n-propoxyphenyl)thiophene, 3,4- di(2-methoxyphenylphosphino)-2,5-di(3-n-propoxyphenyl)thiophene, 3,4-di(2- methoxyphenylphosphino)-2,5-di(4-n-propoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)- 2,5-di(2-n-butoxyphenyl)thiophene, 3,4-di(2-methoxyphenylphosphino)-2,5-di(3-4-di(isopropylphosphino)-2,5-diethylthiophene, 3,4-di(di-n-propylphosphino)-2,5-diethylthiophene, 3,4-di(diisobutylphosphino)-2,5-diethylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diethylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diethylthiophene, 3,4-di(diphenylphosphino)-2,5-diethylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diethylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diethylthiophene, 3,4-di(dimethylphosphino)-2,5-diisopropylthiophene, 3,4-di(diethylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-n-propylphosphino)-2,5-diisopropylthiophene, 3,4-di(diisobutylphosphino)-2,5-diisopropylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diisopropylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diisopropylthiophene, 3,4-di(diphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(dimethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-n-propylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diisobutylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diphenylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dimethylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(diethylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-n-propylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(diisobutylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(diphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dimethylphosphino)-2,5-diphenylthiophene, 3,4-di(diethylphosphino)-2,5-diphenylthiophene, 3,4-di(di-n-propylphosphino)-2,5-diphenylthiophene, 3,4-di(diisobutylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diphenylthiophene, 3,4-di(diphenylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diphenylthiophene,4-di(di-p-tolylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diphenylthiophene, 3,4-di(di-methylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-ethylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-n-propylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-isobutylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-cyclopentylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-cyclohexylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-phenylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-di-p-tolylthiophene.

[0019] To achieve the above object, the present application also provides a preparation method of the solid catalyst component for olefin polymerization as described above, wherein the preparation method of the internal electron donor comprises the following steps:

[0020] Step 1, reacting the compound of formula II with halogen element X2 to obtain the compound of formula III;

[0021] Step 2, reacting the compound of formula III with n-BuLi and PR1R2Cl to obtain the internal electron donor of formula I:

[0022]

[0023] wherein X is halogen, R1, R2, R3 and R4 are the same or different, selected from hydrogen atom, C1-C20 linear or branched alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 alkoxyaryl. 20 20 20 20 20

[0024] The preparation method of the solid catalyst component for olefin polymerization as described in the present application, wherein the reaction temperature of step 1 is 15-30℃ and the reaction temperature of step 2 is -78℃-room temperature.

[0025] The preparation method of the solid catalyst component for olefin polymerization as described in the present application, wherein it comprises the following steps:

[0026] Step a, mixing the carrier with the partial titanium-containing compound and reacting at -30 to -10℃;

[0027] Step b, adding the internal electron donor into the reaction mixture obtained in step a and reacting at 60-150℃;

[0028] ​​​​​Step c, mixing the remaining titanium-containing compound with the reaction mixture obtained in step b, and reacting at 60-150°C to obtain the solid catalyst component for olefin polymerization.

[0029] The method for preparing the solid catalyst component for olefin polymerization according to the present application, wherein the sum of the partial titanium-containing compound and the remaining titanium-containing compound is the total amount of the titanium-containing compound added in the preparation of the solid catalyst component for olefin polymerization.

[0030] To achieve the above-mentioned purpose, the present application further provides a catalyst for olefin polymerization, which comprises the above-mentioned solid catalyst component for olefin polymerization.

[0031] The present application has the following advantages:

[0032] The solid catalyst component for olefin polymerization according to the present application uses a diphosphine compound containing a thiophene structure as an internal electron donor. The lone pair electrons of the phosphorus atom and the sulfur atom in the internal electron donor can stabilize the central metal titanium, so that the catalyst has higher activity in the polymerization of olefins.

[0033] The phosphorus atom and the sulfur atom in the internal electron donor of the present application provide two different chemical environments, and at the same time, the spatial structure provided by the thiophene skeleton is combined. When the obtained catalyst is used for the polymerization of olefins, the prepared polymer has relatively high isotacticity and better molecular weight distribution under better activity. DETAILED DESCRIPTION

[0034] The following detailed description of the embodiments of the present application is based on the premise of the technical solutions of the present application, and detailed implementation methods and processes are given, but the protection scope of the present application is not limited to the following embodiments. The experimental methods not specified in the following embodiments are usually carried out under conventional conditions.

[0035] The present application provides a solid catalyst component for olefin polymerization, which comprises a carrier, a titanium-containing compound and an internal electron donor, and the internal electron donor has the following formula I structure:

[0036]

[0037] wherein R1, R2, R3 and R4 are the same or different, selected from hydrogen atom, C1-C 20 linear or branched alkyl group, C3-C 20 cycloalkyl group, C6-C 20 aryl group, C7-C 20 aralkyl group and C7-C 20 alkoxyaryl group. Further, R1, R2, R3 and R4 are preferably C1-C 10 linear or branched alkyl group, C3-C 10 cycloalkyl group, C6-C 10aryl, C7-C20aralkyl, or C7-C20aralkoxy. In one embodiment, R1and R2are the same, and in another embodiment, R3and R4are the same. 10 aryl, C7-C20aralkyl, or C7-C20aralkoxy. In one embodiment, R1and R2are the same, and in another embodiment, R3and R4are the same. 10 aryl, C7-C20aralkyl, or C7-C20aralkoxy. In one embodiment, R1and R2are the same, and in another embodiment, R3and R4are the same.

[0038] The solid catalyst component for olefin polymerization of the present application uses a bis-phosphine compound containing a thiophene structure as an internal electron donor. The lone pair electrons of the phosphorus atom and the sulfur atom in the internal electron donor can stabilize the central metal titanium, so that the catalyst has higher activity in the polymerization of olefins. In addition, the phosphorus atom and the sulfur atom of the internal electron donor provide two different chemical environments, while combining the spatial structure provided by the thiophene skeleton, so that the resulting catalyst used in the polymerization of olefins makes the prepared polymer have better isotacticity and a wider molecular weight distribution.

[0039] In one embodiment, in the electron donor of the present application, R1, R2, R3and R4are selected from methyl, ethyl, propyl, butyl, phenyl and the like, and further, the electron donor is selected from at least one compound of 3,4-bis(dimethylphosphino)-thiophene, 3,4-bis(diethylphosphino)-thiophene, 3,4-bis(di-n-propylphosphino)-thiophene, 3,4-bis(diisopropylphosphino)-thiophene, 3,4-bis(di-n-butylphosphino)-thiophene, 3,4-bis(diisobutylphosphino)-thiophene, 3,4-bis(di-n-pentylphosphino)-thiophene, 3,4-bis(dicyclopentylphosphino)-thiophene, 3,4-bis(di-n-hexylphosphino)-thiophene, 3,4-bis(dicyclohexylphosphino)-thiophene, 3,4-bis(diphenylphosphino)-thiophene, 3,4-bis(di-p-tolylphosphino)-thiophene, 3,4-bis(di-m-tolylphosphino)-thiophene, 3,4-bis(di-p-methoxyphenylphosphino)-thiophene, 3,4-bis(di-m-methoxyphenylphosphino)-thiophene, 3,4-bis(di-o-methoxyphenylphosphino)-thiophene, 3,4-bis(dimethylphosphino)-2-methylthiophene, 3,4-bis(diethylphosphino)-2-methylthiophene, 3,4-bis(di-n-propylphosphino)-2-methylthiophene, 3,4-bis(diisopropylphosphino)-2-methylthiophene, 3,4-bis(di-n-butylphosphino)-2-methylthiophene, 3,4-bis(diisobutylphosphino)-2-methylthiophene, 3,4-bis(di-n-pentylphosphino)-2-methylthiophene, 3,4-bis(dicyclopentylphosphino)-2-methylthiophene, 3,4-bis(di-n-hexylphosphino)-2-methylthiophene, 3,4-bis(dicyclohexylphosphino)-2-methylthiophene, 3,4-bis(diphenylphosphino)-2-methylthiophene, 3,4-bis(di-p-tolylphosphino)-2-methylthiophene, 3,4-bis(di-m-tolylphosphino)-2-methylthiophene, 3,4-bis(di-p-methoxyphenylphosphino)-2-methylthiophene, 3,4-bis(di-m-methoxyphenylphosphino)-2-methylthiophene, 3,4-bis(di-o-methoxyphenylphosphino)-2-methylthiophene, 3,4-bis(dimethylphosphino)-2-ethylthiophene, 3,4-bis(diethylphosphino)-2-ethylthiophene, 3,4-bis(di-n-propylphosphino)-2-ethylthiophene, 3,4-bis(diisobutylphosphino)-2-ethylthiophene, 3,4-bis(dicyclopentylphosphino)-2-ethylthiophene, 3,4-bis(dicyclohexylphosphino)-2-ethylthiophene, 3,4-bis(diphenylphosphino)-2-ethylthiophene, 3,4-bis(di-p-tolylphosphino)-2-ethylthiophene, 3,4-bis(di-p-methoxyphenylphosphino)-2-ethylthiophene, 3,4-bis(dimethylphosphino)-2-isopropylthiophene, 3,4-bis(diethylphosphino)-2-isopropylthiophene, 3,4-bis(di-n-propylphosphino)-2-isopropylthiophene, 3,4-bis(diisobutylphosphino)-2-isopropylthiophene, 3,4-bis(dicyclopentylphosphino)-2-isopropylthiophene, 3,4-di(cyclohexylphosphino)-2-isopropylthiophene, 3,4-di(diphenylphosphino)-2- isopropylthiophene, 3,4-di(di-p-tolylphosphino)-2-isopropylthiophene, 3,4-di(di-p- methoxyphenylphosphino)-2-isopropylthiophene, 3,4-di(dimethylphosphino)-2- cyclopentylthiophene, 3,4-di(diethylphosphino)-2-cyclopentylthiophene, 3,4-di(di-n- propylphosphino)-2-cyclopentylthiophene, 3,4-di(diisobutylphosphino)-2- cyclopentylthiophene, 3,4-di(dicyclopentylphosphino)-2-cyclopentylthiophene, 3,4- di(dicyclohexylphosphino)-2-cyclopentylthiophene, 3,4-di(diphenylphosphino)-2- cyclopentylthiophene, 3,4-di(di-p-tolylphosphino)-2-cyclopentylthiophene, 3,4-di- (di-p-methoxyphenylphosphino)-2-cyclopentylthiophene, 3,4-di(dimethylphosphino)- 2-phenylthiophene, 3,4-di(diethylphosphino)-2-phenylthiophene, 3,4-di(di-n- propylphosphino)-2-phenylthiophene, 3,4-di(diisobutylphosphino)-2-phenylthiophene, 3,4-di(dicyclopentylphosphino)-2-phenylthiophene, 3,4-di(dicyclohexylphosphino)- 2-phenylthiophene, 3,4-di(diphenylphosphino)-2-phenylthiophene, 3,4-di(di-p- tolylphosphino)-2-phenylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2- phenylthiophene, 3,4-di(dimethylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4- di(diethylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(di-n-propylphosphino)-2- (4-methoxyphenyl)thiophene, 3,4-di(diisobutylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(dicyclopentylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4- di(dicyclohexylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(diphenylphosphino)- 2-(4-methoxyphenyl)thiophene, 3,4-di(di-p-tolylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(di-p-methoxyphenylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4- di(dimethylphosphino)-2,5-dimethylthiophene, 3,4-di(diethylphosphino)-2,5- dimethylthiophene, 3,4-di(di-n-propylphosphino)-2,5-dimethylthiophene, 3,4-di-4-di(n-propylphosphino)-2,5-diethylthiophene, 3,4-di(diisobutylphosphino)-2,5-diethylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diethylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diethylthiophene, 3,4-di(diphenylphosphino)-2,5-diethylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diethylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diethylthiophene, 3,4-di(dimethylphosphino)-2,5-diisopropylthiophene, 3,4-di(diethylphosphino)-2,5-diisopropylthiophene, 3,4-di(n-propylphosphino)-2,5-diisopropylthiophene, 3,4-di(isobutylphosphino)-2,5-diisopropylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diisopropylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diisopropylthiophene, 3,4-di(diphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(dimethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(n-propylphosphino)-2,5-di-n-butylthiophene, 3,4-di(isobutylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diphenylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dimethylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(diethylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(n-propylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(isobutylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(diphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dimethylphosphino)-2,5-diphenylthiophene, 3,4-di(diethylphosphino)-2,5-diphenylthiophene, 3,4-di(n-propylphosphino)-2,5-diphenylthiophene, 3,4-di(isobutylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diphenylthiophene, 3,4-di(diphenylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diphenylthiophene,4-Di(diphenylphosphino)-2,5-diphenylthiophene, 3,4-Di(di-p-tolylphosphino)-2,5-diphenylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2,5-diphenylthiophene, 3,4-Di(dimethylphosphino)-2,5-di-p-tolylthiophene, 3,4-Di(diethylphosphino)-2,5-di-p-tolylthiophene, 3,4-Di(di-n-propylphosphino)-2,5-di-p-tolylthiophene, 3,4-di... (Diisobutylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(diphenylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-di-p-tolylthiophene.

[0040] In one embodiment, the carrier of the present invention is magnesium halide, which is known in the art, and more preferably an alcoholysis of magnesium halide. The present invention does not particularly limit the magnesium halide alcoholysis; conventional magnesium halide alcoholysis in the art is acceptable. In another embodiment, in the magnesium halide alcoholysis, the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium chloromethoxy, and magnesium chloroethoxy, and more specifically, magnesium chloride; the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol, and more specifically, ethanol.

[0041] In one embodiment, the titanium-containing compound has the general formula Ti(OR'). n X (4-n) Where R' is C1 to C 20 Alkyl groups, C6-C 20 aryl or C7~C 20 The aralkyl group, X is a halogen, and n is an integer 0 ≤ n < 4. In another embodiment, the titanium-containing compound is selected from one of tetraethoxytitanium, tetrabutoxytitanium, chlorotrialkoxytitanium, dichlorodialkoxytitanium, trichloroalkoxytitanium, titanium tetrachloride, or titanium tetrabromide, preferably titanium tetrachloride.

[0042] In one embodiment, based on the total weight of the solid catalyst components for olefin polymerization, the solid catalyst components for olefin polymerization include: 1-20 wt% internal electron donor, 0.5-8 wt% titanium-containing compound (calculated as titanium), and 10-25 wt% support. The catalyst disclosed in this invention also includes halogen atoms, the content of which is affected by magnesium halides, titanium-containing compounds, etc., and is generally 40-70 wt% halogen atoms.

[0043] In one embodiment, the present invention also provides a method for preparing the above-described internal electron donor, comprising the following steps:

[0044] Step 1, reacting the compound of formula II with halogen element X2 to obtain the compound of formula III;

[0045] Step 2, reacting the compound of formula III with n-BuLi and PR1R2Cl to obtain the internal electron donor of formula I;

[0046]

[0047] wherein X is halogen, R1, R2, R3 and R4 are the same or different, selected from hydrogen atom, C1-C20 linear or branched alkyl, C3-C20 cyclic alkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 alkoxyaryl. 20 20 20 20 20

[0048] In step 1 of the present application, the compound of formula II is reacted with halogen element X2 to obtain the compound of formula III, and the reaction temperature is 15-30°C, for example, room temperature. In step 2, the compound of formula III is reacted with n-BuLi at a reaction temperature of, for example, -78°C, and the obtained product is further reacted with PR1R2Cl at a reaction temperature of, for example, room temperature, and the internal electron donor of formula I is obtained after post-treatment.

[0049] In one embodiment, the present application further provides a method for preparing a solid catalyst component for olefin polymerization, comprising the following steps:

[0050] Step a, mixing the carrier with a partial titanium-containing compound and reacting at -30 to -10°C;

[0051] Step b, adding the internal electron donor to the reaction mixture obtained in step a and reacting at 60-150°C;

[0052] Step c, mixing the remaining titanium-containing compound with the reaction mixture obtained in step b and reacting at 60-150°C to obtain the solid catalyst component for olefin polymerization.

[0053] wherein the sum of the partial titanium-containing compound and the remaining titanium-containing compound is the total amount of the titanium-containing compound added in the preparation of the solid catalyst component for olefin polymerization. In one embodiment, the mass ratio of the partial titanium-containing compound to the remaining titanium-containing compound is 1-5:5-1.

[0054] The solid catalyst component for olefin polymerization of the present application needs to be added with a certain amount of cocatalyst when used for olefin polymerization. In one embodiment, in order to obtain better polymerization effect, the present application adds an aluminum alkyl compound (cocatalyst component 1) and an alkoxy silane compound (cocatalyst component 2) as cocatalysts.

[0055] ​​​​​In another embodiment, the alkylaluminum compound is of the general formula AlR" m X' (3-m) wherein R" is a C1-C20 alkyl group, a C6-C20 aryl group or a C7-C20 aralkyl group; X' is a halogen; and m is an integer satisfying 0 < m < 3. In yet another embodiment, the alkylaluminum compound of the present application is selected from one of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, preferably triethylaluminum or triisobutylaluminum.

[0056] In another embodiment, the alkoxysilane compound is selected from one of dimethoxydimethylsilane, diethoxydimethylsilane or dimethoxydiphenylsilane, preferably dimethoxydiphenylsilane.

[0057] The amount of the solid catalyst component for olefin polymerization and the cocatalyst can be adjusted according to the need. In one embodiment, the molar ratio of titanium in the solid catalyst component for olefin polymerization to aluminum in the cocatalyst is 1:1 to 1:2000, preferably 1:1 to 1:500, and the molar ratio of titanium in the solid catalyst component for olefin polymerization to silicon in the cocatalyst is 1:1 to 1:50, preferably 1:1 to 1:20.

[0058] The present application does not particularly limit the manner and process conditions for the solid catalyst component for olefin polymerization and the cocatalyst to be used for olefin polymerization, and the conventional manner and process conditions in the art can be used. In one embodiment, the olefin polymerization is propylene polymerization, and the temperature for the olefin polymerization is 0 to 80°C, preferably 20 to 70°C.

[0059] The technical solutions of the present application will be further described in detail below through specific examples.

[0060] The evaluation and analysis methods used in the following examples and comparative examples are as follows:

[0061] The Ti content in the catalyst is determined by spectrophotometry (722S type):

[0062] Under the protection of inert gas, 0.2000 g of the sample is dissolved in 20 mL of sulfuric acid (volume ratio of sulfuric acid to water is 1:4); 9 mL of heptane is extracted in three times, each time with 5 min of oscillation, and the organic matter is separated; the organic phase is placed in a 10 mL volumetric flask and diluted with heptane (for determination of the organic content). The inorganic phase is diluted with water to a 50 mL volumetric flask, and shaken well for use. Two 2 mL portions of the inorganic phase to be tested are taken, placed in a 25 mL volumetric flask, 1 mL of 3% (m / v) hydrogen peroxide is added, diluted with sulfuric acid (volume ratio of sulfuric acid to water is 1:9) to the scale, and shaken well. After 10 min, the blank is used as the reference liquid, 3 cm cuvette is used, and the absorbance is determined at a wavelength of 410 nm. The corresponding value is found from the fitting straight line of the titanium standard for content calculation.

[0063] The content of the internal electron donor compound was determined by gas chromatography (Techcomp GC7900): the above organic phase was analyzed by gas chromatography with heptane as a reference, and the content was calculated according to the peak area ratio of the sample to the pure substance solution.

[0064] Determination of molecular weight distribution: high-temperature gel chromatography analysis was performed using a Waters Alliance GPC 2000 gel permeation chromatograph produced by the U.S. Waters Company to determine the relative molecular mass and its distribution of the sample, the mobile phase solvent was o-dichlorobenzene, the flow rate was 1.0 mL / min, and the determination temperature was 135°C.

[0065] Determination of polymer melt flow rate: μPXRZ-400C was used.

[0066] Synthesis of internal electron donor compound

[0067] In a specific embodiment, the present application provides a detailed synthesis process of the internal electron donor 3,4-bis(diphenylphosphino)-2,5-dimethylthiophene, as follows:

[0068] 2,5-dimethylthiophene 1.0 g and NaOAc 1.9 g were added to 50 mL of CH2Cl2 and reacted at room temperature in the dark for 5 min, then cooled to 0°C, while gradually adding Br2 0.96 mL, after the addition was completed, the temperature was raised to room temperature, and after 2 h of reaction, a 10% Na2S2O3 solution of Na2S2O3 was added, the aqueous phase was separated, the organic phase was extracted with CH2Cl2, the organic phase was washed with water, and the organic phase was dried over anhydrous MgSO4, then column chromatography was performed with petroleum ether as the eluent to obtain 3,4-dibromo-2,5-dimethylthiophene as a colorless solid 1.87 g, with a yield of 75%.

[0069] 3,4-dibromo-2,5-dimethylthiophene 6 g was added to 70 mL of THF under a nitrogen atmosphere, cooled to -78°C, and 18.8 mL of n-butyllithium in n-hexane was slowly added dropwise, the temperature was maintained at -78°C, and after stirring for 1 h, 8.41 mL of diphenylphosphine chloride was added, the temperature was raised to room temperature, and after 5 h of reaction, the reaction was quenched with water, the organic phase was extracted with CH2Cl2, dried, and the organic solvent was evaporated, and column chromatography was performed to obtain a white solid 7.42 g, with a yield of 69%. The obtained white solid was subjected to nuclear magnetic determination, 31 P NMR (CDCI3, 120 MHz) δ: -21.45.

[0070] The internal electron donor compounds used in the following examples are synthesized in the same way, only the corresponding substrate is replaced, for example, to synthesize the internal electron donor 3,4-bis(diisobutylphosphino)thiophene of Example 1, replace the substrate 2,5-dimethylthiophene in the synthesis of the internal electron donor with thiophene and the diphenylphosphine chloride with diisobutylphosphine chloride, use the same amount of thiophene as 2,5-dimethylthiophene and the same amount of diisobutylphosphine chloride as diphenylphosphine chloride.

[0071] Example 1

[0072] Preparation of the solid catalyst component: under anhydrous and anaerobic conditions, 5.0 g of particles of microspheroidal alcoholate of magnesium chloride (home-made, preparation procedure according to CN 1110281 A, average particle size 50 μm, specific surface 150-230 m 2 / g, molar ratio between alcohol and magnesium chloride content 2.85:1, formula MgCl2-2.85CH3CH2OH) are added to 140 ml of titanium tetrachloride liquid at -20°C, after 1 hour of reaction the temperature is gradually increased to 60°C; 1.4 g of 3,4-bis(diisobutylphosphino)thiophene are added, the temperature is gradually increased to 120°C, the reaction is maintained for 2 hours and then filtered; 140 ml of titanium tetrachloride are added again, the reaction is maintained for 1 hour at 120°C and filtered. Washing with 100 ml of hexane at 60°C for 5 times and with 30 ml of hexane at room temperature for 1 time, drying under vacuum give the solid catalyst component.

[0073] Bulk polymerization: in a 10 1 stainless steel autoclave, vacuum dried and thoroughly replaced with nitrogen and propylene, 2 kg of propylene, triethylaluminium and methylcyclohexyldimethoxysilane are added, molar ratio between titanium and aluminium 1:200, molar ratio between titanium and silicon 1:20; 30 mg of the above catalyst and 0.3 g of hydrogen are added, the temperature is increased to 70°C, the reaction is maintained for 1 hour, the temperature is decreased to room temperature, the pressure is released and the polymer is obtained.

[0074] The polymerization results are reported in Table 1.

[0075] Example 2

[0076] The catalyst is prepared and the propylene polymerization is carried out as in Example 1, only in the preparation of the catalyst 3,4-bis(diphenylphosphino)thiophene is used instead of 3,4-bis(diisobutylphosphino)thiophene, the amount of 3,4-bis(diphenylphosphino)thiophene added is 1.0 g.

[0077] The polymerization results are reported in Table 1.

[0078] Example 3

[0079] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0080] The polymerization results are shown in Table 1.

[0081] Example 4

[0082] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0083] The polymerization results are shown in Table 1.

[0084] Example 5

[0085] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0086] The polymerization results are shown in Table 1.

[0087] Example 6

[0088] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0089] The polymerization results are shown in Table 1.

[0090] Example 7

[0091] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0092] The polymerization results are shown in Table 1.

[0093] Example 8

[0094] The catalyst was prepared in the same manner as in Example 1 except that 3,4-bis (di-n-butylphosphino) -2-methylthiophene was used instead of 3,4-bis (diisobutylphosphino) thiophene in the catalyst preparation process. The amount of 3,4-bis (di-n-butylphosphino) -2-methylthiophene added was 0.7 g.

[0095] The polymerization results are shown in Table 1.

[0096] Example 9

[0097] The catalyst was prepared in the same manner as in Example 1 except that 3,4- bis(dicyclohexylphosphino)-2,5-dimethylthiophene was used instead of 3,4- bis(diisobutylphosphino)thiophene in the catalyst preparation process, and the amount of 3,4-bis(dicyclohexylphosphino)-2,5-dimethylthiophene used was the same as in Example 1.

[0098] The polymerization results are shown in Table 1.

[0099] Example 10

[0100] The catalyst was prepared in the same manner as in Example 1 except that 3,4- bis(diphenylphosphino)-2,5-dimethylthiophene was used instead of 3,4- bis(diisobutylphosphino)thiophene in the catalyst preparation process, and the amount of 3,4-bis(diphenylphosphino)-2,5-dimethylthiophene used was 1.6 g.

[0101] The polymerization results are shown in Table 1.

[0102] Example 11

[0103] The catalyst was prepared in the same manner as in Example 1 except that 3,4- bis(di-p-tolylphosphino)-2,5-dimethylthiophene was used instead of 3,4- bis(diisobutylphosphino)thiophene in the catalyst preparation process, and the amount of 3,4-bis(di-p-tolylphosphino)-2,5-dimethylthiophene used was the same as in Example 1.

[0104] The polymerization results are shown in Table 1.

[0105] Example 12

[0106] The catalyst was prepared in the same manner as in Example 1 except that 3,4- bis(diphenylphosphino)-2,5-diethylthiophene was used instead of 3,4- bis(diisobutylphosphino)thiophene in the catalyst preparation process, and the amount of 3,4-bis(diphenylphosphino)-2,5-diethylthiophene used was the same as in Example 1.

[0107] The polymerization results are shown in Table 1.

[0108] Example 13

[0109] The catalyst was prepared in the same manner as in Example 1 except that 3,4- bis(diphenylphosphino)-2,5-diisopropylthiophene was used instead of 3,4- bis(diisobutylphosphino)thiophene in the catalyst preparation process, and the amount of 3,4-bis(diphenylphosphino)-2,5-diisopropylthiophene used was 1.0 g.

[0110] The polymerization results are shown in Table 1.

[0111] Example 14

[0112] The catalyst was prepared according to the method of Example 1, except that 3,4-bis(diphenylphosphino)-2,5-diphenylthiophene was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0113] The polymerization results are shown in Table 1.

[0114] Example 15

[0115] The catalyst was prepared according to the method of Example 1, except that 3,4-bis(diphenylphosphino)-2,5-diphenylthiophene was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0116] The polymerization results are shown in Table 1.

[0117] Comparative Example 1

[0118] The catalyst was prepared according to the method of Example 1, except that phenyl bis(benzenesulfonyl)phosphine oxide (synthesis method according to CN101787088A) was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0119] The polymerization results are shown in Table 1.

[0120] Comparative Example 2

[0121] The catalyst was prepared according to the method of Example 1, except that phthalate was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0122] The polymerization results are shown in Table 1.

[0123] Comparative Example 3

[0124] The catalyst was prepared according to the method of Example 1, except that 9,9-bis(methoxymethyl)fluorene (synthesis method according to CN02127846.6) was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0125] The polymerization results are shown in Table 1.

[0126] Comparative Example 4

[0127] The catalyst was prepared according to the method of Example 1, except that 2,3-diisopropyl succinic acid diethyl ester was used instead of 3,4-bis(diisobutylphosphino)thiophene in the catalyst preparation process.

[0128] The polymerization results are shown in Table 1.

[0129] Comparative Example 5

[0130] The catalyst was prepared according to the procedure of Example 2, except that 6,6'-dimethoxy-2,2'-bis(di(4-methoxyphenylphosphino))-1,1'-biphenyl was used in place of 3,4-bis(diisobutylphosphino)thiophene.

[0131] Comparative Example 6

[0132] The catalyst was prepared according to the procedure of Example 4, except that bis(2-thiophenecarboxylic acid)-2,4-pentanediyl ester was used in place of 3,4-bis(diisobutylphosphino)thiophene.

[0133] Table 1. Results of propylene polymerization tests with catalysts

[0134]

[0135]

[0136] As shown in Table 1, the solid catalyst components of the embodiments of the present application used for olefin polymerization exhibit high catalyst activity when used for propylene polymerization, and the resulting polymers have comparable isotacticity and wider molecular weight distribution.

[0137] Of course, the present application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications to the present application according to the present application without departing from the spirit and essence of the present application, and these corresponding changes and modifications shall all fall within the protection scope of the present application.

Claims

1. A solid catalyst component for olefin polymerization, comprising a support, a titanium-containing compound, and an internal electron donor, characterized in that, The internal electron donor has the following structure: Formula I: Among them, R1, R2, R3, and R4 may be the same or different, and are selected from hydrogen atoms, C1 to C4 atoms. 20 Straight-chain or branched alkyl groups, C3-C4 20 cycloalkyl, C6-C 20 aryl, C7~C 20 Aryl groups and C7-C 20 alkoxyaryl.

2. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, R1, R2, R3, and R4 are selected from C1 to C2. 10 Straight-chain or branched alkyl groups, C3-C4 10 cycloalkyl, C6-C 10 aryl, C7~C 10 Aryl groups or C7-C 10 alkoxyaryl.

3. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, Based on the total weight of the solid catalyst components for olefin polymerization, the solid catalyst components for olefin polymerization include: 1-20 wt% internal electron donor and 0.5-8 wt% titanium-containing compound (calculated as titanium).

4. The solid catalyst component for olefin polymerization according to claim 3, characterized in that, The carrier is an ethanolate of magnesium halide, wherein the magnesium halide is selected from at least one of magnesium chloride, magnesium bromide, magnesium chloromethoxy, and magnesium chloroethoxy; and the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, and isobutanol.

5. The solid catalyst component for olefin polymerization according to claim 4, characterized in that, In the magnesium halide alcohol, the magnesium halide is magnesium chloride and the alcohol is ethanol.

6. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The general formula of the titanium-containing compound is Ti(OR'). n X (4－n) Where R' is C1 to C 20 Alkyl groups, C6-C 20 aryl or C7~C 20 The aryl group, where X is a halogen and n is an integer 0 ≤ n < 4.

7. The solid catalyst component for olefin polymerization according to claim 1, characterized in that, The internal electron donor is selected from at least one of the following compounds: 3,4-di(dimethylphosphino)-thiophene, 3,4-di(diethylphosphino)-thiophene, 3,4-di(di-n-propylphosphino)-thiophene, 3,4-di(diisopropylphosphino)-thiophene, 3,4-di(di-n-butylphosphino)-thiophene, 3,4-di(diisobutylphosphino)-thiophene, 3,4-di(di-n-pentylphosphino)-thiophene, 3,4-di(dicyclopentylphosphino)-thiophene, 3,4-di(di-n-hexylphosphino)-thiophene, 3,4-di(dicyclohexylphosphino)-thiophene, 3,4-di(diphenylphosphino)-thiophene, 3,4-di(di-p-tolylphosphino)-thiophene, 3,4-di(di-m-tolylphosphino)-thiophene, 3,4-di(di-p-tolylphosphino)-thiophene. Methoxyphenylphosphino)-thiophene, 3,4-di(di-m-methoxyphenylphosphino)-thiophene, 3,4-di(di-o-methoxyphenylphosphino)-thiophene, 3,4-di(dimethylphosphino)-2-methylthiophene, 3,4-di(diethylphosphino)-2-methylthiophene, 3,4-di(di-n-propylphosphino)-2-methylthiophene, 3,4-di(diisopropylphosphino)-2-methylthiophene, 3,4-di(di-n-butylphosphino)-2-methylthiophene, 3,4-di(diisobutylphosphino)-2-methylthiophene, 3,4-di(di-n-pentylphosphino)-2-methylthiophene, 3,4-di(dicyclopentylphosphino)-2-methylthiophene, 3,4-di(di-n-hexylphosphino)-2-methylthiophene, 3,4-di(di-n-ethyl ... Cyclohexylphosphino)-2-methylthiophene, 3,4-di(diphenylphosphino)-2-methylthiophene, 3,4-di(di-p-tolylphosphino)-2-methylthiophene, 3,4-di(di-m-tolylphosphino)-2-methylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(di-m-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(di-o-methoxyphenylphosphino)-2-methylthiophene, 3,4-di(dimethylphosphino)-2-ethylthiophene, 3,4-di(di-n-propylphosphino)-2-ethylthiophene, 3,4-di(diisobutylphosphino)-2-ethylthiophene, 3,4-di(dicyclopentylphosphino)- 2-Ethiothiophene, 3,4-Di(dicyclohexylphosphino)-2-ethylthiophene, 3,4-Di(diphenylphosphino)-2-ethylthiophene, 3,4-Di(di-p-tolylphosphino)-2-ethylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2-ethylthiophene, 3,4-Di(dimethylphosphino)-2-isopropylthiophene, 3,4-Di(diethylphosphino)-2-isopropylthiophene, 3,4-Di(di-n-propylphosphino)-2-isopropylthiophene, 3,4-Di(diisobutylphosphino)-2-isopropylthiophene, 3,4-Di(dicyclopentylphosphino)-2-isopropylthiophene, 3,4-Di(dicyclohexylphosphino)-2-isopropylthiophene, 3,4-Di(di-p-tolylphosphino)-2-isopropylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2-isopropylthiophene, 3,4-Di(dimethylphosphino)-2-cyclopentylthiophene, 3,4-Di(diethylphosphino)-2-cyclopentylthiophene, 3,4-Di(di-n-propylphosphino)-2-cyclopentylthiophene, 3,4-Di(diisobutylphosphino)-2-cyclopentylthiophene, 3,4-Di(dicyclopentylphosphino)-2-cyclopentylthiophene, 3,4-Di(dicyclohexylphosphino)-2-cyclopentylthiophene, 3,4-Di(diphenylphosphino)-2-cyclopentylthiophene, 3,4-Di(di-p-tolylphosphino)-2-cyclopentylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2-cyclopentylthiophene, 3,4-di (Dimethylphosphino)-2-phenylthiophene, 3,4-di(diethylphosphino)-2-phenylthiophene, 3,4-di(di-n-propylphosphino)-2-phenylthiophene, 3,4-di(diisobutylphosphino)-2-phenylthiophene, 3,4-di(dicyclopentylphosphino)-2-phenylthiophene, 3,4-di(dicyclohexylphosphino)-2-phenylthiophene, 3,4-di(diphenylphosphino)-2-phenylthiophene, 3,4-di(di-p-tolylphosphino)-2-phenylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2-phenylthiophene, 3,4-di(dimethylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(diethylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-di(di-n-propylphosphino) 3,4-Di(diisobutylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(dicyclopentylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(dicyclohexylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(diphenylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(di-p-tolylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2-(4-methoxyphenyl)thiophene, 3,4-Di(dimethylphosphino)-2,5-dimethylthiophene, 3,4-Di(diethylphosphino)-2,5-dimethylthiophene, 3,4-Di(di-n-propylphosphino)-2, 5-Dimethylthiophene, 3,4-Di(diisobutylphosphino)-2,5-dimethylthiophene, 3,4-Di(dicyclopentylphosphino)-2,5-dimethylthiophene, 3,4-Di(dicyclohexylphosphino)-2,5-dimethylthiophene, 3,4-Di(diphenylphosphino)-2,5-dimethylthiophene, 3,4-Di(di-p-tolylphosphino)-2,5-dimethylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2,5-dimethylthiophene, 3,4-Di(dimethylphosphino)-2,5-diethylthiophene, 3,4-Di(diethylphosphino)-2,5-diethylthiophene, 3,4-Di(di-n-propylphosphino)-2,5-diethylthiophene, 3,4-Di(diisobutylphosphino)-2,5-diethylthiophene, 3,4-Di(dicyclopentylphosphino)-2,5-diethylthiophene, 3,4-Di(dicyclohexylphosphino)-2,5-diethylthiophene, 3,4-Di(diphenylphosphino)-2,5-diethylthiophene, 3,4-Di(di-p-tolylphosphino)-2,5-diethylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2,5-diethylthiophene, 3,4-Di(dimethylphosphino)-2,5-diisopropylthiophene, 3,4-Di(diethylphosphino)-2,5-diisopropylthiophene, 3,4-Di(di-n-propylphosphino)-2,5-diisopropylthiophene, 3,4-Di(diisobutylphosphino)-2,5-diisopropylthiophene, 3,4-Di(dicyclopentylphosphino)-2,5-diisopropylthiophene, 3,4 -Di(dicyclohexylphosphino)-2,5-diisopropylthiophene, 3,4-di(diphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diisopropylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-diisopropylthiophene, 3,4-di(dimethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diethylphosphino)-2,5-di-n-butylthiophene, 3,4-di(di-n-propylphosphino)-2,5-di-n-butylthiophene, 3,4-di(diisobutylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-di-n-butylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-di-n-butylthiophene, 3,4-Di(diphenylphosphino)-2,5-di-n-butylthiophene, 3,4-Di(di-p-tolylphosphino)-2,5-di-n-butylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2,5-di-n-butylthiophene, 3,4-Di(dimethylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(diethylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(di-n-propylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(diisobutylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(dicyclopentylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(dicyclohexylphosphino)-2,5-dicyclohexylthiophene, 3,4-Di(diphenylphosphino)-2,5-dicyclohexylthiophene Phenophenanthrene, 3,4-di(di-p-tolylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-dicyclohexylthiophene, 3,4-di(dimethylphosphino)-2,5-diphenylthiophene, 3,4-di(diethylphosphino)-2,5-diphenylthiophene, 3,4-di(di-n-propylphosphino)-2,5-diphenylthiophene, 3,4-di(diisobutylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-diphenylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-diphenylthiophene, 3,4-di(diphenylphosphino)-2,5-diphenylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-diphenylthiophene, 3,4-Di(di-p-methoxyphenylphosphino)-2,5-diphenylthiophene, 3,4-di(dimethylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(diethylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-n-propylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(diisobutylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(dicyclopentylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(dicyclohexylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(diphenylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-tolylphosphino)-2,5-di-p-tolylthiophene, 3,4-di(di-p-methoxyphenylphosphino)-2,5-di-p-tolylthiophene.

8. The method for preparing the solid catalyst component for olefin polymerization according to any one of claims 1-7, characterized in that, The preparation method of an internal electron donor includes the following steps: Step 1: React compound II with halogen element X2 to obtain compound III; Step 2: React the compound of formula III with n-BuLi and PR1R2Cl to obtain the internal electron donor of formula I; Where X is a halogen, and R1, R2, R3, and R4 may be the same or different, and are selected from hydrogen atoms, C1 to C4 atoms. 20 Straight-chain or branched alkyl groups, C3-C 20 cycloalkyl, C6-C 20 aryl, C7~C 20 alkylaryl and C7~C 20 alkoxyaryl groups.

9. The method for preparing the solid catalyst component for olefin polymerization according to claim 8, characterized in that, The reaction temperature for step 1 is 15–30°C, and the reaction temperature for step 2 is -78°C to 25°C.

10. The method for preparing the solid catalyst component for olefin polymerization according to claim 8, characterized in that, The preparation of solid catalyst components includes the following steps: Step a: The support is mixed with a portion of the titanium-containing compound and reacted at -30 to -10°C; Step b: Add the internal electron donor to the reaction mixture obtained in step a, and carry out the reaction at 60–150 °C; Step c: The remaining titanium-containing compound is mixed with the reaction mixture obtained in step b, and the reaction is carried out at 60–150 °C to obtain a solid catalyst component for olefin polymerization.

11. The method for preparing the solid catalyst component for olefin polymerization according to claim 10, characterized in that, The sum of the titanium-containing compounds and the remaining titanium-containing compounds is the total amount of titanium-containing compounds added in the preparation of the solid catalyst components for olefin polymerization.

12. A catalyst for olefin polymerization, characterized in that, Includes the solid catalyst component for olefin polymerization as described in any one of claims 1-7.

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