CN113773423A

CN113773423A - Solid catalyst component for preparing olefin polymer and application thereof

Info

Publication number: CN113773423A
Application number: CN202010517095.XA
Authority: CN
Inventors: 李昌秀; 冯华升; 刘静; 高明智; 周俊领; 刘海涛
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: 2020-06-09
Filing date: 2020-06-09
Publication date: 2021-12-10

Abstract

The invention discloses a solid catalyst component for preparing olefin polymers, which comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises a first internal electron donor compound with a general formula (I) and a second internal electron donor compound with a general formula (II) or (III). The invention also discloses a catalyst for olefin polymerization. The catalyst provided by the invention can keep high polymerization activity, high isotactic index and wider molecular weight distribution of the polymer, greatly improve hydrogen regulation sensitivity, and has excellent comprehensive performance, thereby being very beneficial to the development of resins with different grades.

Description

Solid catalyst component for preparing olefin polymer and application thereof

Technical Field

The invention belongs to the field of olefin polymerization, and particularly relates to a solid catalyst component for preparing an olefin polymer and application thereof.

Background

Since the fifty years, propylene polymerization catalysts were developed from the first TiCl generations₃AlCl₃/AlEt₂Cl system and second generation of TiCl₃/AlEt²Cl system, magnesium chloride of the third generation as a carrier, monoester or aromatic dibasic acid ester as an internal electron donor, and TiCl with silane as an external electron donor₄·ED·MgCl₂/AlR₃The catalytic polymerization activity of the ED system and the catalyst and the isotacticity of the obtained polypropylene are greatly improved. In the prior art, a titanium catalyst system for propylene polymerization mostly uses magnesium, titanium, halogen and an electron donor as basic components, wherein an internal electron donor compound is one of essential components in the catalyst component. With the development of electron donor compounds, polyolefin catalysts are also continuously updated. At present, the internal electron donor used in industry is mainly phthalate, and the catalyst system has higher activity and high stereoregularity. Phthalates have attracted considerable attention due to their associated environmental and medical problems. Therefore, researchers in this field are all working on developing internal electron donor compounds of polyolefin catalysts that can replace phthalates.

Most of the electron donors reported at present are oxygen, nitrogen, phosphorus and sulfur-containing compounds. In these catalytic polymerization systems, the electron donor has varying degrees of influence on the activity, stereospecificity, molecular weight distribution and polymer properties.

Patents CN1436766A and CN1552740A both disclose a carboxylic acid diol ester internal electron donor and a preparation method thereof. Although the prepared catalyst is used for propylene polymerization and has the characteristics of high polymerization activity and wide polymer molecular weight distribution, when the spherical catalyst containing the carboxylic glycol ester internal electron donor is used for propylene polymerization, the stereotactic ability is poor, and the isotacticity of the obtained polypropylene is low. Patent CN201210352894.1 reports that when a phosphate compound and a diol ester are compounded for propylene polymerization, a polymer with a wider molecular weight distribution can be obtained, but the polymerization activity is lower.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a solid catalyst component for preparing olefin polymers aiming at the defects of the prior art, and the catalyst with excellent comprehensive performance can be obtained by using a diaryl phosphate compound and a diol ester compound with special structures to be compounded as an internal electron donor. When the catalyst is used for propylene polymerization reaction, the catalyst has high activity, good stereospecificity and hydrogen regulation sensitivity, and wide polymer molecular weight distribution, and is beneficial to the development of polymer grades.

To this end, a first aspect of the present invention provides a solid catalyst component for the preparation of olefin polymers, comprising magnesium, titanium, halogen and an internal electron donor compound, said internal electron donor compound comprising a first internal electron donor compound of formula (I) and a second internal electron donor compound of formula (II) or (III),

in the general formula (I), R₁Is C₁-C₁₅Straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl or C₇-C₂₀And said C is aralkyl, and₁-C₁₅straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl and C₇-C₂₀The hydrogen on the aralkyl carbon of (a) is optionally takenSubstituent groups;

R₂selected from hydrogen, halogen atoms, C₁-C₁₀Straight chain alkyl of (2) and C₃-C₁₀And said C is a branched alkyl group of₁-C₁₀Straight chain alkyl of (2) and C₃-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with a substituent;

in the general formula (II), R₃And R₄Identical or different, independently selected from C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the arylcarbon of (a) is optionally substituted with a substituent;

R₅、R₆、R₇and R₈Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the arylcarbon of (a) may optionally be substituted by a substituent, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring;

in the general formula (III), R₉And R₁₀Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀Aryl of (2), R₉And R₁₀Optionally bonded to form a ring;

R₁₁and R₁₂Identical or different, independently selected from halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀Of hydrocarbon aryl or C₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the arylcarbon of (a) is optionally substituted with a substituent;

R₁₃and R₁₄Identical or different, independently selected from hydrogen and C₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂And said C is a branched alkyl group of₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂The hydrogen on the branched alkyl carbon of (a) may be optionally substituted with a substituent.

According to a preferred embodiment of the solid catalyst component according to the invention, the substituents are chosen from hydroxyl, amino, C₁-C₆Alkyl-substituted amino (e.g. -NHCH)₃or-N (CH)₃)₂) CHO, -COOH, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), C₁-C₆Alkyl (e.g. methyl, ethyl or isopropyl) and C₁-C₆Alkoxy (e.g., methoxy, ethoxy, n-propoxy, or isopropoxy).

In the present invention, the term "branched alkyl group" is a branched alkyl group, a branched alkenyl group or a branched alkynyl group, "cyclic alkyl group" is a cycloalkyl group, a cycloalkenyl group or a cyclic alkynyl group, "hydrocarbon aryl group" is an alkylaryl group, an alkenylaryl group or an alkynylaryl group, and "aromatic alkyl group" is an arylalkyl group, an arylalkenyl group or an arylalkynyl group.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₁Is C₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl or C₇-C₁₅And said C is an aralkyl group₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl and C₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents selected from the group consisting of.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₁Is C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₉Straight chain alkyl group of (1), C₁₀-C₁₂Straight chain alkyl group of (1), C₃-C₄Branched alkyl of C₅-C₇Branched alkyl of C₈-C₁₀Branched alkyl of C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl or C₁₃-C₁₅An aralkyl group of (2).

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₁Is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenethyl or phenylpropyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₂Is hydrogen, halogen atom, C₁-C₈Straight chain alkyl or C₃-C₁₀And said C is a branched alkyl group of₁-C₈Straight chain alkyl of (2) and C₃-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₂Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₈Straight chain alkyl group of (1), C₃-C₅Branched alkyl of C₆-C₇Branched alkyl or C₈-C₁₀Branched alkyl groups of (a).

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₂Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl or hexyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄Identical or different, independently selected from C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄The same is true.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄Are not identical.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃Is selected from C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅And said C is an aromatic hydrocarbon group₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the carbon of the arene group of (a) may be optionally substituted with one or more substituents, such as phenyl, benzyl, phenethyl and phenylpropyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₄Is selected from C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅And said C is an aromatic hydrocarbon group₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the carbon of the arene group of (a) may be optionally substituted with one or more substituents, such as phenyl, benzyl, phenethyl and phenylpropyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₅、R₆、R₇And R₈Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted by one or more substituents, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₅、R₆、R₇And R₈Identical or different, independently selected from C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl of C₆-C₈Branched alkyl of C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅And said C is an aromatic hydrocarbon group₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl of C₆-C₈Branched alkyl of C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₅Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl or C₆-C₈Branched alkyl of (2) is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₆Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl or C₆-C₈Branched alkyl of (2) is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₇Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl or C₆-C₈Branched alkyl of (2) is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₈Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl or C₆-C₈Branched alkyl of (2) is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉And R₁₀Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅Aralkyl of (2), R₉And R₁₀Optionally bonded to form a ring.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉And R₁₀The same is true.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉And R₁₀Are not identical.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉Selected from hydrogen, halogen atoms, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈Such as hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₀Selected from hydrogen, halogen atoms, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈Branched alkyl radicals of (2), e.g. hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propylAlkyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂Identical or different, independently selected from halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents selected from the group consisting of.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂The same is true.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂Are not identical.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁Is selected from C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents, e.g., methyl, ethyl, n-propyl, isopropylAlkyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₂Is selected from C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈The hydrogen on the branched alkyl carbon of (a) may be optionally substituted with one or more substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄Identical or different, independently selected from hydrogen and C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A) and C₃-C₁₀And said C is a branched alkyl group of₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A) and C₃-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄The same is true.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄Are not identical.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃Selected from hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents selected from, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₄Selected from hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents selected from, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the present invention, the solid catalyst component comprises a magnesium compound, a titanium compound and a reaction product of the general formula (I) with an internal electron donor compound represented by the general formula (II) or (III).

According to a preferred embodiment of the solid catalyst component of the present invention, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor compound is 1 (0.5-150) to (0.02-0.4).

According to a preferred embodiment of the solid catalyst component of the present invention, the molar ratio of the first internal electron donor and the second internal electron donor compound is (1-100): (100-1), preferably (1-50): (50-1), and more preferably (1-20): (20-1).

According to a preferred embodiment of the solid catalyst component of the present invention, the magnesium compound comprises one or more selected from the group consisting of magnesium dihalides, alkoxymagnesium, alkylmagnesium, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides in which one of the halogen atoms of the molecular formula has been replaced by an alkoxy or haloalkoxy group, preferably an alcoholate of magnesium dihalide and/or magnesium dihalide. Preference is given to magnesium dihalides or alcoholates of magnesium dihalides, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.

According to a preferred embodiment of the solid catalyst component according to the invention, the titanium compound comprises TiX_m(OR¹)_4-mOne or more of the compounds, wherein R¹Is C₁-C₂₀X is halogen, and m is more than or equal to 1 and less than or equal to 4.

According to some embodiments of the invention, R¹Is C₁-C₂₀Alkyl of (3), preferably C₁-C₁₀Alkyl, more preferably C₁-C₆An alkyl group.

According to some embodiments of the invention, X is selected from fluorine, chlorine, bromine and iodine.

According to a preferred embodiment of the solid catalyst component of the present invention, the titanium compound preferably comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium, more preferably titanium tetrachloride.

In a second aspect the present invention provides a catalyst system for the polymerisation of olefins comprising the reaction product of:

component a, the solid catalyst component according to the first aspect of the present invention;

component b, an alkyl aluminum compound; and

optionally component c, an external electron donor compound.

According to a preferred embodiment of the present invention, the external electron donor compound comprises a compound represented by the general formula (IV):

R² _kSi(OR³)_4-k (IV)

in the general formula (IV), k is more than or equal to 0 and less than or equal to 3; r²Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r³Is alkyl, cycloalkyl, aryl, haloalkyl or amino.

According to a preferred embodiment of the invention, R²Is C₁-C₁₀Alkyl of (C)₃-C₁₀Cycloalkyl of, C₆-C₂₀Aryl of (C)₁-C₁₀A haloalkyl group, an amino group, a halogen atom or a hydrogen atom.

According to a preferred embodiment of the invention, R³Is C₁-C₁₀Alkyl of (C)₃-C₁₀Cycloalkyl of, C₆-C₂₀Aryl of (C)₁-C₁₀A haloalkyl or amino group.

According to a preferred embodiment of the present invention, the molar ratio of component a, component b and component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).

According to a third aspect of the present invention, there is provided a prepolymerized catalyst for olefin polymerization comprising the solid catalyst component according to the first aspect of the present invention and/or a prepolymer obtained by prepolymerizing an olefin with the catalyst system according to the second aspect of the present invention, wherein the prepolymer has a prepolymerization ratio of 0.1 to 1000g of the olefin polymer per g of the catalyst component(ii) a The olefin has the general formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.

In a fourth aspect, the present invention provides a process for the polymerisation of olefins carried out in the presence of a solid catalyst component according to the first aspect of the present invention and/or a catalyst system according to the second aspect of the present invention and/or a prepolymerised catalyst according to the third aspect of the present invention. The olefin may be of the formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl group of (1). The olefin is preferably ethylene, propylene and/or 1-butene.

The solid catalyst component for olefin polymerization provided by the invention has the following advantages:

(1) by using an alkoxy diaryl phosphate compound and a diol ester compound with special structures to be compounded as an internal electron donor, the prepared catalyst has high activity and stereoregularity, and particularly has good hydrogen regulation sensitivity;

(2) when the catalyst is used for propylene polymerization, the molecular weight distribution of the obtained polymer is wider.

Detailed Description

In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.

As mentioned above, the existing olefin polymerization catalysts are to be improved in all aspects, and because compounds with extremely strong corrosiveness and instability are used in the synthesis process, the catalysts are not beneficial to environmental protection and safety. At present, the catalyst component for olefin polymerization with high activity, good stereospecificity, good hydrogen regulation sensitivity, wide molecular weight distribution of the obtained polymer and other excellent comprehensive properties needs to be researched and developed.

The first aspect of the present invention provides a solid catalyst component for the preparation of olefin polymers, comprising magnesium, titanium, halogen and an internal electron donor compound, the internal electron donor compound comprising a first internal electron donor compound of formula (I) and a second internal electron donor compound of formula (II) or (III),

in the general formula (I), R₁Is C₁-C₁₅Straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl or C₇-C₂₀And said C is aralkyl, and₁-C₁₅straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl and C₇-C₂₀The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent;

R₅、R₆、R₇and R₈Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear chain of (2)Alkenyl radical, C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the arylcarbon of (a) may optionally be substituted by a substituent, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring;

R₁₃and R₁₄Same or differentSame, independently selected from hydrogen and C₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂And said C is a branched alkyl group of₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂The hydrogen on the branched alkyl carbon of (a) may be optionally substituted with a substituent.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₁Is C₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl of, C₇-C₁₅And said C is an aralkyl group₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl of, C₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents selected from the group consisting of.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (I), R₁Is C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₉Straight chain alkyl group of (1), C₁₀-C₁₂Straight chain alkyl group of (1), C₃-C₄Branched alkyl of (5)Base, C₅-C₇Branched alkyl of C₈-C₁₀Branched alkyl of C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl or C₁₃-C₁₅An aralkyl group of (2).

According to the solid catalyst component of the present invention, the compound of formula (I) is selected from, but not limited to, the following compounds:

diphenylmethyl phosphate, diphenylethyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenyl-n-butyl phosphate, diphenylisobutyl phosphate, diphenyl-t-butyl phosphate, diphenyl-n-pentyl phosphate, diphenylisoamyl phosphate, diphenylhexyl phosphate, diphenylheptyl phosphate, diphenyloctyl phosphate, diphenylnonyl phosphate, diphenylbenzyl phosphate, di-2-tolyl-methyl phosphate, di-2-tolyl-ethyl phosphate, di-2-tolyl-n-propyl phosphate, di-2-tolyl-isopropyl phosphate, di-2-tolyl-n-butyl phosphate, di-2-tolyl-isobutyl phosphate, di-2-tolyl-t-butyl phosphate, di-2-tolyl-n-pentyl phosphate, di-tert-butyl phosphate, di-2-tolyl phosphate, di-n-pentyl phosphate, di-octyl phosphate, di-hexyl phosphate, di-tert-hexyl phosphate, di-benzyl phosphate, di-butyl phosphate, di-2-tolyl-n-butyl phosphate, di-pentyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-2-pentyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-2-benzyl phosphate, di-butyl phosphate, di-2-butyl phosphate, di-butyl phosphate, di (2-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (2-tolyl) octyl phosphate, di (2-tolyl) nonyl phosphate, di (2-tolyl) benzyl phosphate, di (4-tolyl) methyl phosphate, di (4-tolyl) ethyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (4-tolyl) hexyl phosphate, Di (4-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) nonyl phosphate, di (4-tolyl) benzyl phosphate, di (4-cumyl) methyl phosphate, di (4-cumyl) ethyl phosphate, di (4-cumyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) n-butyl phosphate, di (4-cumyl) isobutyl phosphate, di (4-cumyl) tert-butyl phosphate, di (4-cumyl) n-pentyl phosphate, di (4-cumyl) isopentyl phosphate, di (4-cumyl) hexyl phosphate, di (4-cumyl) heptyl phosphate, di (4-cumyl) octyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) hexyl phosphate, di (4-cumyl) heptyl phosphate, di (4-isopropyl) butyl phosphate, di (4-isopropyl) heptyl phosphate, di (4-isopropyl) butyl phosphate, n-propyl phosphate, n-butyl phosphate, One or more of di (4-cumyl) octyl phosphate, di (4-cumyl) nonyl phosphate, and di (4-cumyl) benzyl phosphate.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄Identical or different, independently selected from C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅And said C is an aromatic hydrocarbon group₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄The same is phenyl, benzyl, phenethyl or phenylpropyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₃And R₄Different from phenyl, benzyl, phenylethyl and phenylpropyl.

According to a preferred embodiment of the solid catalyst component of the present invention, in the general formula (II), R₈Is hydrogen, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl or C₆-C₈Branched alkyl of (2) is, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butylA radical or a pentyl radical.

According to the solid catalyst component of the present invention, the compound in the general formula (II) is selected from, but not limited to, the following compounds:

1, 2-phenylene dibenzoate, 1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 4-methyl-1, 2-phenylene dibenzoate, 4-methyl-1, 2-phenylene bis (2-methylbenzoate), 4-methyl-1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 4-tert-butyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene bis (2-methylbenzoate), 4-tert-butyl-1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 3, 6-dimethyl-1, 2-phenylene dibenzoate, and the like, 3, 6-dichloro-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3-tert-butyl-5-methyl-1, 2-phenylene dibenzoate, 3, 5-di-tert-butyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene bis (4-methylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylene bis (4-ethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylene bis (4-ethoxybenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (4-fluorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (4-chlorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (2,4, 6-trimethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (1-naphthoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (2-naphthoate), 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, and the like.

Solid catalysis according to the inventionA preferred embodiment of the reagent component, in the general formula (III), R₉And R₁₀Same or different, independently selected from hydrogen, halogen atom, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈Branched alkyl of R₉And R₁₀Optionally bonded to form a ring.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉And R₁₀Likewise, hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₉And R₁₀Not identical, independently selected from hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂Identical or different, independently selected from C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂Likewise, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₁And R₁₂Different from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄Identical or different, independently selected from hydrogen and C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀And said C is a branched alkyl group of₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents selected from the group consisting of.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄The same is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl.

According to a preferred embodiment of the solid catalyst component of the invention, in the general formula (III), R₁₃And R₁₄Different from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and pentyl.

According to the solid catalyst component of the present invention, the compound of formula (III) is selected from, but not limited to, the following compounds:

2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (4-methylbenzoate), 2, 4-pentanediol di (3-methylbenzoate), 2, 4-pentanediol di (2-methylbenzoate), 2, 4-pentanediol di (4-ethylbenzoate), 2, 4-pentanediol di (4-n-propylbenzoate), 2, 4-pentanediol di (4-isopropylbenzoate), 2, 4-pentanediol di (4-n-butylbenzoate), 2, 4-pentanediol di (4-isobutylbenzoate), 2, 4-pentanediol di (4-tert-butylbenzoate), 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol di (4-methylbenzoate), 3-ethyl-2, 4-pentanediol di (4-ethylbenzoate), 3-ethyl-2, 4-pentanediol di (4-n-propylbenzoate), 3-ethyl-2, 4-pentanediol di (4-isopropylbenzoate), 3-ethyl-2, 4-pentanediol di (4-n-butylbenzoate), 3-ethyl-2, 4-pentanediol di (4-isobutyl benzoate), 3-ethyl-2, 4-pentanediol di (4-tert-butylbenzoate), 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 3-chloro-2, 4-pentanediol dibenzoate, 3-bromo-2, 4-pentanediol dibenzoate, 3, 5-heptanediol bis (4-methylbenzoate), 3, 5-heptanediol bis (4-ethylbenzoate), 3, 5-heptanediol bis (4-n-propylbenzoate), 3, 5-heptanediol bis (4-isopropylbenzoate), 3, 5-heptanediol bis (4-n-butylbenzoate), 3, 5-heptanediol bis (4-isobutyl benzoate), 3, 5-heptanediol bis (4-tert-butylbenzoate), 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol bis (4-methylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-ethylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-propylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isopropylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-butylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isobutyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-tert-butylbenzoate), 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 4-chloro-3, 5-heptanediol dibenzoate, 4-bromo-3, 5-heptanediol dibenzoate, and the like.

In some embodiments of the invention, the magnesium compound comprises one or more of a magnesium dihalide, an alkoxy magnesium, an alkyl magnesium, a hydrate or alcoholate of a magnesium dihalide, and a derivative of a magnesium dihalide in which one halogen atom of the formula is replaced by an alkoxy group or a haloalkoxy group; preferably, the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide; more preferably, the magnesium compound is an alcoholate of a magnesium dihalide, such as magnesium dichloride, magnesium dibromide, magnesium diiodide and alcoholates thereof.

In some embodiments of the invention, the titanium compound comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium chlorotriethoxylate, titanium dichlorodiethoxide, and titanium trichloromonoethoxylate; preferably, the titanium compound is titanium tetrachloride.

In the invention, the solid catalyst component can be obtained by dissolving a magnesium compound in a solvent system containing a hydrocarbon compound and an alcohol compound, then mixing a titanium compound with the solution at the temperature of minus 40-40 ℃, adding an electron donor compound at the temperature of minus 40-150 ℃, and washing by an inert diluent.

The hydrocarbon compound comprises straight chain or branched C₆-C₁₂Alkane and C₆-C₁₅The aromatic hydrocarbon of (2) is, for example, hexane, heptane, octane, nonane, decane, benzene, toluene, xylene, etc.

The alcohol compound comprises aliphatic alcohol, alicyclic alcohol and aromatic alcohol, wherein the aliphatic alcohol is straight chain or branched chain C₁-C₁₀Aliphatic alcohols, alicyclic alcohols being C₃-C₁₀The aromatic alcohol is C₆-C₂₀Aryl or alkylaryl alcohols of (a); such as ethanol, propanol, butanol, pentanol, hexanol, octanol, isooctanol, and the like, or mixtures thereof.

The inert diluent is selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene and xylene.

The solid catalyst component described in the present invention can be prepared by the following method: the solid catalyst component was prepared according to the method disclosed in patent CN 1040379. Firstly, mixing a magnesium compound with an organic alcohol compound according to a molar ratio of 2-5 and an inert solvent, heating to 120-150 ℃, and reacting for 1-5 hours according to a molar ratio of magnesium/anhydride of 5-10. Then adding the alcohol compound cooled to room temperature into the titanium compound solution precooled to minus 15 to minus 40 ℃ according to the molar ratio of titanium to magnesium of 20-50, heating to 90-110 ℃, adding an internal electron donor compound selected from the compounds shown in the general formulas (I) and (II) according to the molar ratio of magnesium to electron donor of 2-10, reacting at the temperature of 100 ℃ and 130 ℃ for 1-3 hours, and filtering to separate solid particles. Then adding the solid particles into the titanium compound solution according to the molar ratio of titanium to magnesium of 20-50, stirring and reacting at the temperature of 100-130 ℃ for 1.5-3 hours, and filtering to separate the solid particles. Finally, washing the solid particles by using an inert solvent with the temperature of 50-80 ℃, and drying to obtain the solid catalyst component.

component b, an alkyl aluminum compound; and

optionally component c, an external electron donor compound.

R² _kSi(OR³)_4-k (IV)

In the catalyst system of the invention, the alkyl aluminum compound has a general formula of AlR³ _nX_3-nA compound of (1), wherein R³Is hydrogen or alkyl with 1-20 carbon atoms, X is halogen, and n is a number which is more than 1 and less than or equal to 3. Specifically, the aluminum chloride can be selected from one or more of triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-octyl aluminum, diethyl aluminum monohydrogen, diisobutyl aluminum monohydrogen, diethyl aluminum monochloride, diisobutyl aluminum monochloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride. Preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.

For the application of olefin polymers with high stereoregularity, an external electron donor compound is added, for example, the general formula R² _kSi(OR³)_4-kIn the formula, k is more than or equal to 0 and less than or equal to 3, R²And R³Is the same or different alkyl, cycloalkyl, aryl, haloalkyl, R²And may be a halogen or hydrogen atom. Preferably, R²And R³Each independently is C₁-C₁₀Alkyl radical, C₃-C₁₀Cycloalkyl radical, C₆-C₁₂Aryl radical, C₁-C10 haloalkyl. Examples of the organosilicon compound include: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, diisobutyldiethoxysilane, dibutyldimethoxysilane, preferably cyclohexylmethyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane.

In a third aspect, the present invention provides a prepolymerised catalyst for the polymerisation of olefinsAn agent comprising a prepolymer obtained by prepolymerizing an olefin with the solid catalyst component according to the first aspect of the present invention and/or the catalyst system according to the second aspect of the present invention, wherein the prepolymer has a prepolymerization ratio of 0.1 to 1000g of olefin polymer per g of catalyst component. The olefin has the general formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl group of (1). The olefin is preferably ethylene, propylene and/or 1-butene.

The expression "prepolymerized catalyst" as used in the present invention refers to a catalyst which has undergone a polymerization step with a relatively low degree of conversion. According to the invention, the prepolymerization can be carried out using the same alpha-olefin as the olefin used for the polymerization, the olefin to be subjected to the prepolymerization preferably being ethylene, propylene or 1-butene. In particular, it is particularly preferred to carry out the prepolymerization with ethylene or a mixture of one or more alpha-olefins in a remaining amount of up to 20 mol%. Preferably, the degree of conversion of the prepolymerized catalyst component is from about 0.2 to 500 grams of polymer per gram of solid catalyst component.

The expression "prepolymerized olefin" as used herein means an alpha-olefin, preferably ethylene and/or propylene, which is used in a prepolymerization reaction with the solid catalyst component or catalyst system as described herein to obtain a prepolymerized catalyst.

The prepolymerization step can be carried out at a temperature of-20 ℃ to 80 ℃, preferably 0-50 ℃, in liquid or gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation. For the preparation of polymers in amounts of from 0.5 to 20g/g of catalyst component, batch prepolymerization of the catalyst of the invention with ethylene is particularly preferred. The polymerization pressure is 0.01-10 MPa.

In a fourth aspect, the present invention provides a process for the polymerisation of olefins carried out in the presence of a solid catalyst component according to the first aspect of the present invention and/or a catalyst system according to the second aspect of the present invention and/or a prepolymerised catalyst according to the third aspect of the present invention. The olefin may be of the formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl group of (1). The olefin is preferably ethylenePropylene and/or 1-butene.

The catalysts of the invention are also suitable for the production of polyethylene and copolymers of ethylene with alpha-olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene.

The catalyst of the present invention may be added directly to the reactor for use in the polymerization process. Alternatively, the catalyst may be prepolymerized before being fed into the first polymerization reactor.

The olefin polymerization reaction of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in an operation combining liquid phase and gas phase polymerization stages. Conventional techniques such as slurry processes, gas phase fluidized beds and the like are employed wherein the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, particularly the homopolymerization of propylene or the copolymerization of propylene with other olefins. The following reaction conditions are preferably employed: the polymerization temperature is 0-150 ℃. Preferably, the polymerization temperature is 60 to 90 ℃.

The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

The following examples are given for the purpose of illustrating the invention and are not to be construed as limiting the invention.

The test method of the invention is as follows:

(1) polymer isotactic index II: as determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight of the polymer (g) to 2, which was obtained by drying the residue to a constant weight, was defined as the isotactic index.

(2) Melt index MI: measured using a melt index apparatus at 230 ℃ under a pressure of 2.16kg according to ASTM D1238-99 Standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.

(3) Polymer molecular weight distribution MWD (MWD ═ Mw/Mn): measured at 150 ℃ by gel permeation chromatography using PL-GPC220 with trichlorobenzene as a solvent (standard: polystyrene, flow rate: 1.0mL/min, column: 3xPlgel 10um M1 xED-B300 x7.5nm).

Examples 1 to 7 and comparative examples 1 to 5

(1) Preparation of solid catalyst component a

Under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent into a 500ml reactor provided with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 1.1g of phthalic anhydride, and continuously maintaining the temperature of 130 ℃ to react for 1 hour to obtain an alcohol compound; the alcohol hydrate was cooled to room temperature.

Under the protection of nitrogen, the alcohol compound is dropwise added into 120ml of titanium tetrachloride solution precooled to minus 22 ℃, the temperature is slowly increased to 100 ℃, 6mmol of the compound internal electron donor compound shown in the table 1 is added, the temperature is increased to 110 ℃ and maintained for 2 hours, and the mixture is filtered while the mixture is hot. Then, 120ml of titanium tetrachloride was added thereto, the temperature was raised to 110 ℃ to react for 1 hour, and the solid particles were filtered, washed 4 times with anhydrous hexane, and dried to obtain a solid catalyst component a.

(2) Experiment on propylene polymerization

The solid catalyst components obtained above were separately subjected to propylene polymerization. The propylene polymerization procedure was: a stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and 2.5mmol of AlEt is added₃And 0.l mmol of dicyclopentyldimethoxysilane as an external electron donor compound, adding 8-10mg of solid catalyst component and 1.2NL of hydrogen, introducing 2.3L of liquid propylene, heating to 70 ℃, and maintaining the temperature for 1 hour; and (3) reducing the temperature and relieving the pressure to obtain PP powder of examples 1-7 and comparative examples 1-5. The data are shown in Table 1.

TABLE 1 propylene polymerization results

Wherein:

a: bis (4-tolyl) benzyl phosphate 4, 6-nonanediol dibenzoate (molar ratio) ═ 10:1

B: diphenyl tert-butyl phosphate 3, 5-heptanediol di-p-isobutyl benzoate (molar ratio) ═ 1:9

C: di (4-cumyl) n-nonyl phosphate 2, 4-pentanediol dibenzoate (molar ratio) ═ 5:1

D: diphenylmethyl phosphate 3-ethyl-2, 4-pentanediol di-n-butylbenzoate (molar ratio) ═ 1:1

E: tributyl phosphate 2, 4-pentanediol dibenzoate (molar ratio) ═ 5:1

F: triphenyl phosphate 2, 4-pentanediol dibenzoate (molar ratio) ═ 5:1

Diphenyl tert-butyl phosphate 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate (molar ratio) 8:1

H: bis (4-tolyl) methyl phosphate 2, 3-naphthalene dibenzoate (molar ratio) ═ 1:6

I: bis (4-cumenyl) n-nonyl phosphate 4-methyl-1, 2-phenylenedi (2-methylbenzoate) (molar ratio) ═ 1:1

As can be seen from Table 1, the catalyst system provided by the invention can greatly improve the hydrogen response while keeping high polymerization activity and isotactic index of the catalyst and wide molecular weight distribution of the obtained polymer, and the obtained polymer has excellent comprehensive performance, which is very beneficial to the development of different grades of resins.

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 component for preparing olefin polymers comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound comprises a first internal electron donor compound with a general formula (I) and a second internal electron donor compound with a general formula (II) or (III),

in the general formula (I),

R₁is C₁-C₁₅Straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl or C₇-C₂₀And said C is aralkyl, and₁-C₁₅straight chain alkyl group of (1), C₃-C₁₅Branched alkyl of C₃-C₁₅Cycloalkyl and C₇-C₂₀The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent;

in the general formula (II), the compound represented by the formula (II),

R₃and R₄Identical or different, independently selected from C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₅A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the arylcarbon of (a) is optionally substituted with a substituent;

in the general formula (III),

R₉and R₁₀Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀Aryl of (2), R₉And R₁₀Optionally bonded to form a ring;

R₁₁and R₁₂Identical or different, independently selected from halogen atoms, C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀And said C is an aromatic hydrocarbon group₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A), C₃-C₁₀A branched hydrocarbon group of₃-C₁₀A cycloalkyl group of₆-C₂₀Aryl of (C)₇-C₂₀And C is a hydrocarbon aryl group₇-C₂₀The hydrogen on the aromatic carbon of (a) is optionally substituted with a substituent；

R₁₃And R₁₄Identical or different, independently selected from hydrogen and C₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂And said C is a branched alkyl group of₁-C₁₂Straight chain alkyl group of (1), C₂-C₁₂Linear alkenyl of (A) and C₃-C₁₂The hydrogen on the branched alkyl carbon of (a) is optionally substituted with a substituent,

preferably, the substituents are selected from hydroxy, amino, C₁-C₆Alkyl-substituted amino, -CHO, -COOH, halogen atom, C₁-C₆Alkyl and C₁-C₆Alkoxy group of (2).

2. The solid catalyst component according to claim 1 in which in the general formula (I), R is₁Is C₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl or C₇-C₁₅And said C is an aralkyl group₁-C₁₂Straight chain alkyl group of (1), C₃-C₁₀Branched alkyl of C₃-C₁₂Cycloalkyl and C₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with one or more substituents;

R₂is hydrogen, halogen atom, C₁-C₈Straight chain alkyl or C₃-C₁₀And said C is a branched alkyl group of₁-C₈Straight chain alkyl of (2) and C₃-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents,

preferably, R₁Is C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₉Straight chain alkyl group of (1), C₁₀-C₁₂Straight chain alkyl group of (1), C₃-C₄Branched alkyl of C₅-C₇Branched alkyl of C₈-C₁₀Branched alkyl of C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl or C₁₃-C₁₅Aralkyl of (b) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, benzyl, phenethyl or phenylpropyl,

more preferably, said compound of formula (I) is selected from the group consisting of diphenylmethyl phosphate, diphenylethyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenyl-n-butyl phosphate, diphenylisobutyl phosphate, diphenyl-t-butyl phosphate, diphenyl-n-pentyl phosphate, diphenylisopentyl phosphate, diphenylhexyl phosphate, diphenylheptyl phosphate, diphenyloctyl phosphate, diphenylnonyl phosphate, diphenylbenzyl phosphate, di-2-tolyl methyl phosphate, di-2-tolyl ethyl phosphate, di-2-tolyl-n-propyl phosphate, di-2-tolyl isopropyl phosphate, di-2-tolyl-n-butyl phosphate, di-2-tolyl isobutyl phosphate, di-2-tolyl-t-butyl phosphate, di-2-tolyl-n-butyl phosphate, diphenyl-n-propyl phosphate, diphenylisopropyl phosphate, diphenylethyl phosphate, diphenylisopropyl phosphate, diphenylmethyl phosphate, diphenylisopropyl phosphate, tert-2-butyl phosphate, and mixtures thereof, Di (2-tolyl) n-pentyl phosphate, di (2-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (2-tolyl) octyl phosphate, di (2-tolyl) nonyl phosphate, di (2-tolyl) benzyl phosphate, di (4-tolyl) methyl phosphate, di (4-tolyl) ethyl phosphate, di (4-tolyl) n-propyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (2-tolyl) hexyl phosphate, di (2-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) isopropyl phosphate, di (4-tolyl) n-butyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) t-butyl phosphate, di (4-tolyl) n-pentyl phosphate, di (4-tolyl) isoamyl phosphate, di (4-tolyl) isobutyl phosphate, di (4-tolyl) butyl phosphate, di (4-butyl) butyl phosphate, di (4-tolyl) butyl phosphate, di (4-butyl) butyl phosphate, di (4-butyl phosphate, di-butyl) butyl phosphate, di-butyl phosphate, di (4-butyl phosphate, di-butyl phosphate, n-butyl phosphate, di-butyl phosphate, and the like, Di (4-tolyl) hexyl phosphate, di (4-tolyl) heptyl phosphate, di (4-tolyl) octyl phosphate, di (4-tolyl) nonyl phosphate, di (4-tolyl) benzyl phosphate, di (4-cumyl) methyl phosphate, di (4-cumyl) ethyl phosphate, di (4-cumyl) n-propyl phosphate, di (4-cumyl) isopropyl phosphate, di (4-cumyl) n-butyl phosphate, di (4-cumyl) isobutyl phosphate, di (4-cumyl) tert-butyl phosphate, di (4-cumyl) n-pentyl phosphate, di (4-cumyl) isoamyl phosphate, di (4-cumyl) hexyl phosphate, One or more of di (4-cumyl) heptyl phosphate, di (4-cumyl) octyl phosphate, di (4-cumyl) nonyl phosphate and di (4-cumyl) benzyl phosphate.

3. The solid catalyst component according to claim 1 or 2, characterized in that in the general formula (II), R is₃And R₄Identical or different, independently selected from C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted with a substituent,

R₅、R₆、R₇and R₈Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₁₀Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted by one or more substituents, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring;

preferably, R₃And R₄Same or different, independently selected from C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅Aralkyl of (2), said C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the arylcarbon of (a) is optionally substituted with one or more substituents,

R₅、R₆、R₇and R₈Identical or different, independently selected from hydrogen and C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl of C₆-C₈Branched alkyl of C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅And said C is aralkyl, and₁-C₃straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₃-C₅Branched alkyl of C₆-C₈Branched alkyl of C₆-C₈Aryl of (C)₉-C₁₁Aryl of (C)₁₂-C₁₅Aryl of (C)₇-C₉Alkylaryl of, C₁₀-C₁₂Alkylaryl of, C₁₃-C₁₅Alkylaryl of, C₇-C₉Aralkyl of (2), C₁₀-C₁₂Aralkyl and C₁₃-C₁₅The hydrogen on the aralkyl carbon of (a) may be optionally substituted by one or more substituents, R₅、R₆、R₇And R₈Any two adjacent groups may be bonded to form a ring;

more preferably, the compound of formula (II) is selected from 1, 2-phenylene dibenzoate, 1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 4-methyl-1, 2-phenylene dibenzoate, 4-methyl-1, 2-phenylene bis (2-methylbenzoate), 4-methyl-1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 4-tert-butyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene bis (2-methylbenzoate), 4-tert-butyl-1, 2-phenylene bis (2,4, 6-trimethylbenzoate), 3, 6-dimethyl-1, 2-phenylene dibenzoate, 3, 6-dichloro-1, 2-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene dibenzoate, 3-tert-butyl-5-methyl-1, 2-phenylene dibenzoate, 3, 5-di-tert-butyl-1, 2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1, 2-phenylene bis (4-methylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylene bis (4-ethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (4-ethoxybenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (4-fluorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (4-chlorobenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenebis (2,4, 6-trimethylbenzoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (1-naphthoate), 3-methyl-5-tert-butyl-1, 2-phenylenedi (2-naphthoate), 1, 2-naphthalene dibenzoate, and 2, 3-naphthalene dibenzoate.

4. The solid catalyst component according to any one of claims 1 to 3, characterized in that in the general formula (III), R is₉And R₁₀Identical or different, independently selected from hydrogen, halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅Aralkyl of (2), R₉And R₁₀Optionally bonded to form a ring;

R₁₁and R₁₂Identical or different, independently selected from halogen atoms, C₁-C₈Straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl or C of₇-C₁₅And said C is aralkyl, and₁-C₈straight chain alkyl group of (1), C₂-C₈Linear alkenyl of (A), C₃-C₈Branched alkyl of C₃-C₈Cycloalkyl of, C₆-C₁₅Aryl of (C)₇-C₁₅Alkylaryl and C of₇-C₁₅The hydrogen on the aralkyl carbon of (a) is optionally substituted with one or more substituents selected from the group consisting of;

R₁₃and R₁₄Identical or different, independently selected from hydrogen and C₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A) and C₃-C₁₀And said C is a branched alkyl group of₁-C₁₀Straight chain alkyl group of (1), C₂-C₁₀Linear alkenyl of (A) and C₃-C₁₀The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents.

5. The solid catalyst component according to any one of claims 1 to 4, characterized in that in the general formula (III), R is₉And R₁₀Same or different, independently selected from hydrogen, halogen atom, C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈Branched alkyl radicals of, e.g. hydrogen, fluorine, chlorineBromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl, R₉And R₁₀Optionally bonded to form a ring;

R₁₁and R₁₂Identical or different, independently selected from C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈Branched alkyl of (2) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl, and C is₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₆Linear alkenyl of (A), C₃-C₅Branched alkyl and C₆-C₈The hydrogen on the branched alkyl carbon of (a) is optionally substituted with one or more substituents;

R₁₃and R₁₄Identical or different, independently selected from hydrogen and C₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀Branched alkyl of (2) is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or pentyl, and C is₁-C₃Straight chain alkyl group of (1), C₄-C₆Straight chain alkyl group of (1), C₇-C₁₀Straight chain alkyl group of (1), C₂-C₄Linear alkenyl of (A), C₅-C₇Linear alkenyl of (A), C₈-C₁₀Linear alkenyl of (A), C₃-C₅Branched alkyl of C₆-C₉Branched alkyl and C₉-C₁₀The hydrogen on the branched alkyl carbon of (A) is optionally selectedSubstituted by one or more substituents selected from the group consisting of,

more preferably, the compound of formula (III) is selected from the group consisting of 2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (4-methylbenzoate), 2, 4-pentanediol di (3-methylbenzoate), 2, 4-pentanediol di (2-methylbenzoate), 2, 4-pentanediol di (4-ethylbenzoate), 2, 4-pentanediol di (4-n-propylbenzoate), 2, 4-pentanediol di (4-isopropylbenzoate), 2, 4-pentanediol di (4-n-butylbenzoate), 2, 4-pentanediol di (4-isobutylbenzoate), 2, 4-pentanediol di (4-tert-butylbenzoate), 3-methyl-2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (4-n-butylbenzoate), 2, 4-pentanediol di (4-butylbenzoate), 2, 4-methyl-pentanediol dibenzoate, 2, 4-pentanediol dibenzoate, and mixtures thereof, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol di (4-methylbenzoate), 3-ethyl-2, 4-pentanediol di (4-ethylbenzoate), 3-ethyl-2, 4-pentanediol di (4-n-propylbenzoate), 3-ethyl-2, 4-pentanediol di (4-isopropylbenzoate), 3-ethyl-2, 4-pentanediol di (4-n-butylbenzoate), 3-ethyl-2, 4-pentanediol di (4-isobutylbenzoate), 3-ethyl-2, 4-pentanediol di (4-tert-butylbenzoate), 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 3-chloro-2, 4-pentanediol dibenzoate, 3-bromo-2, 4-pentanediol dibenzoate, 3, 5-heptanediol bis (4-methylbenzoate), 3, 5-heptanediol bis (4-ethylbenzoate), 3, 5-heptanediol bis (4-n-propylbenzoate), 3, 5-heptanediol bis (4-isopropylbenzoate), 3, 5-heptanediol bis (4-n-butylbenzoate), 3, 5-heptanediol bis (4-isobutyl benzoate), 3, 5-heptanediol bis (4-tert-butylbenzoate), 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol bis (4-methylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-ethylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-propylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isopropylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-n-butylbenzoate), 4-ethyl-3, 5-heptanediol bis (4-isobutyl benzoate), 4-ethyl-3, 5-heptanediol bis (4-tert-butylbenzoate), 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 4-chloro-3, 5-heptanediol dibenzoate, and 4-bromo-3, 5-heptanediol dibenzoate.

6. The solid catalyst component according to any of claims 1 to 5, wherein the solid catalyst component comprises the reaction product of a magnesium compound, a titanium compound and an internal electron donor compound, preferably the molar ratio of magnesium compound, titanium compound and internal electron donor compound is 1 (0.5-150) to (0.02-0.4);

and/or the molar ratio of the first internal electron donor compound to the second internal electron donor compound is (1-100): (100-1), preferably (1-50): (50-1), and more preferably (1-20): (20-1).

7. The solid catalyst component according to any one of claims 1 to 6, characterized in that the magnesium compound comprises one or more selected from magnesium dihalides, magnesium alkoxides, magnesium alkyls, hydrates or alcoholates of magnesium dihalides and derivatives of magnesium dihalides of which one halogen atom of the molecular formula is replaced by an alkoxy or haloalkoxy group, preferably magnesium dihalides and/or magnesium dihalide alcoholates;

and/or the titanium compound comprises a compound selected from TiX_m(OR¹)_4-mOne or more of the compounds, wherein R¹Is C₁-C₂₀X is halogen, m is more than or equal to 1 and less than or equal to 4; the titanium compound is preferably one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium; more preferably titanium tetrachloride.

8. A catalyst system for the polymerization of olefins comprising the reaction product of:

component a, a solid catalyst component according to any one of claims 1 to 7;

component b, an alkyl aluminum compound; and

optionally component c, an external electron donor compound, preferably said external electron donor compound comprises a compound of formula (IV):

R² _kSi(OR³)_4-k(IV)

in the general formula (IV), k is more than or equal to 0 and less than or equal to 3; r²Is an alkyl, cycloalkyl, aryl, haloalkyl, amino, halogen or hydrogen atom; r³Is alkyl, cycloalkyl, aryl, haloalkyl or amino, preferably, R²Is C₁-C₁₀Alkyl of (C)₃-C₁₀Cycloalkyl of, C₆-C₂₀Aryl of (C)₁-C₁₀A haloalkyl group of (a), an amino group, a halogen atom or a hydrogen atom; r³Is C₁-C₁₀Alkyl of (C)₃-C₁₀Cycloalkyl of, C₆-C₂₀Aryl of (C)₁-C₁₀Haloalkyl or amino of (a);

preferably, the molar ratio of the component a to the component b to the component c is 1 (5-1000) to (0-500) in terms of titanium to aluminum to silicon; preferably 1 (25-100) to (25-100).

9. A prepolymerized catalyst for olefin polymerization comprising the solid catalyst component according to any one of claims 1 to 7 and/or a prepolymer obtained by prepolymerizing the catalyst system according to claim 8 with an olefin, wherein the prepolymer has a prepolymerization ratio of 0.1 to 1000g of olefin polymer per g of catalyst component; the olefin has the general formula CH₂Wherein R is hydrogen or C₁-C₆Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.

10. A process for the polymerization of olefins having the general formula CH, in the presence of a solid catalyst component according to any of claims 1 to 7 and/or a catalyst system according to claim 8 and/or a prepolymerized catalyst according to claim 9₂Wherein R is hydrogen or C₁-C₆Alkyl groups of (a); the olefin is preferably ethylene, propylene and/or 1-butene.