CN113754801B

CN113754801B - Solid catalyst for preparing olefin polymer and solid catalyst system

Info

Publication number: CN113754801B
Application number: CN202010506715.XA
Authority: CN
Inventors: 林洁; 张晓帆; 黄庭; 付梅艳; 孙竹芳; 夏先知; 周俊领; 张军辉; 赵惠; 郭子芳; 严立安; 施展
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2020-06-05
Filing date: 2020-06-05
Publication date: 2023-02-28
Anticipated expiration: 2040-06-05
Also published as: CN113754801A

Abstract

The invention provides a solid catalyst for preparing olefin polymers, which comprises the following components or the reaction product of the following components: the electron donor comprises a magnesium element, a titanium element, halogen, a first internal electron donor and a second internal electron donor, wherein the first internal electron donor comprises a column aromatic hydrocarbon compound shown as a formula (I), and the second internal electron donor is selected from one or more of an alcohol ester compound, an aromatic carboxylic acid ester compound, a diether compound and a succinate compound. By introducing the columnar aromatic hydrocarbon compound shown in the formula (I) or the derivative thereof as an internal electron donor into the solid catalyst component, the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be improved.

Description

Solid catalyst for preparing olefin polymer and solid catalyst system

Technical Field

The invention relates to the field of olefin polymerization, in particular to a solid catalyst and a solid catalyst system for preparing an olefin polymer.

Background

As is well known, when a solid titanium catalyst component containing magnesium, titanium, halogen and an internal electron donor compound as basic components is used in olefin polymerization, the internal electron donor compound plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight and the like, and the development of the internal electron donor compound has an extraordinary significance in the updating of catalysts.

At present, the research on internal electron donors at home and abroad mainly focuses on fatty acid ester and aromatic acid ester compounds (such as patent CN85100997A and derivative patents thereof); diethers and diketones (as in patents CN1042547a and CN1054139 a); succinate compounds (such as patent CN 1313869A); glycol ester compounds (such as patent CN 1453298A) and the like.

Although the catalyst prepared by taking the compound as the internal electron donor is widely applied, the compound has certain problems in practical application. For example, the catalyst using the binary aromatic carboxylic ester compound has low catalytic activity, and the molecular weight distribution of the obtained polymer is narrow; although the catalyst using 1,3-diether compounds has higher activity and good hydrogen regulation sensitivity, the molecular weight distribution of the obtained polymer is narrow, which is not beneficial to the development of different grades of polymers; the succinate compound is used as an internal electron donor, and the method has the advantages that the molecular weight distribution of the synthesized polypropylene is wider, and the defect that the stereospecificity of the polymer needs to be improved.

Disclosure of Invention

In view of the problems in the prior art, an object of the present invention is to provide a solid catalyst for preparing an olefin polymer, wherein a pillared aromatic hydrocarbon compound represented by formula (I) or a derivative thereof is introduced as an internal electron donor into a solid catalyst component, so that the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be increased.

It is a second object of the present invention to provide a catalyst system for the polymerization of olefins comprising the solid catalyst component provided for the first object.

The third object of the present invention is to provide an application corresponding to the first object and the second object.

The fourth object of the present invention is to provide a process for polymerizing olefins corresponding to the second object.

In order to achieve one of the purposes, the technical scheme adopted by the invention is as follows:

a solid catalyst for the polymerization of olefins comprising the following components or the reaction product of the following components: magnesium element, titanium element, halogen, a first internal electron donor and a second internal electron donor,

wherein the first internal electron donor comprises a columnar aromatic hydrocarbon compound shown as a formula (I),

in the formula (I), the compound is shown in the specification,

is a basic unit, wherein M ₁ 、M ₂ 、M ₃ 、M ₄ 、R ₁ And R ₂ The same or different, each independently selectedFrom hydrogen, hydroxy, cyano, nitro, amino, -CHO, -R ₃ CHO、-C(O)R ₄ 、-C(O)OH、-R ₃ C(O)OH、-C(O)OR ₄ 、-R ₃ C(O)OR ₄ 、-OR ₄ 、-R ₃ OR ₄ Halogen atom, C with or without substituents ₁ -C ₁₀ Alkyl and C with or without substituents ₁ -C ₁₀ Alkoxy, wherein R ₃ Is C with or without substituents ₁ -C ₆ Alkylene radical, R ₄ Is C with or without substituents ₁ -C ₆ An alkyl group, the substituent being selected from the group consisting of a hydroxyl group, an amino group, -CHO, -C (O) OH, a halogen atom, C ₁ -C ₆ Alkyl radical, C ₁ -C ₆ Alkoxy and heteroatoms;

n represents the number of basic units and is an integer of 3-20;

when the adjacent group within the base unit or between adjacent base units is-C (O) R ₄ 、-C(O)OR ₄ 、-R ₃ C(O)OR ₄ 、-OR ₄ 、-R ₃ OR ₄ C with or without substituents ₁ -C ₁₀ Hydrocarbyl and C with or without substituents ₁ -C ₁₀ Hydrocarbyloxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

the second internal electron donor is selected from one or more of alcohol ester compounds, aromatic carboxylic acid ester compounds, diether compounds and succinate compounds.

According to the present invention, the base unit may also be head-to-head connected as shown in the following formula (a), thereby forming an isomer. Said isomers are also intended to be within the scope of the present invention.

The inventor of the present application has found that by introducing a columnar aromatic hydrocarbon compound represented by formula (I) or a derivative thereof as an internal electron donor into a solid catalyst component, the stereospecificity of the catalyst can be improved, and the molecular weight of a polymerization product can be increased.

According to the invention, M on different base units ₁ 、M ₂ 、M ₃ 、M ₄ 、R ₁ And R ₂ May be the same or different.

In some preferred embodiments of the invention, in formula (I), M ₁ 、M ₂ 、M ₃ And M ₄ The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C ₁ -C ₁₀ Alkyl, halogen atom substituted C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy and halogen substituted C ₁ -C ₁₀ An alkoxy group.

In some preferred embodiments of the invention, R ₁ And R ₂ The same or different, each independently selected from hydrogen, C with or without substituent ₁ -C ₁₀ Alkyl and C with or without substituents ₁ -C ₁₀ An alkoxy group.

In some preferred embodiments of the invention, n is an integer from 4 to 10, such as 4,5,6,7, 8, 9, 10. In some preferred embodiments of the invention, n is an integer from 4 to 7.

In some preferred embodiments of the invention, in formula (I), M ₁ 、M ₂ 、M ₃ And M ₄ The same or different, each independently selected from hydrogen, hydroxy, amino, -CHO, fluoro, chloro, bromo, iodo, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

In some preferred embodiments of the invention, R ₁ And R ₂ The same or different, each independently selected from hydrogen, C with or without substituent ₁ -C ₆ Alkyl and C with or without substituents ₁ -C ₆ An alkoxy group.

In some preferred embodiments of the invention, in formula (I), M ₁ And M ₂ Are the same or different and are each independently selected from C ₁ -C ₆ An alkoxy group.

In some preferred embodiments of the present invention, in formula (I), M ₃ And M ₄ Are all hydrogen.

In some preferred embodiments of the present invention, the column arene compound represented by formula (I) is selected from one or more of the following compounds:

compound A1: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound A2: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound A3: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound B1: m ₁ ＝M ₂ ＝OCH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound B2: m ₁ ＝M ₂ ＝OCH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound B3: m ₁ ＝M ₂ ＝OCH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound C1: m ₁ ＝M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound C2: m ₁ ＝M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound C3: m ₁ ＝M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound D1: m ₁ ＝M ₂ ＝OCH(CH ₃ ) ₂ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound D2: m ₁ ＝M ₂ ＝OCH(CH ₃ ) ₂ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound D3: m ₁ ＝M ₂ ＝OCH(CH ₃ ) ₂ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound E1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound E2: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound E3: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound F1: m ₁ ＝OCH ₃ ；M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound F2: m ₁ ＝OCH ₃ ；M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound F3: m ₁ ＝OCH ₃ ；M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound G1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound G2: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound G3: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound H1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝I；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound H2: m ₁ ＝OCH ₃ ；M ₂ ＝I；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound H3: m ₁ ＝OCH ₃ ；M ₂ ＝I；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound I1: m ₁ ＝M ₃ ＝OCH ₃ ；M ₂ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound I2: m is a group of ₁ ＝M ₃ ＝OCH ₃ ；M ₂ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound I3: m ₁ ＝M ₃ ＝OCH ₃ ；M ₂ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound J1: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝OCH ₂ CH ₂ CH ₃ ；R ₁ ＝R ₂ ＝H；n＝5；

Compound J2: m is a group of ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝OCH ₂ CH ₂ CH ₃ ；R ₁ ＝R ₂ ＝H；n＝6；

Compound J3: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝OCH ₂ CH ₂ CH ₃ ；R ₁ ＝R ₂ ＝H；n＝7；

Compound K1: m is a group of ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝CH ₃ ；n＝5；

Compound K2: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝CH ₃ ；n＝6；

Compound K3: m is a group of ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝CH ₃ ；n＝7；

Compound L1: m ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝5；

Compound L2: m ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝6；

Compound L3: m is a group of ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝7；

Compound M1: m ₁ ＝M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound M2: m ₁ ＝M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound M3: m ₁ ＝M ₂ ＝CHO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound N1: m ₁ ＝OCH ₃ ；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound N2: m ₁ ＝OCH ₃ ；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound N3: m ₁ ＝OCH ₃ ；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound O1: m ₁ ＝OH；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound O2: m ₁ ＝OH；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound O3: m is a group of ₁ ＝OH；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound P1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝OH；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound P2: m ₁ ＝OCH ₃ ；M ₂ ＝OH；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound P3: m ₁ ＝OCH ₃ ；M ₂ ＝OH；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound Q1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝CH ₃ COO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound Q2: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝CH ₃ COO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound Q3: m ₁ ＝OCH ₃ ；M ₂ ＝CH ₃ COO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

A compound R1: m ₁ ＝OCH ₃ ；M ₂ ＝Ph；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

A compound R2: m ₁ ＝OCH ₃ ；M ₂ ＝Ph；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

A compound R3: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝Ph；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7。

In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (II),

in the formula (II), R ¹ And R ² Identical or different, each independently selected from C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Alkylaryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₁₀ -C ₂₀ The condensed ring aromatic groups are preferably each independently selected from C having or not having a substituent ₁ -C ₁₀ Alkyl, C with or without substituents ₂ -C ₁₀ Alkenyl, C with or without substituents ₃ -C ₁₀ Cycloalkyl, C with or without substituents ₆ -C ₁₀ Aryl, C with or without substituents ₇ -C ₁₀ Alkylaryl, C with or without substituents ₇ -C ₁₀ Aralkyl and C with or without substituents ₁₀ -C ₁₅ A condensed ring aryl group, said substituent being selected from the group consisting of a hydroxyl group, a halogen atom, a cyano group, a nitro group, an amino group, a mono-C ₁ -C ₆ Alkylamino radical, bis-C ₁ -C ₆ One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is twoA divalent linking group, preferably selected from C with or without substituents ₁ -C ₂₀ Alkylene, C with or without substituents ₃ -C ₂₀ Cycloalkylene and C with or without substituents ₆ -C ₂₀ Arylene group, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C ₁ -C ₂₀ Alkyl when the substituent is multiple C ₁ -C ₂₀ When alkyl, the substituents are optionally bonded to one or more rings.

In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),

r 'in the formula (III)' ₁ And R' ₂ Are the same or different and are each independently selected from C ₁ -C ₁₀ Alkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl radical, C ₆ -C ₂₀ Aryl radical, C ₇ -C ₂₀ Aralkyl radical and C ₇ -C ₂₀ Alkylaryl, preferably selected from C ₁ -C ₆ Alkyl radical, C ₂ -C ₆ Alkenyl radical, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ Cycloalkyl radical, C ₆ -C ₁₀ Aryl radical, C ₇ -C ₁₀ Aralkyl radical and C ₇ -C ₁₀ Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in alkoxy; r' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ The same or different, each is independently selected from hydrogen, halogen and C ₁ -C ₂₀ Alkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl radical, C ₇ -C ₂₀ Alkylaryl group, C ₇ -C ₂₀ Aralkyl and C ₁₀ -C ₂₀ Condensed ring aryl, preferably selected from hydrogen, halogen, C ₁ -C ₁₀ Alkyl radical, C ₂ -C ₆ Alkenyl radical, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ Cycloalkyl radical, C ₆ -C ₁₀ Aryl radical, C ₇ -C ₁₀ Alkylaryl group, C ₇ -C ₁₀ Aralkyl and C ₁₀ -C ₁₅ A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with one or more substituents selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in alkoxy; r' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ Optionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ Are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and when n is 0, the substituent is R' ₃ And R' ₄ Is R 'to carbon atom and substituent' ₅ And R' ₆ Is bonded to the carbon atom(s) of (a).

<xnotran> , 4235 zxft 4235- ,3- -4287 zxft 4287- , 5252 zxft 5252- ,4- -6258 zxft 6258 , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- ,2- -6258 zxft 6258- ,4- -6258 zxft 6258- ,6- -6258 zxft 6258- ,4- -6258 zxft 6258- ,5- -6258 zxft 6258- ,4- -6258 zxft 6258- ,4- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , </xnotran> 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2,4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2,4-heptanediol di (m-methylbenzoic acid) ester, 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate 4-Ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6 nonanediol dibenzoate, 5-ethyl-4,6 nonanediol dibenzoate, 5-propyl-7439 zxft Nonanediol dibenzoate, 5-butyl-4,6 nonanediol dibenzoate, 5-ethyl-3825 zxft, 5-octanediol dibenzoate, 5-methyl-5-ethyl-5683 zxft 5483 nonanediol dibenzoate, 5-ethyl-octenol dibenzoate, 5-octanoate, and 5-octanoate, 5,5-dimethyl-4,6 nonanediol dibenzoate, 5-methyl-4-ethyl-4,6 nonanediol dibenzoate, 5-phenyl-4,6 nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate 1,8-naphthyl dibenzoate, 1,8-naphthyl di-4-methylbenzoate, 1,8-naphthyl di-3-methylbenzoate, 1,8-naphthyl di-2-methylbenzoate, 1,8-naphthyl di-4-ethylbenzoate, 1,8-naphthyl di-4-n-propylbenzoate, 1,8-naphthyl di-4-isopropylbenzoate, 1,8-naphthyl di-4-n-butylbenzoate, 1,8-naphthyl di-4-isobutylbenzoate, 1,8-naphthyl di-4-tert-butylbenzoate, 1,8-naphthyl di-4-phenylbenzoate, 58 zxft 6258-naphthyl di-4-fluorobenzoate, 623-z6258-naphthyl di-4-fluorobenzoate, and di-4-fluorobenzoic acid -1,8-naphthyl ester.

In some preferred embodiments of the present invention, the aromatic carboxylic acid ester compound is selected from compounds represented by formula (IV),

in the formula (IV), each R ³ Identical or different, each independently selected from the group consisting of ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₁ -C ₈ Alkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₅ -C ₁₀ Cycloalkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₆ -C ₁₅ Aryl, with or without C ₁ -C ₆ C of alkyl and halogen substituents ₇ -C ₁₅ Alkaryl or with or without radicals selected from C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₁₅ Aralkyl group of (1); r ₄ -R ₇ Can be the same or different, and are independently selected from hydrogen, halogen, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₁ -C ₈ Alkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₅ -C ₁₀ Cycloalkyl, with or without C ₁ -C ₆ C of alkyl and halogen substituents ₆ -C ₂₀ Aryl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₂₀ Alkaryl or with or without radicals selected from C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₂₀ An aralkyl group.

In some preferred embodiments of the present invention, the aromatic carboxylic acid ester-based compound is preferably a phthalic acid carboxylic acid ester-based compound; more preferably, the aromatic carboxylic acid ester compound is one or more selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and still more preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate.

In some preferred embodiments of the invention, the diether compound is selected from 1,3-diether compounds, more preferably from 1,3-diether compounds of formula (V),

r 'in the formula (V)' ₁ 、R' ₂ 、R' ₃ 、R' ₄ 、R' ₅ And R' ₆ The same or different, each independently selected from hydrogen, halogen, C with or without substituent ₁ -C ₂₀ Alkyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₇ -C ₂₀ An alkaryl group; r' ₇ And R' ₈ Identical or different, each independently selected from C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, with or without substituents C ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₇ -C ₂₀ Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino radical, bis-C ₁ -C ₁₀ Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; optionally, R' ₁ 、R' ₂ 、R' ₃ 、R' ₄ 、R' ₅ And R' ₆ Two or more phases ofAnd are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

In some preferred embodiments of the invention the diether compound is selected from the group consisting of 2- (2-ethylhexyl) 1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -3925-dimethoxypropane, 5483 zxft 3527-dimethoxypropane, 2-dicyclohexyl-359692-dimethoxypropane, 2-349634963427 zxft-dipropyl-359635-dimethoxypropane, 2- (2-cyclohexylethyl) -359635 zxft 3527-dimethoxypropane, 2-359692-dipropyl-359692-dimethoxypropane, 2-359635-diethylzft-359692-3425-dimethoxypropane, 2- (2-3-359635-dipropyl-3227-dimethoxypropane, 2-3-dipropylzxft-35963427-dimethoxypropane, 2-dipropylzxft-359635-dipropylzxft-dimethoxypropane, 2-359635-dipropylzxft-3227-dimethoxypropane, 3425-dipropylzxft-dimethoxypropane, 3227-3-dipropylzxft-dimethoxypropane, 2-3-dipropylzxft-3227-35963425-dipropylzxft-35963425-dimethoxypropane, 3-3296-dimethoxypropane, and-dipropylzft-3-dipropylzft-359692, 3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isoamyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis (methoxymethyl) -cyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, -tetramethylcyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, -tetramethylcyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, tetraphenylcyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, -tetrafluorocyclopentadiene, 1,1-bis (methoxymethyl) -3,4-dicyclopentylcyclopentadiene, 1,1-bis (methoxymethyl) indene, 1,1-bis (methoxymethyl) -2,3-dimethoxyindene, 1,1-bis (methoxymethyl) -2,3,6,7-tetrafluoroindene, 1,1-bis (methoxymethyl) -4,5,6,7-tetrafluoroindene, 1,1-bis (methoxymethyl) 4,7-dimethylindene, 1,1-bis (methoxymethyl) -3,6-dimethylindene, 1,1-bis (methoxymethyl) -4-phenylindene, 1,1-bis (methoxymethyl) -4-phenyl-2-methylindene 1,1-bis (methoxymethyl) -4-tetracyclohexylindene, 1,1-bis (methoxymethyl) -7- (3,3,3-trifluoropropyl) phenylindene, 1,1-bis (methoxymethyl) -7-cyclopentylindene, 1,1-bis (methoxymethyl) -7-isopropylindene, 1,1-bis (methoxymethyl) -7-cyclohexylindene, 1,1-bis (methoxymethyl) -7-tert-butylindene, 1,1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1,1-bis (methoxymethyl) -7-phenylindene, 1,1-bis (methoxymethyl) -2-phenylindene, 9,9-bis (methoxymethyl) fluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -1,8-difluorofluorene, 9,9-bis (methoxymethyl) -1,2,3,4-tetrahydrofluorene, 9,9-bis (methoxymethyl) -4-tert-butylfluorene, 1,1-bis- (methoxymethyl) -67 zxft 3567-cyclohexadiene, 1,1-bis- (methoxymethyl) -benzonaphthalene, 3592-bis (methoxymethyl) -benzonaphthalene 7,7-bis- (methoxymethyl) -2,5-norbornadiene, 9,9-bis- (methoxymethyl) -1,4-methane dihydronaphthalene, 9,9-bis- (methoxymethyl) -9,9-methane dihydroanthracene, 9,9-bis- (methoxymethyl) -1-phenyl-9,9-dihydronaphthalene, 9,9-bis- (methoxymethyl) -9,9-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -58 zxft 6258-tetramethylcyclopentadiene.

In some preferred embodiments of the present invention, the first internal electron donor is present in an amount of 0.001wt% to 30wt%, preferably 0.01wt% to 20wt%, and more preferably 0.1wt% to 15wt%, based on the total amount of the solid catalyst.

In some preferred embodiments of the present invention, the second internal electron donor is present in an amount of 0.001wt% to 30wt%, preferably 1wt% to 30wt%, more preferably 1wt% to 25wt%, based on the total amount of the solid catalyst.

In some preferred embodiments of the present invention, the molar ratio of the first internal electron donor to the second internal electron donor in the solid catalyst is (1-100): (100-1), preferably (1-50): (50-1), and more preferably (1-20): (20-1).

According to the invention, the solid catalyst component comprises a titanium element, a magnesium element and an internal electron donor, and is a reaction product of a titanium compound, a magnesium compound and the internal electron donor. Since the present invention improves the performance of the olefin polymerization catalyst by changing the external electron donor, the method of preparing the solid catalyst component by the above reaction in the present invention may be performed according to a method conventionally used in the art, for example, refer to methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc., the disclosure of which is incorporated herein by reference.

The preparation method of the solid catalyst component in the present invention includes, but is not limited to, the following methods:

the method comprises the following steps: adding an inert solvent into a magnesium compound, adding an organic epoxy compound and an organic phosphorus compound, dissolving, adding a precipitation aid and a titanium compound, and precipitating a solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium tetrahalide and inert diluent.

The method 2 comprises the following steps: dissolving solid magnesium compound in organic alcohol compound such as 2-ethylhexanol in inert solvent such as decane or toluene, adding precipitation assistant and titanium compound after dissolving, and precipitating solid; adding an internal electron donor to make it be carried on the solid, and treating with titanium compound and inert diluent.

The method 3 comprises the following steps: dispersing a magnesium halide alcohol compound into a titanium compound at a low temperature (such as below-5 ℃), heating to a high temperature (such as above 50 ℃), adding an internal electron donor compound in the heating process, filtering, treating the obtained precipitate with the titanium compound, and washing the precipitate to obtain the solid catalyst component.

The method 4 comprises the following steps: preparing an alkoxy magnesium carrier and an inert diluent into a suspension, then reacting with a mixture formed by a titanium compound and the inert diluent, filtering, carrying out contact reaction on the obtained precipitate, the titanium compound and an internal electron donor compound, and washing the precipitate to obtain the solid catalyst component.

According to a preferred embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) precooled to-15 to-40 ℃ is mixed with a magnesium compound, and the temperature of the mixture is raised to 90 to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.

According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, and for example, the magnesium compound may be selected from at least one of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group. According to a preferred embodiment of the invention, the magnesium compound is an alcoholate of magnesium dihalide.

According to a preferred embodiment of the invention, the alcoholate of magnesium dihalide has a spherical magnesium alcoholate of formula (VI),

MgX ₂ ·m(R’OH)·nE·qH ₂ o type (VI)

In formula (VI): x is chlorine or bromine; r' is C ₁ -C ₄ Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), m is 0.5 to 4.0; e is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester which can be used as an electron donor and is known in the art, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0 to 0.8.

According to a preferred embodiment of the invention, in formula (VI), X is chlorine or bromine; r' is C1-C4 alkyl, m is 1.5-3.5; n and q are both 0.

According to a preferred embodiment of the invention, the magnesium compound is MgCl ₂ ·m(CH ₃ CH ₂ OH), m is 1.5-3.5.

According to some embodiments of the present invention, the preparation of the magnesium dihalide alcoholate can be carried out according to methods known in the art, for example, with reference to the method disclosed in CN1330086 a.

According to a preferred embodiment of the invention, the preparation process of the alcoholate of magnesium dihalide comprises: (1) Mixing anhydrous magnesium dihalide with alcohol compound (R' OH), and reacting at 90-140 deg.C to obtain magnesium halide alcohol compound; (2) Shearing the magnesium halide alcohol compound in a dispersion medium, and cooling in an inert medium after shearing to obtain the spherical magnesium halide alcohol compound. The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide. Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like. Wherein the shearing means shearing the magnesium halide alcoholate by external shearing force, for example, high-speed stirring method (such as CN 1330086), spraying method (such as US 6020279), super-gravity rotating bed (such as CN 1580136A) and emulsifying machine method (CN 1463990A) and the like.

According to a preferred embodiment of the present invention, in order to further increase the purity of the magnesium compound, the obtained alcohol hydrate of spherical magnesium halide is further subjected to washing and drying steps.

According to the invention, the alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctyl alcohol (2-ethylhexanol) and a mixed halogenating agent under an inert atmosphere. The mixed halogenating agent is a combination of a halogen and a halogen compound, a non-limiting selection of which are: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercuric chloride, mercuric bromide, mercuric iodide, ethoxymagnesium iodide, methoxymagnesium iodide, isopropylmagnesium iodide, hydrogen chloride, chloroacetyl chloride, and the like.

According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. According to a preferred embodiment of the present invention, the titanium compound has a structure represented by formula (VII),

Ti(OR”) _4-k X _k formula (VII)

In formula (VII): r' is C1-C20 alkyl, X is F, cl or Br; k is an integer of 0 to 4.

According to a preferred embodiment of the invention, in formula (VII): r' is C1-C10 alkyl.

According to a preferred embodiment of the invention, in formula (VII): r' is C1-C5 alkyl.

According to a preferred embodiment of the invention, for example, in formula (VII): r' is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.

According to a preferred embodiment of the invention, in formula (VII): and X is Cl.

According to a preferred embodiment of the present invention, the titanium compound is at least one selected from the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro-monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride.

In the present invention, the inert solvent and the inert diluent are solvents commonly used in the art, and specifically, for example, one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane and decane may be used, and hexane is preferable. According to a preferred embodiment of the invention, the titanium compound is titanium tetrachloride.

In order to achieve the second purpose, the invention adopts the following technical scheme:

a catalyst system for the polymerisation of olefins comprising the following components or the reaction product of the following components:

1) A solid catalyst component comprising the above solid catalyst;

2) A co-catalyst component comprising an organoaluminum compound; and

optionally, 3) an external electron donor compound.

In some preferred embodiments of the present invention, the organoaluminum compound has the formula AlR ⁸ _d X ¹ _3-d In the formula, R ⁸ Is hydrogen or C _l ～C ₂₀ Hydrocarbyl radical, X ¹ Is halogen atom, d is more than 0 and less than or equal to 3; preferably, the organoaluminium compound is selected from Al (CH) ₃ ) ₃ 、Al(CH ₂ CH ₃ ) ₃ 、Al(i-Bu) ₃ 、AlH(CH ₂ CH ₃ ) ₂ 、AlCl(CH ₂ CH ₃ ) ₂ 、AlH(i-Bu) ₂ 、AlCl _1.5 (CH ₂ CH ₃ ) _1.5 、AlCl(CH ₂ CH ₃ ) ₂ And AlCl ₂ (CH ₂ CH ₃ ) More preferably Al (CH) ₂ CH ₃ ) ₃ And/or Al (i-Bu) ₃ More preferably, the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5 to 5000): 1, preferably (20 to 2000): 1.

Since only the internal electron donor component of the olefin polymerization catalyst component is improved in the olefin polymerization catalyst of the present invention, the kind and content of the external electron donor in the olefin polymerization catalyst of the present invention are not particularly limited. Preferably, the molar ratio of the aluminum in the alkyl aluminum compound to the external electron donor compound is (0.1-500): 1, more preferably (1-200): 1; or no external electron donor is used.

According to the present invention, the external electron donor compound may be any of various external electron donor compounds commonly used in the art for achieving the above object, such as: one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. The organosilicon compound is preferred, and the silane compound is more preferred.

According to the invention, the silane compound is selected from compounds shown in a formula (II),

in the formula (II), R ₅ To R ₈ The same or different, each independently selected from hydrogen and C ₁ -C ₁₀ Alkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₁ -C ₁₀ Alkoxy radical, C ₂ -C ₁₀ Alkenyloxy radical, C ₂ -C ₁₀ Alkynyl, C ₂ -C ₁₀ Alkynyloxy, C ₃ -C ₁₀ Cycloalkyl radical, C ₆ -C ₁₅ Aryl and amino, preferably hydrogen, C ₁ -C ₆ Alkyl radical, C ₃ -C ₆ Cycloalkyl radical, C ₆ -C ₁₀ Aryl and amino, said R ₃ To R ₆ Optionally containing substituents selected from halogen atoms, C ₁ -C ₆ Alkyl radical, C ₃ -C ₆ Cycloalkyl radical, C ₆ -C ₁₀ One or more of aryl and amino.

According to the invention, the silane compounds are selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-t-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, one or more of vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.

In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:

the application of the solid catalyst or the catalyst system in the field of olefin polymerization, especially propylene polymerization.

According to the present invention, the olefin polymerization includes homopolymerization and copolymerization of olefins.

According to the invention, the olefin has the general formula CH ₂ = CHR where R is hydrogen or C ₁ -C ₆ And the olefin polymerization can be homopolymerization of a single olefin or copolymerization of a plurality of olefins, and also can be a combination of a single olefin homopolymerization process and a plurality of olefin copolymerization processes.

According to some preferred embodiments of the present invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.

According to some preferred embodiments of the invention, the olefin is ethylene, propylene and/or 1-butene.

In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:

an olefin polymerization process comprising: the olefin is polymerized in the presence of the catalyst system described above.

In some preferred embodiments of the present invention, the polymerization conditions include: the temperature is 0-150 ℃, preferably 50-90 ℃; the pressure is 0.01MPa to 10MPa, preferably 0.1MPa to 5MPa; the time is 0.1h to 5h, preferably 0.2h to 3h.

According to some embodiments of the invention, both the catalyst system and the prepolymerized catalyst composition may be used in the polymerization of olefins.

According to some preferred embodiments of the present invention, both the catalyst system and the prepolymerized catalyst composition may be used in the homopolymerization of propylene or in the copolymerization with other olefins.

According to the present invention, the catalyst system of the present invention may be directly added to a reactor for use in a polymerization process, or the catalyst system and a prepolymerized catalyst composition obtained by prepolymerizing an olefin may be added to the reactor for polymerization.

According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, or using conventional techniques such as slurry processes, gas phase fluidized beds, etc.

According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component ^-5 -5×10 ^-5 Mol/l.

According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent may be 0.2X 10 based on the titanium element in the solid catalyst component ^-5 -2×10 ^-5 Mol/l.

In the present invention, the hydrocarbon group may be selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl and alkaryl groups.

In the present invention, alkyl means a straight or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

In the present invention, examples of the alkenyl group may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl.

In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.

In the present invention, examples of the cycloalkyl group may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl.

In the present invention, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.

In the present invention, examples of the aryl group may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl.

In the present invention, aralkyl means an alkyl group having an aryl substituent, and examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.

In the present invention, the alkylaryl group means an aryl group having an alkyl substituent with a carbon number of 7 to 20, and examples thereof may include, but are not limited to: methylphenyl, ethylphenyl.

In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexoxy.

In the present invention, examples of the condensed ring aryl group may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl.

In the present invention, the heteroatom means an atom generally contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, si, B and the like.

The invention adopts the columnar aromatic hydrocarbon compound shown in the formula (I) or the derivative thereof as the internal electron donor, and the columnar aromatic hydrocarbon compound or the derivative thereof is compounded with other types of internal electron donors for use, thereby improving the molecular weight of the prepared polymerization product.

Detailed Description

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

In the present invention, the compound represented by formula (I) can be prepared by referring to the existing literature, for example, the compounds F1, L1, N1 and O1 can be prepared by referring to the literature Angew.chem.int.Ed.2020,59,3994-3999 (DOI: 10.1002/anie.201913055); compounds P1, Q1, R1 can be prepared according to the document org.Lett.2019,21,3976-3980 (DOI: 10.1021/acs.orglett.9b01123).

In the following examples, the test methods involved are as follows:

1. composition of the catalyst component: using liquid nuclear magnetism ¹ H-NMR；

2. Determination of titanium content in catalyst: carrying out colorimetric determination by adopting an ultraviolet-visible spectrophotometer type 722;

3. polymerization activity of catalyst: the amount of polymer obtained in kg over time is divided by the amount of catalyst added in g.

4. Weight average molecular weight: high temperature sol-gel chromatography, measured with reference to the standard GB/T36214.4-2018.

5. Polymer isotactic index: reference is made to the standard GB/T2412-2008.

Preparation example 1

This preparation example is intended to illustrate the preparation of a magnesium compound.

Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1.

Preparation example 2

This preparation example is intended to illustrate the preparation of the solid catalyst component.

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 0.3mmol of compound B3 and 5mmol of diisobutyl phthalate as internal electron donors in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride twice, washing with hexane five times, and drying in vacuum to obtain the titanium-containing solid catalyst component Z1.

Preparation example 3

A solid catalyst component Z2 was prepared in the manner of preparation example 2. The only difference from preparation 2 is that compound L1 is used instead of compound B3 in preparation 2.

Preparation example 4

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with stirring, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of diisobutyl phthalate as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for two times, washing with hexane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component D1.

Preparation example 5

Sequentially adding 6.0g of magnesium chloride, 119mL of toluene, 5mL of epichlorohydrin and 15.6mL of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, and maintaining for 2.5 hours until the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour ₄ 70mL, slowly heating to 80 ℃, and gradually separating out solids in the heating process; adding 0.3mmol of compound F1 and 5mmol of 3-methyl-2,4-pentanediol dibenzoate as internal electron donors, maintaining the temperature for 1 hour, filtering, adding 80mL of toluene, and washing twice to obtain a solid precipitate. Then toluene 60mL was added ₄ 40mL, heating to 100 ℃, treating for 2 hours, discharging the filtrate, adding 60mL of toluene ₄ 40mL, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, washing for two times in the boiling state, adding 60mL of hexane, and washing for two times at normal temperature to obtain a solid catalyst component Z3.

Preparation example 6

A solid catalyst component Z4 was prepared in the same manner as in preparation example 5. The only difference from preparation example 5 was that compound G1 was used instead of compound F1 in preparation example 5.

Preparation example 7

A solid catalyst component Z5 was prepared in the manner of preparation example 5. The only difference from preparation example 5 was that compound Q1 was used instead of compound F1 in preparation example 5.

Preparation example 8

Sequentially adding 6.0g of magnesium chloride, 119mL of toluene, 5mL of epichlorohydrin and 15.6mL of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen, heating to 50 ℃ under stirring, and maintaining for 2.5 hours until the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour ₄ 70mL, slowly heating to 80 ℃, and gradually separating out solids in the heating process; 6mmol of 3-methyl-2 was added,4-pentanediol dibenzoate is used as an internal electron donor, the temperature is maintained for 1 hour, after filtration, 80mL of toluene is added, and the solid precipitate is obtained after washing twice. Then toluene 60mL was added ₄ 40mL, heating to 100 ℃, treating for 2 hours, discharging the filtrate, adding toluene 60mL ₄ 40mL, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; adding 60mL of toluene, washing for three times in a boiling state, adding 60mL of hexane, washing for two times in a boiling state, adding 60mL of hexane, and washing for two times at normal temperature to obtain a solid catalyst component D2.

Preparation example 9

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 0.3mmol of the mixture J and 5mmol of 2-isopropyl-2-isoamyl-1,3-dimethoxypropane as internal electron donors in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering to remove liquid, adding titanium tetrachloride for two times, washing with hexane five times, and drying in vacuum to obtain a titanium-containing solid catalyst component Z6.

Preparation example 10

A solid catalyst component Z7 was prepared in the same manner as in preparation example 9. The only difference from preparation 9 is that compound R1 is used instead of mixture J in preparation 9.

Preparation example 11

Adding 100mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of the spherical magnesium chloride alcoholate prepared in preparation example 1, slowly heating to 110 ℃, adding 6mmol of 2-isopropyl-2-isoamyl-1,3-dimethoxypropane as an internal electron donor in the heating process, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for treatment twice, washing with hexane for five times, and drying in vacuum to obtain a titanium-containing solid catalyst component D3.

Preparation example 12

To 3mmol of 1, 4-diethoxybenzene was added anhydrous chloroform (50 mL), and stirred uniformly, to the mixture was added 9mmol of paraformaldehyde and 0.45mmol of ferric chloride, reacted at 30 ℃ for 2 to 3 hours, washed with 50mL of water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate = 30) to give compound B3.

Preparation example 13

Compound G1 was prepared in the manner of preparation 12. The only difference from preparation 12 is that 1-methoxy-4-2-chloroethoxybenzene is used to replace 1,4-diethoxybenzene in preparation 12.

Preparation example 14

This preparation serves to illustrate the preparation of mixture J.

3mmol 1, 4-dimethoxy-2,5-diethoxybenzene anhydrous chloroform (50 mL) was added and stirred well, 9mmol paraformaldehyde and 0.45mmol ferric chloride were added to the mixture, reacted at 30 ℃ for 2-3h, washed with 50mL water, the aqueous phase was extracted with dichloromethane, the organic phase was dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography (petroleum ether/ethyl acetate = 30) to give a mixture J comprising compound J1, compound J2, and compound J3. It was found by nuclear magnetic analysis that the molar ratio of J1: J2: J3 (mole ratio) =1:0.68:0.04.

for the purpose of analysis, the contents of the components of the solid catalyst prepared in the above preparation example are shown in Table 1.

TABLE 1

Examples 1 to 7 and comparative examples 1 to 3

Examples 1-7 and comparative examples 1-3 are provided to illustrate the catalyst systems provided by the present invention and their applications.

In a 48 channel parallel pressure reactor (reaction volume 20 mL), 5mNL of hydrogen gas was charged; filling propylene gas to about 1MPa, and adding 5mL of liquid propylene; based on triethyl aluminum (calculated by aluminum element): external electron donor: adding triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio (by titanium element) of 500; injecting a certain amount of mixed liquid (containing 0.02mg of solid catalyst component) into a reactor; the reaction was carried out at 70 ℃ for 1 hour.

Discharging and calculating the activity of the catalyst; the isotactic index and the weight-average molecular weight of the polymer were measured, and the results are shown in Table 2.

TABLE 2

Note: the external electron donor is cyclohexylmethyldimethoxysilane.

As can be seen from Table 2, the introduction of the compound of formula (I) or its derivatives into the olefin polymerization catalyst component can significantly improve the stereospecificity of the catalyst and the molecular weight of the polymer while maintaining a high polymerization activity. According to the characteristics, the catalyst system provided by the invention has higher activity and is particularly suitable for high-rigidity polyolefin products with low melt index and high isotactic index.

Examples 8 to 9

Examples 8-9 illustrate the effect of adjusting the molar ratio of compound B3 and diisobutylphthalate on the results of the experiments. Different solid catalyst components were prepared in the same manner as in preparation example 2, and tested in the same manner as in example 1, while varying the amount of the compound B3 added. Calculating the activity of the catalyst; the isotactic index and the weight-average molecular weight of the polymer were also measured, and the results are shown in Table 3.

TABLE 3

From the data in Table 3, it is understood that the amount of compound B3 added can be adjusted, and the properties of the polymerization product can be adjusted by changing the amount of compound B3 added.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims

1. A solid catalyst for the preparation of an olefin polymer comprising the following components or the reaction product of the following components: magnesium element, titanium element, halogen, a first internal electron donor and a second internal electron donor,

in the formula (I), the compound is shown in the specification,

is a basic unit, wherein M ₁ 、M ₂ 、M ₃ 、M ₄ The same or different, each independently selected from hydrogen, hydroxy, phenyl, -CHO, -R ₃ CHO、-C(O)R ₄ 、-C(O)OH、-R ₃ C(O)OH、-C(O)OR ₄ 、-R ₃ C(O)OR ₄ 、-OR ₄ 、-R ₃ OR ₄ Halogen atom, C with or without substituents ₁ -C ₁₀ Alkyl and C with or without substituents ₁ -C ₁₀ Alkoxy, wherein R ₃ Is C with or without substituents ₁ -C ₆ Alkylene radical, R ₄ Is C with or without substituents ₁ -C ₆ An alkyl group, the substituent being selected from the group consisting of hydroxy, -CHO, -C (O) OH, halogen atom, C ₁ -C ₆ Alkyl radical, C ₁ -C ₆ An alkoxy group; r ₁ And R ₂ The same or different, each independently selected from hydrogen, hydroxyl, halogen atom, C with or without substituent ₁ -C ₁₀ An alkyl group;

n represents the number of basic units and is an integer of 3-20;

when adjacent groups within or between adjacent base units are-C (O) R ₄ 、-C(O)OR ₄ 、-R ₃ C(O)OR ₄ 、-OR ₄ 、-R ₃ OR ₄ C with or without substituents ₁ -C ₁₀ Alkyl and C with or without substituents ₁ -C ₁₀ When alkoxy, two adjacent groups are optionally linked to each other to form a cyclic structure selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

the second internal electron donor is selected from one or more of alcohol ester compounds, aromatic carboxylic acid ester compounds, diether compounds and succinate compounds;

the alcohol ester compound is selected from a diol ester compound shown in a formula (II),

in the formula (II), R ¹ And R ² Identical or different, each independently selected from C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Alkylaryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₁₀ -C ₂₀ A fused ring aryl group; m is a divalent linking group;

the aromatic carboxylic ester compound is selected from compounds shown in a formula (IV),

in the formula (IV), each R ³ Identical or different, each independently selected from the group consisting of ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₁ -C ₈ Alkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₅ -C ₁₀ Cycloalkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₆ -C ₁₅ Aryl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₁₅ Alkylaryl or with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₁₅ Aralkyl group of (1); r ₄ -R ₇ Can be the same or different, and are each independently selected from hydrogen, halogen, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₁ -C ₈ Alkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₅ -C ₁₀ Cycloalkyl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₆ -C ₂₀ Aryl, with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₂₀ Alkylaryl or with or without C ₁ -C ₆ C of substituents of alkyl radicals and halogen atoms ₇ -C ₂₀ Aralkyl group;

the diether compound is 1,3-diether compound shown in formula (V),

r 'in the formula (V)' ₁ 、R' ₂ 、R' ₃ 、R' ₄ 、R' ₅ And R' ₆ The same or different, each independently selected from hydrogen, halogen, C with or without substituent ₁ -C ₂₀ Alkyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₇ -C ₂₀ An alkaryl group; r' ₇ And R' ₈ Identical or different, each independently selected from C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl and C with or without substituents ₇ -C ₂₀ Alkylaryl, said substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino radical, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and hetero atoms; optionally, R' ₁ 、R' ₂ 、R' ₃ 、R' ₄ 、R' ₅ And R' ₆ Two or more of which are bonded to each other to form a saturated or unsaturated monocyclic or polycyclic ring.

2. The solid catalyst according to claim 1, wherein in the formula (I), M is ₁ 、M ₂ 、M ₃ And M ₄ The same or different, each independently selected from hydrogen, hydroxy, phenyl, -CHO, fluoro, chloro, bromo, iodo, C ₁ -C ₁₀ Alkyl, halogen atom substituted C ₁ -C ₁₀ Alkyl radical, C ₁ -C ₁₀ Alkoxy and halogen substituted C ₁ -C ₁₀ An alkoxy group; r ₁ And R ₂ The same or different, each independently selected from hydrogen, C with or without substituent ₁ -C ₁₀ An alkyl group; n is 4-An integer of 10.

3. The solid catalyst according to claim 2, wherein in the formula (I), M is ₁ 、M ₂ 、M ₃ And M ₄ The same or different, each independently selected from hydrogen, hydroxy, phenyl, -CHO, fluoro, chloro, bromo, iodo, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group; r ₁ And R ₂ The same or different, each independently selected from hydrogen, C with or without substituent ₁ -C ₆ An alkyl group; n is an integer of 4 to 7.

4. The solid catalyst according to claim 3, wherein in the formula (I), M is ₁ And M ₂ Are the same or different and are each independently selected from C ₁ -C ₆ An alkoxy group.

5. The solid catalyst according to any one of claims 1 to 4, wherein the pillar arene compound represented by formula (I) is selected from one or more of the following compounds:

Compound D1: m is a group of ₁ ＝M ₂ ＝OCH(CH ₃ ) ₂ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound E1: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ CH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound G1: m ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound G2: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound G3: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝OCH ₂ CH ₂ Cl；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound H1: m ₁ ＝OCH ₃ ；M ₂ ＝I；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

A compound I1: m ₁ ＝M ₃ ＝OCH ₃ ；M ₂ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound I2: m ₁ ＝M ₃ ＝OCH ₃ ；M ₂ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound J2: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝OCH ₂ CH ₂ CH ₃ ；R ₁ ＝R ₂ ＝H；n＝6；

Compound K1: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝CH ₃ ；n＝5；

Compound K3: m ₁ ＝M ₂ ＝OCH ₃ ；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝CH ₃ ；n＝7；

Compound L1: m is a group of ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝5；

Compound L2: m is a group of ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝6；

Compound L3: m ₁ ＝OH；M ₃ ＝H；M ₂ ＝M ₄ ＝Br；R ₁ ＝R ₂ ＝H；n＝7；

Compound N1: m is a group of ₁ ＝OCH ₃ ；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound O2: m is a group of ₁ ＝OH；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝6；

Compound O3: m ₁ ＝OH；M ₂ ＝M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7；

Compound P1: m ₁ ＝OCH ₃ ；M ₂ ＝OH；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

Compound Q1: m ₁ ＝OCH ₃ ；M ₂ ＝CH ₃ COO；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝5；

A compound R3: m ₁ ＝OCH ₃ ；M ₂ ＝Ph；M ₃ ＝M ₄ ＝H；R ₁ ＝R ₂ ＝H；n＝7。

6. The solid catalyst according to any one of claims 1 to 4, wherein in the formula (II), R is ¹ And R ² Identical or different, each independently selected from C with or without substituents ₁ -C ₁₀ Alkyl, C with or without substituents ₂ -C ₁₀ Alkenyl, C with or without substituents ₃ -C ₁₀ Cycloalkyl, with or without substituents C ₆ -C ₁₀ Aryl, C with or without substituents ₇ -C ₁₀ Alkylaryl, C with or without substituents ₇ -C ₁₀ Aralkyl and C with or without substituents ₁₀ -C ₁₅ A condensed ring aryl group, the substituent is selected from hydroxyl, halogen atom, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino radical, bis-C ₁ -C ₆ One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is selected from C containing or not containing substituent ₁ -C ₂₀ Alkylene, C with or without substituents ₃ -C ₂₀ Cycloalkylene and C with or without substituents ₆ -C ₂₀ Arylene radical, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C ₁ -C ₂₀ Alkyl when the substituent is multiple C ₁ -C ₂₀ When alkyl, the substituents are optionally bonded to one or more rings.

7. The solid catalyst according to claim 6, wherein the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by the formula (III),

r 'in the formula (III)' ₁ And R' ₂ Are the same or different and are each independently selected from C ₁ -C ₁₀ Alkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl radical, C ₆ -C ₂₀ Aryl radical, C ₇ -C ₂₀ Aralkyl and C ₇ -C ₂₀ An alkaryl group; r' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ The same or different, each is independently selected from hydrogen, halogen and C ₁ -C ₂₀ Alkyl radical, C ₂ -C ₁₀ Alkenyl radical, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl radical, C ₆ -C ₂₀ Aryl radical, C ₇ -C ₂₀ Alkylaryl group, C ₇ -C ₂₀ Aralkyl and C ₁₀ -C ₂₀ A condensed ring aryl group, wherein n is an integer of 0 to 10.

8. Solid catalyst according to claim 7, characterized in that in formula (III), R' ₁ And R' ₂ Are the same or different and are each independently selected from C ₁ -C ₆ Alkyl radical, C ₂ -C ₆ Alkenyl radical, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ CycloalkanesBase, C ₆ -C ₁₀ Aryl radical, C ₇ -C ₁₀ Aralkyl and C ₇ -C ₁₀ Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in alkoxy; r' ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ The same or different, each is independently selected from hydrogen, halogen and C ₁ -C ₁₀ Alkyl radical, C ₂ -C ₆ Alkenyl radical, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ Cycloalkyl radical, C ₆ -C ₁₀ Aryl radical, C ₇ -C ₁₀ Alkylaryl group, C ₇ -C ₁₀ Aralkyl and C ₁₀ -C ₁₅ A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in the alkoxy group; r' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ Optionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; or, R' ₃ 、R’ ₄ 、R’ ₅ 、R’ ₆ And R' ¹ -R’ ²ⁿ Two or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring; wherein n is an integer of 1-8, and when n is 0, the substituent is R' ₃ And R' ₄ Is R 'to carbon atom and substituent' ₅ And R' ₆ Is bonded to the carbon atom(s) of (a).

9. The solid catalyst according to claim 8, wherein in the formula (III), n is an integer of 2 to 6.

10. <xnotran> 6 , , 4235 zxft 4235- ,3- -4287 zxft 4287- , 5252 zxft 5252- ,4- -6258 zxft 6258 , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- , 6258 zxft 6258- ,2- -6258 zxft 6258- ,4- -6258 zxft 6258- ,6- -6258 zxft 6258- ,4- -6258 zxft 6258- ,5- -6258 zxft 6258- ,4- -6258 zxft 6258- ,4- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , 6258 zxft 6258- -6258 zxft 6258- , </xnotran> 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di (p-chlorobenzoic acid) ester, 6-methyl-2,4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2,4-heptanediol di (m-methylbenzoic acid) ester, 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate 4-Ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-4-ethyl-3,5-octanediol dibenzoate, 2-methyl-6-ethyl-3,5-octanediol dibenzoate, 5-methyl-4,6 nonanediol dibenzoate, 5-ethyl-4,6 nonanediol dibenzoate, 5-propyl-7439 zxft Nonanediol dibenzoate, 5-butyl-4,6 nonanediol dibenzoate, 5-ethyl-3825 zxft, 5-octanediol dibenzoate, 5-methyl-5-ethyl-5683 zxft 5483 nonanediol dibenzoate, 5-ethyl-octenol dibenzoate, 5-octanoate, and 5-octanoate, 5,5-dimethyl-4,6 nonanediol dibenzoate, 5-methyl-4-ethyl-4,6 nonanediol dibenzoate, 5-phenyl-4,6 nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-phenylene dibenzoate, 3,5-diisopropyl-1,2-phenylene dibenzoate, 3,6-dimethyl-1,2-phenylene dibenzoate, 4-tert-butyl-1,2-phenylene dibenzoate, 1,2-naphthalene dibenzoate, 2,3-naphthalene dibenzoate 1,8-naphthyl dibenzoate, 1,8-naphthyl di-4-methylbenzoate, 1,8-naphthyl di-3-methylbenzoate, 1,8-naphthyl di-2-methylbenzoate, 1,8-naphthyl di-4-ethylbenzoate, 1,8-naphthyl di-4-n-propylbenzoate, 1,8-naphthyl di-4-isopropylbenzoate, 1,8-naphthyl di-4-n-butylbenzoate, 1,8-naphthyl di-4-isobutylbenzoate, 1,8-naphthyl di-4-tert-butylbenzoate, 1,8-naphthyl di-4-phenylbenzoate, 58 zxft 6258-naphthyl di-4-fluorobenzoate, 623-z6258-naphthyl di-4-fluorobenzoate, and di-4-fluorobenzoic acid -1,8-naphthyl ester.

11. The solid catalyst according to any one of claims 1 to 4, wherein the aromatic carboxylic acid ester compound is a phthalic acid carboxylic acid ester compound.

12. The solid catalyst according to claim 11, wherein the aromatic carboxylic acid ester compound is selected from one or more of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate.

13. The solid catalyst according to claim 12, wherein the aromatic carboxylic acid ester compound is diisobutyl phthalate.

14. The solid catalyst according to any one of claims 1 to 4, characterized in that, the diether compound is selected from the group consisting of 2- (2-ethylhexyl) 1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-25 zxft 3725-dimethoxypropane, 3526 zxft 3592-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1,3-dimethoxypropane, 2,2-di-sec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis (methoxymethyl) -cyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, -tetramethylcyclopentadiene, 1,1-bis (methoxymethyl) -2,3,4,5, <xnotran> - , 3826 zxft 3826- ( ) -3828 zxft 3828, - , 3925 zxft 3925- ( ) -5483 zxft 5483, - , 5678 zxft 5678- ( ) -7439 zxft 7439- , 8624 zxft 8624- ( ) , 9696 zxft 9696- ( ) -3235 zxft 3235- , 3292 zxft 3292- ( ) -3426 zxft 3426- , 3474 zxft 3474- ( ) -3567 zxft 3567- , 3592 zxft 3592- ( ) 3725 zxft 3725- , 4235 zxft 4235- ( ) -4287 zxft 4287- , 5252 zxft 5252- ( ) -4- , 6258 zxft 6258- ( ) -4- -2- , 6258 zxft 6258- ( ) -4- , 6258 zxft 6258- ( ) -7- (6258 zxft 6258- ) , 6258 zxft 6258- ( ) -7- , 6258 zxft 6258- ( ) -7- , 6258 zxft 6258- ( ) -7- , 6258 zxft 6258- ( ) -7- - , 6258 zxft 6258- ( ) -7- - -2- , </xnotran> 1,1-bis (methoxymethyl) -7-phenylindene, 1,1-bis (methoxymethyl) -2-phenylindene, 9,9-bis (methoxymethyl) fluorene, 9,9-bis (methoxymethyl) -2,7-dicyclopentylfluorene, 9,9-bis (methoxymethyl) -1,8-dichlorofluorene, 9,9-bis (methoxymethyl) -1,8-difluorofluorene, 3567-bis (methoxymethyl) -1,2,3,4-tetrahydrofluorene, 9,9-bis (methoxymethyl) -4-tert-butylfluorene, 1,1-bis- (methoxymethyl) -2,5-cyclohexadiene, 1,1-bis- (methoxymethyl) -benzonaphthalene, 5258 zxft 62626258-bis (methoxymethyl) -626258-bis (methoxymethyl) -6258-methyl-6258-bis (methoxymethyl) -62xft 6258-58-bis (methoxymethyl) -58-vinylbenzene, 58-bis (methoxymethyl) -62xft-6258-vinylbenzene, and-58-bis (methoxymethyl) -3558-vinylbenzene.

15. The solid catalyst according to any one of claims 1 to 4, characterized in that,

based on the total amount of the solid catalyst, the content of the first internal electron donor is 0.001-30 wt%; and/or

Based on the total amount of the solid catalyst, the content of the second internal electron donor is 0.001-30 wt%; and/or

In the solid catalyst, the molar ratio of the first internal electron donor to the second internal electron donor is (1-100) to (100-1).

16. The solid catalyst according to claim 15,

based on the total amount of the solid catalyst, the content of the first internal electron donor is 0.01-20 wt%; and/or

Based on the total amount of the solid catalyst, the content of the second internal electron donor is 1-30 wt%; and/or

In the solid catalyst, the molar ratio of the first internal electron donor to the second internal electron donor is (1-50) to (50-1).

17. The solid catalyst according to claim 15,

based on the total amount of the solid catalyst, the content of the first internal electron donor is 0.1-15 wt%; and/or

Based on the total amount of the solid catalyst, the content of the second internal electron donor is 1-25 wt%; and/or

In the solid catalyst, the molar ratio of the first internal electron donor to the second internal electron donor is (1-20) to (20-1).

18. A catalyst system for the polymerisation of olefins comprising the following components or the reaction product of the following components:

1) A solid catalyst component comprising the solid catalyst of any one of claims 1-17;

2) A co-catalyst component comprising an organoaluminum compound; and

optionally, 3) an external electron donor compound.

19. The catalyst system of claim 18, wherein the organoaluminum compound has the formula AlR ¹ _d X ¹ _3-d In the formula, R ¹ Is hydrogen or C _l ～C ₂₀ Hydrocarbyl radical, X ¹ Is halogen atom, and d is more than 0 and less than or equal to 3.

20. The catalyst system according to claim 19, characterized in that the organoaluminum compound is selected from Al (CH) ₃ ) ₃ 、Al(CH ₂ CH ₃ ) ₃ 、Al(i-Bu) ₃ 、AlH(CH ₂ CH ₃ ) ₂ 、AlCl(CH ₂ CH ₃ ) ₂ 、AlH(i-Bu) ₂ 、AlCl _1.5 (CH ₂ CH ₃ ) _1.5 、AlCl(CH ₂ CH ₃ ) ₂ And AlCl ₂ (CH ₂ CH ₃ ) One or more of (a).

21. The catalyst system of claim 20, wherein the organoaluminum compound is Al (CH) ₂ CH ₃ ) ₃ And/or Al (i-Bu) ₃ 。

22. The catalyst system according to claim 18, wherein the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (5-5000): 1.

23. The catalyst system according to claim 22, wherein the molar ratio of the aluminum element in the organoaluminum compound to the titanium element in the solid catalyst component is (20-2000): 1.

24. Use of a solid catalyst according to any one of claims 1 to 17 or a catalyst system according to any one of claims 18 to 23 in the field of olefin polymerisation.

25. Use of a solid catalyst according to any one of claims 1-17 or a catalyst system according to any one of claims 18-23 in the field of propylene polymerization.

26. An olefin polymerization process comprising: subjecting an olefin to a polymerization reaction in the presence of the catalyst system of any one of claims 18-23.

27. The olefin polymerization process of claim 26, wherein the polymerization conditions comprise: the temperature is 0-150 ℃; the pressure is 0.01MPa to 10MPa; the time is 0.1h to 5h.

28. The olefin polymerization process of claim 27, wherein the polymerization conditions comprise: the temperature is 50-90 ℃; the pressure is 0.1MPa to 5MPa; the time is 0.2h to 3h.