CN112300302B - Twelve-membered ring compound and application thereof - Google Patents

Abstract

The invention relates to a twelve-membered ring compound and application thereof, in particular to application of the twelve-membered ring compound shown in a formula A as an electron donor, especially an external electron donor in a catalyst system for olefin polymerization. The invention also relates to a catalyst system for the polymerization of olefins comprising: 1) A solid catalyst component containing magnesium, titanium, halogen and an internal electron donor; 2) An alkyl aluminum compound; and 3) an external electron donor; wherein the external electron donor comprises a compound shown as a formula A. The catalyst system provided by the invention has higher stereospecificity.

Description

Twelve-membered ring compound and application thereof

Technical Field

The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a twelve-membered ring compound and application thereof in the field of olefin polymerization catalysts.

Background

It is known that the activity, stereospecificity, hydrogen sensitivity and copolymerization properties of Ziegler-Natta type polyolefin catalysts are important technical parameters in order to meet the demands of industrial production and to produce products with excellent properties. Catalysts having excellent comprehensive properties have been the target of efforts of polyolefin resin manufacturers and research and development institutions.

The core Ziegler-Natta catalyst used as polyolefin technology mainly comprises magnesium/titanium/internal electron donor, and the catalyst is often matched with aluminum alkyl and external electron donor together to form a complete catalyst system. The external electron donor has the remarkable characteristics of rich types, flexible and controllable addition, large influence on various performances of the catalyst and the like, so that the regulation and control of the overall performance of the catalyst by selecting a proper external electron donor is an important direction for the research and development of the catalyst.

Disclosure of Invention

The inventors of the present invention have found that the compounds of formula a can be used as electron donors, in particular external electron donors, in catalyst systems for the polymerization of Ziegler-Natta olefins. When a catalyst system comprising a twelve-membered ring compound represented by formula A as an external electron donor is used for olefin polymerization, the stereospecificity of the catalyst can be improved.

In a first aspect, the present invention provides the use of a compound of formula A as an electron donor, in particular an external electron donor, in a catalyst system for the polymerization of olefins,

in the formula A, the components of the compound,

M ₁ to M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl, when two adjacent groups on the benzene ring are each selected from R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ In the case of heteroaryl groups, two adjacent groups may optionally form a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and combinations thereof,

wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and aryl groupsAny of alkyl, heterocycloalkyl, and heteroaryl may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

In a second aspect, the present invention provides a catalyst system for the polymerization of olefins comprising:

1) A solid catalyst component containing magnesium, titanium, halogen and an internal electron donor;

2) An alkyl aluminum compound; and

3) An external electron donor;

wherein the external electron donor comprises a compound shown as a formula A,

in the formula A, the components of the compound,

M ₁ to M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl, when two adjacent groups on the benzene ring are each selected from R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ In the case of the heteroaryl group,two adjacent groups may optionally form a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

Any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

In a third aspect, the present invention provides a prepolymerized catalyst composition for olefin polymerization comprising a prepolymer obtained by prepolymerizing the catalyst system according to the second aspect with an olefin.

According to some embodiments of the invention, the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of solid catalyst component.

According to some preferred embodiments of the invention, the prepolymer has a prepolymerization multiple of 0.2 to 500g of olefin polymer per g of solid catalyst component.

According to some preferred embodiments of the invention, the prepolymer has a prepolymerization multiple of 0.5 to 20g of olefin polymer per g of solid catalyst component.

According to some embodiments of the invention, the temperature of the prepolymerization is from-20 to 80℃and the polymerization pressure is preferably from 0 to 5MPa.

According to some preferred embodiments of the invention, the temperature of the prepolymerization is 0-50 ℃.

According to some embodiments of the invention, the pre-polymerization is performed in liquid or in gas phase.

In a fourth aspect, the present invention provides a process for the polymerization of olefins, wherein the olefins are polymerized in the presence of the catalyst system according to the second aspect and/or the prepolymerized catalyst composition according to the third aspect, the olefins having the general formula CH ₂ =chr, wherein R is hydrogen or C ₁ -C ₆ Alkyl, said olefin polymerization may be a homo-polymerization of a single said olefin or a co-polymerization of a plurality of said olefins.

According to some preferred embodiments of the 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 a fifth aspect, the present invention provides the use of a catalyst system according to the second aspect and/or a pre-polymerisation catalyst composition according to the third aspect in an olefin polymerisation reaction.

The invention adopts the twelve-membered ring compound shown in the formula A as an external electron donor and alkyl aluminum as a cocatalyst, and can improve the stereospecificity of a catalyst system by being matched with a solid catalyst component.

Detailed Description

In a first aspect, the present invention provides the use of a compound of formula A as an electron donor, in particular an external electron donor, in a catalyst system for the polymerization of olefins,

in the formula A, the components of the compound,

M ₁ to M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl, when two adjacent groups on the benzene ring are each selected from R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ In the case of heteroaryl groups, two adjacent groups may optionally form a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and combinations thereof,

wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may optionally be used Is substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the invention, in formula a, M ₁ To M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, wherein R _a Selected from C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl groups.

According to some embodiments of the invention, in formula A, M ₁ To M ₁₆ Selected from hydrogen, hydroxy, amino, halogen, aldehyde, and C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some preferred embodiments of the invention, in formula A, M ₁ To M ₁₆ Not both hydrogen.

According to some embodiments of the invention, in formula a, M ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ And M ₁₆ Each independently selected from hydrogen and C ₁ -C ₆ An alkyl group.

According to some embodiments of the invention, in formula a, M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ And M ₁₅ Selected from hydroxy, amino, halogen, aldehyde, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some embodiments of the invention, M ₁ 、M ₅ 、M ₉ 、M ₁₃ The same applies.

According to some embodiments of the invention, M ₂ 、M ₆ 、M ₁₀ 、M ₁₄ The same applies.

According to some embodiments of the invention, M ₃ 、M ₇ 、M ₁₁ 、M ₁₅ The same applies.

According to some embodiments of the invention, M ₄ 、M ₈ 、M ₁₂ 、M ₁₆ The same applies.

According to some embodiments of the invention, R _a Selected from C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl and C ₇ -C ₁₀ Aralkyl, wherein any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, and carboxyl.

According to some embodiments of the invention, in formula a, R ₁ To R ₈ Each independently selected from hydrogen, C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, in said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groupsOptionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the invention, in formula a, R ₁ To R ₈ The same or different, each independently selected from hydrogen and C ₁ -C ₆ Alkyl, C ₁ -C ₆ The alkyl group may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the invention, R ₁ To R ₈ Independently selected from hydrogen and C ₁ -C ₆ An alkyl group.

According to some embodiments of the invention, R ₁ 、R ₃ 、R ₅ 、R ₇ The same applies.

According to some embodiments of the invention, R ₂ 、R ₄ 、R ₆ 、R ₈ The same applies.

According to some embodiments of the invention, R ₁ To R ₈ All the same.

According to a preferred embodiment of the invention, M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ And M ₁₅ Is C ₁ -C ₈ An alkoxy group; and M is ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ 、M ₁₆ Selected from hydrogen, hydroxy, amino, halogen, aldehyde, and C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some embodiments of the invention, the structure of the compound of formula a is as shown in formula A1, A2 or A3.

According to some embodiments of the invention, the twelve-membered ring compound represented by formula a or a derivative thereof is selected from at least one of the following compounds:

Compound a: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound B: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound C: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound D: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH(CH ₃ ) ₂ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound E: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound F: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound G: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound H: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound I: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OH，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound J: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OH，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound K: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝NH ₂ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound L: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝Cl，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound M: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝Br，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound N: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝I，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound O: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝CHO，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound P: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ Br，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound Q: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ Cl；

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound R: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OH；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H。

According to some embodiments of the invention, the olefin has the formula CH ₂ =chr, wherein R is hydrogen or C ₁ -C ₁₂ Is a hydrocarbon group or an aryl group.

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; the olefin polymerization may be a homo-polymerization of a single said olefin or a co-polymerization of a plurality of said olefins.

In a second aspect, the present invention provides a catalyst system for the polymerization of olefins comprising:

1) A solid catalyst component containing magnesium, titanium, halogen and an internal electron donor;

2) An alkyl aluminum compound; and

3) An external electron donor;

wherein the external electron donor comprises a compound shown as a formula A,

in the formula A, the components of the compound,

M ₁ to M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl, when two adjacent groups on the benzene ring are each selected from R _a C(O)-、R _a O-、C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ In the case of heteroaryl groups, two adjacent groups may optionally form a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring and combinations thereof,

wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ Heteroaryl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the catalyst systems provided herein, formula A, M ₁ To M ₁₆ The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl, R _a C(O)-、R _a O-、C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, wherein R _a Selected from C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl groups.

According to some embodiments of the catalyst systems provided herein, formula A, M ₁ To M ₁₆ Selected from hydrogen, hydroxy, amino, halogen, aldehyde, and C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some preferred embodiments of the invention, in formula A, M ₁ To M ₁₆ Not both hydrogen.

According to some embodiments of the catalyst systems provided herein, formula A, M ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ And M ₁₆ Each independently selected from hydrogen and C ₁ -C ₆ An alkyl group.

According to some embodiments of the catalyst systems provided herein, formula A, M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ And M ₁₅ Selected from hydroxy, amino, halogen, aldehyde, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some embodiments of the catalyst system of the invention, M ₁ 、M ₅ 、M ₉ 、M ₁₃ The same applies.

According to some embodiments of the catalyst system of the invention, M ₂ 、M ₆ 、M ₁₀ 、M ₁₄ The same applies.

According to some embodiments of the catalyst system of the invention, M ₃ 、M ₇ 、M ₁₁ 、M ₁₅ The same applies.

According to some embodiments of the catalyst system of the invention, M ₄ 、M ₈ 、M ₁₂ 、M ₁₆ The same applies.

According to some embodiments of the catalyst systems provided herein, R _a Selected from C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl and C ₇ -C ₁₀ Aralkyl, wherein any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, and carboxyl.

According to some embodiments of the catalyst system of the present invention, in formula a, R ₁ To R ₈ Each independently selected from hydrogen, C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the catalyst system of the present invention, in formula a, R ₁ To R ₈ The same or different, each independently selected from hydrogen and C ₁ -C ₆ Alkyl, C ₁ -C ₆ The alkyl group may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

According to some embodiments of the catalyst system of the invention, R ₁ To R ₈ Independently selected from hydrogen and C ₁ -C ₆ An alkyl group.

According to some embodiments of the catalyst system of the invention, R ₁ 、R ₃ 、R ₅ 、R ₇ The same applies.

According to some embodiments of the catalyst system of the invention, R ₂ 、R ₄ 、R ₆ 、R ₈ The same applies.

According to some embodiments of the catalyst system of the invention, R ₁ To R ₈ All the same.

According to a preferred embodiment of the invention, M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ And M ₁₅ Is C ₁ -C ₈ An alkoxy group; and M is ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ 、M ₁₆ Selected from hydrogen, hydroxy, amino, halogen, aldehyde, and C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

According to some embodiments of the catalyst system of the present invention, the structure of the compound represented by formula a is represented by formula A1, A2 or A3.

According to an embodiment of the catalyst system of the present invention, the twelve-membered ring compound represented by formula a or a derivative thereof is selected from at least one of the following compounds:

Compound a: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound B: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound C: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound D: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH(CH ₃ ) ₂ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound E: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound F: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound G: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound H: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound I: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OH，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound J: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OH，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound K: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝NH ₂ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound L: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝Cl，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound M: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝Br，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound N: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝I，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound O: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝CHO，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound P: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OCH ₃ ；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₂ CH ₂ Br，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound Q: m is M ₂ ＝M ₃ ＝M ₆ ＝M ₇ ＝M ₁₀ ＝M ₁₁ ＝M ₁₄ ＝M ₁₅ ＝OCH ₂ CH ₂ Cl；

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H；

Compound R: m is M ₂ ＝M ₆ ＝M ₁₀ ＝M ₁₄ ＝OH；M ₃ ＝M ₇ ＝M ₁₁ ＝M ₁₅ ＝OCH ₂ CH ₃ ，

M ₁ ＝M ₄ ＝M ₅ ＝M ₈ ＝M ₉ ＝M ₁₂ ＝M ₁₃ ＝M ₁₆ ＝H，R ₁ ＝R ₂ ＝R ₃ ＝R ₄ ＝R ₅ ＝R ₆ ＝R ₇ ＝R ₈ ＝H。

According to the invention, in order to further improve the comprehensive performance of the catalyst system, one or more other types of donor compounds can be additionally added as a compound external electron donor, and the other external electron donors comprise at least one selected from silane compounds, ester compounds, ether compounds and ketone compounds and compounds thereof.

According to the present invention, the content of the compound represented by formula a may vary within a wide range. According to some embodiments of the invention, the molar ratio of the compound of formula A to the other external electron donor compound is (1-100): (100:1).

According to a preferred embodiment of the invention, the molar ratio of the compound of formula A to the other external electron donor compounds is (1-50): (50:1).

According to a preferred embodiment of the invention, the molar ratio of the compound of formula A to the other external electron donor compounds is (1-20): (20:1).

According to some embodiments of the invention, the external electron donor further comprises a silane-based compound.

According to a preferred embodiment of the present invention, the silane compound has a structure represented by formula B:

in the formula B, R ₁ To R ₄ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₁ -C ₁₀ Alkoxy, C ₂ -C ₁₀ Alkenyloxy, C ₂ -C ₁₀ Alkynyl, C ₂ -C ₁₀ Alkynyloxy, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₅ Aryl and amino groups, said alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, aryl and amino groups optionally being selected from halogen, C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl and amino.

According to a preferred embodiment of the invention, in formula B, R ₁ To R ₄ The same or different are each independently selected from hydrogen, C ₁ -C ₆ Alkyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl and amino groups, which are optionally selected from halogen, C ₁ -C ₆ Alkyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl and amino.

According to a preferred embodiment of the present invention, the silane-based compound is selected from the group consisting of 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, allylethoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldimethoxysilane, allyltrimethoxysilane, aminotriaethoxysilane, aminotrimethylsilane, triethylaminosilsilane, trimethylaminomethylsilane, trimethylaminosilane, n-butylaminosilane, triethylaminosilane, trimethylaminosilane, trimethylaminomethylsilane, n-butylaminosilane, triethylaminosilane, and triethylaminosilane, at least one of ethylaminotri-n-butylsilane and ethylaminotriisobutylsilane.

According to some embodiments of the invention, the internal electron donor is selected from at least one of a diether compound, an alcohol ester compound, an aromatic carboxylate compound, a succinate compound, and a ketone compound.

According to some embodiments of the invention, the diether compound is a 1, 3-diether compound of formula C,

in the formula C, R ^Ⅰ 、R ^Ⅱ 、R ^Ⅲ 、R ^Ⅳ 、R ^Ⅴ And R is ^Ⅵ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₂₀ Alkyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl and C ₇ -C ₂₀ An alkylaryl group; r VII and R ^Ⅷ Identical or different, each independently selected from C ₁ -C ₂₀ Alkyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl and C ₇ -C ₂₀ Alkylaryl wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl and alkylaryl groups is optionally substituted with one or more substituents selected from the group consisting of C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatoms; alternatively, R ^Ⅰ 、R ^Ⅱ 、R ^Ⅲ 、R ^Ⅳ 、R ^Ⅴ And R is ^Ⅵ To form a saturated or unsaturated single or multiple ring, such as a fluorene ring.

According to a preferred embodiment of the invention, in formula C, R ^Ⅰ 、R ^Ⅱ 、R ^Ⅲ 、R ^Ⅳ 、R ^Ⅴ And R is ^Ⅵ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₁₈ Alkyl, C ₃ -C ₁₈ Cycloalkyl, C ₆ -C ₁₈ Aryl, C ₇ -C ₁₈ Aralkyl and C ₇ -C ₁₈ Alkylaryl groups.

According to a preferred embodiment of the invention, in formula C, R ^Ⅰ 、R ^Ⅱ 、R ^Ⅲ 、R ^Ⅳ 、R ^Ⅴ And R is ^Ⅵ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₁₀ Alkyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl and C ₇ -C ₁₀ Alkylaryl groups.

According to a preferred embodiment of the invention, in formula C, R ^Ⅶ And R is ^Ⅷ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₁₀ Alkyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl and C ₇ -C ₁₀ Alkylaryl groups.

According to a preferred embodiment of the invention, in formula C, R ^Ⅶ And R is ^Ⅷ Each independently selected from hydrogenHalogen, C ₁ -C ₁₀ Alkyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl and C ₇ -C ₁₀ Alkylaryl groups.

According to a preferred embodiment of the invention, in formula C, R ^Ⅲ And R is ^Ⅳ Are bonded to each other to form a saturated or unsaturated single or multiple ring.

According to a preferred embodiment of the invention, in formula C, R ^Ⅶ And R is ^Ⅷ Each independently is C ₁ -C ₁₀ An alkyl group.

According to a preferred embodiment of the present invention, the diether compound is selected from the group consisting of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 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-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2-dimethoxypropyl-1, 3-dimethoxypropane, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 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-di-tert-butyl-1, 3-dimethoxypropane, 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-isopropyl-2-cyclohexyl-2-methyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-methyl-1, 3-dimethoxypropane (4-methyl-cyclopentadienyl) -1, 3-dimethoxy (1, 5-methyl-cyclopentadienyl) -4-methyl-1, 5-dimethoxy propane, 1, 1-bis (methoxymethyl) -2,3,4,5, -tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4,5, -tetraphenylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4,5, -tetrafluorocyclopentadiene, 1-bis (methoxymethyl) -3, 4-dicyclopentadienyl cyclopentadiene, 1, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -2, 3-dimethoxyindene, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene, 1-bis (methoxymethyl) -4,5,6, 7-tetrafluoroindene 1, 1-bis (methoxymethyl) 4, 7-dimethylindene, 1-bis (methoxymethyl) -3, 6-dimethylindene, 1-bis (methoxymethyl) -4-phenylindene 1, 1-bis (methoxymethyl) 4, 7-dimethylindene, 1-bis (methoxymethyl) -3, 6-dimethylindene 1, 1-bis (methoxymethyl) -4-phenylindene, 1, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene 9, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene 1, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methane dihydronaphthalene 9, 9-bis- (methoxymethyl) -1, 4-methane dihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, at least one of 5, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.

According to some embodiments of the invention, the alcohol ester compound is a glycol ester compound of formula D,

in the formula D, R ₁ And R is ₂ Identical or different, each independently selected from C ₁ -C ₂₀ Alkyl, C ₂ -C ₂₀ Alkenyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Alkylaryl, C ₇ -C ₂₀ Aralkyl and C ₁₀ -C ₂₀ Fused ring aryl groups, the alkyl, alkenyl, cycloalkyl, aryl, alkylaryl, arylalkyl, and fused ring aryl groups optionally being substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatoms; m is a divalent linking group.

According to a preferred embodiment of the invention, in formula D, R ₁ And R is ₂ Identical or different, each independently selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Alkylaryl, C ₇ -C ₁₀ Aralkyl and C ₁₀ -C ₁₅ Condensed ring aryl.

According to a preferred embodiment of the invention, in formula D, M is selected from C ₁ -C ₂₀ Alkylene, C ₃ -C ₂₀ Cycloalkylene and C ₆ -C ₂₀ Arylene, said alkylene, cycloalkylene and/or arylene being C ₁ -C ₂₀ Alkyl is substituted and the substituents are optionally bonded to form one or more rings, the carbon atoms or/and hydrogen atoms in M are optionally substituted with nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.

According to some embodiments of the invention, the alcohol ester compound is a glycol ester compound of formula E,

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in the formula E, R ₁ And R is ₂ Identical or different, each independently selected from C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Aralkyl and C ₇ -C ₂₀ Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl groups optionally being selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in the alkoxy group; r is R ₃ 、R ₄ 、R ₅ 、R ₆ And R is ¹ -R ²ⁿ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₂₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Alkylaryl, C ₇ -C ₂₀ Aralkyl and C ₁₀ -C ₂₀ Condensed ring aryl groups, the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, arylalkyl, and condensed ring aryl groups optionally being selected from halogen, C ₁ -C ₆ Alkyl and C ₁ -C ₆ One or more substituents in the alkoxy group; r is R ₃ 、R ₄ 、R ₅ 、R ₆ And R is ¹ -R ²ⁿ Optionally containing heteroatoms which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R ₃ 、R ₄ 、R ₅ 、R ₆ And R is ¹ -R ²ⁿ To form a saturated or unsaturated single ring or a saturated or unsaturated multiple 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 is ₄ Is R as carbon atom and substituent ₅ And R is ₆ Is bonded to a carbon atom of (2);

according to a preferred embodiment of the invention, in formula E, R ₁ And R is ₂ Identical or different, each independently C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl and C ₇ -C ₁₀ Alkylaryl, R ₃ 、R ₄ 、R ₅ 、R ₆ And R is ¹ -R ²ⁿ The same or different, each independently selected from hydrogen, halogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₁₀ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Alkylaryl, C ₇ -C ₁₀ Aralkyl and C ₁₀ -C ₁₅ Condensed ring aryl.

According to a preferred embodiment of the present invention, the glycol ester compound is selected from the group consisting of 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol di-p-methyl benzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol di-o-chlorobenzoate, 3, 5-heptanediol di-p-methoxybenzoate, 3, 5-heptanediol di-o-methoxybenzoate, 3, 5-heptanediol di-m-methoxybenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-heptanediol di-2, 5-dimethyl-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 4-dimethyl-5-heptanediol dibenzoate, 6-dimethyl-4, 5-heptanediol dibenzoate, 4-dimethyl-5-heptanediol dibenzoate, 4-dimethyl-3, 5-dimethyl-heptanediol dibenzoate 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, 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-dimethyl-3, 5-octanediol dibenzoate, 4-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-4, 6-nonanediol dibenzoate, 5-butyl-4, 6-nonanediol dibenzoate, 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, dibenzoate-1, 8-naphthalene, di-4-methylbenzoic acid-1, 8-naphthalene, di-4-ethylbenzoic acid-1, 8-naphthalene, di-4-n-propyl-benzoic acid, 1, 8-naphthalene, 4-diphenyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-isopropyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-diphenyl-4-isopropyl-benzoic acid, 4-isopropyl-4-phenyl-4, 8-naphthalene, 1, 8-naphthalene di-3-fluorobenzoate and 1, 8-naphthalene di-2-fluorobenzoate.

According to some embodiments of the invention, the aromatic carboxylic acid ester compound has a structure as shown in formula F:

in the formula F, each R ₃ Identical or different, independently C ₁ -C ₈ Alkyl, C ₅ -C ₁₀ Cycloalkyl, C ₆ -C ₁₅ Aryl, C ₇ -C ₁₅ Alkylaryl or C ₇ -C ₁₅ Aralkyl group of (C) ₁ -C ₈ Alkyl, C ₃ -C ₁₀ Branched alkyl, C ₅ -C ₁₀ Cycloalkyl, C ₆ -C ₁₅ Aryl, C ₇ -C ₁₅ Alkylaryl or C ₇ -C ₁₅ The hydrogen on the aralkyl carbon may be optionally substituted with a substituent selected from alkanes and halogen atoms, preferably with a substituent selected from C ₁ -C ₆ One or more substituents of an alkyl group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; r is R ₄ -R ₇ May be the same or different and is hydrogen, halogen, C ₁ -C ₆ Alkyl, C ₅ -C ₁₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Alkylaryl or C ₇ -C ₂₀ Aralkyl group, said C ₁ -C ₈ Alkyl, C ₅ -C ₁₀ Cycloalkyl, C ₆ -C ₁₅ Aryl, C ₇ -C ₁₅ Alkylaryl or C ₇ -C ₁₅ The hydrogen on the carbon in the aralkyl group of (2) may optionally be selected from alkanes and halogensSubstituted by substituents of a sub-group, preferably selected from C ₁ -C ₆ One or more substituents of an alkyl group, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

According to a preferred embodiment of the present invention, the aromatic carboxylic acid ester compound is selected from at least one of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate.

According to a preferred embodiment of the present invention, the aromatic carboxylic acid ester compound is a phthalate carboxylic acid ester.

According to a preferred embodiment of the present invention, the aromatic carboxylic acid ester compound is diisobutyl phthalate.

According to some embodiments of the invention, the succinate compound has the structure shown in formula G,

in the formula G, R ₁ And R is ₂ Identical or different, each independently selected from C ₁ -C ₂₀ Alkyl, C ₃ -C ₂₀ Cycloalkyl, C ₆ -C ₂₀ Aryl, C ₇ -C ₂₀ Arylalkyl or C ₇ -C ₂₀ Alkylaryl groups, optionally containing heteroatoms; r is R ₃ 、R ₄ 、R ₅ And R is ₆ The same or different are each independently selected from hydrogen, C ₁ -C ₂₀ Alkyl, cycloalkyl, aryl, arylalkyl or alkylaryl groups optionally containing heteroatoms and the groups may be joined to form a ring.

According to a preferred embodiment of the present invention, the succinate compound is selected from the group consisting of diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropyl succinate, diethyl 2, 3-diisopropyl succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2,3- (bistrimethylsilyl) succinate, diethyl 2- (3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisoamyl succinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutyl succinate diethyl 2-tert-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2, 3-tetramethylsuccinate, diethyl 2, 3-tetraethyl succinate, diethyl 2, 3-tetrapropylsuccinate diethyl 2, 3-diethyl-2, 3-diisopropyldisuccinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2,3- (bistrimethylsilyl) succinate, diisobutyl 2- (3, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisoamyl succinate, diisobutyl 2,3- (1-trifluoromethyl-ethyl) succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate diisobutyl 2, 3-tetramethylsuccinate, diisobutyl 2, 3-tetraethylsuccinate diisobutyl 2, 3-tetrapropylsuccinate, diisobutyl 2, 3-diethyl-2, 3-diisopropyldisuccinate; preferably selected from the group consisting of diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate and diisobutyl 2, 3-diisopropylsuccinate.

According to the invention, the solid catalyst component comprises titanium, magnesium and an internal electron donor, and is the reaction product of a titanium compound, a magnesium compound and an internal electron donor. Since the present invention is to improve the performance of the olefin polymerization catalyst by changing the kinds of the internal and external electron donors, the method of preparing the solid catalyst component in the present invention may be carried out according to a method conventionally used in the art, for example, the method 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:

method 1: adding an inert solvent into a magnesium compound, adding an organic epoxy compound and an organic phosphorus compound, dissolving, and then adding a precipitation aid and a titanium compound to precipitate a solid; adding internal electron donor, loading on solid, and treating with titanium tetrahalide and inert diluent.

Method 2: dissolving solid magnesium compound in organic alcohol compound such as 2-ethylhexanol in inert solvent such as decane or toluene, adding precipitation aid and titanium compound after dissolving, and separating out solid; adding internal electron donor, loading on solid, and treating with titanium compound and inert diluent.

Method 3: dispersing magnesium halide alcohol compound into titanium compound at low temperature (below-5 deg.c), raising temperature to high temperature (above 50 deg.c), adding internal electron donor compound during raising temperature, filtering, treating the precipitate with titanium compound, and washing the precipitate to obtain the solid catalyst component.

Method 4: preparing a suspension by using an alkoxy magnesium carrier and an inert diluent, then reacting with a mixture formed by a titanium compound and the inert diluent, filtering, performing 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 some embodiments of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (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 and the solid phase obtained is treated at least 2 times again with titanium compound and washed with solvent, finally vacuum drying to obtain the solid catalyst component.

According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, for example, the magnesium compound may be selected from at least one of magnesium dihalide, alkoxymagnesium, alkyl magnesium, hydrate of magnesium dihalide, alkoxide of magnesium dihalide, and derivative in which one halogen atom in the magnesium dihalide molecule is substituted with hydrocarbyloxy or halohydrocarbonyloxy. According to a preferred embodiment of the present invention, the magnesium compound is an alkoxide of magnesium dihalide.

According to a preferred embodiment of the present invention, the magnesium dihalide alkoxide has a spherical magnesium alkoxide represented by the formula (I),

MgX ₂ ·m(R’OH)·nE·qH ₂ o type (I)

In formula (I): x is chlorine or bromine; r' is C ₁ -C ₄ (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, and n is 0-1.0, wherein the ether or ester can be ether or ester which is known in the art and can be used as an electron donor, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0-0.8.

According to a preferred embodiment of the invention, in formula (I), X is chloro or bromo; r' is C ₁ -C ₄ M is 1.5 to 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 method of preparing the magnesium dihalide alkoxide may be prepared according to methods well known in the art, for example, with reference to the method disclosed in CN1330086 a.

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

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

According to the invention, the alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctanol (2-ethylhexanol) and a mixed halogenating agent under inert atmosphere. The mixed halogenating agent is a combination of a halogen and a halogen compound, a non-limiting selection of which: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide, magnesium ethoxyiodide, magnesium methoxyiodide, magnesium isopropyliodide, hydrogen chloride, chloroacetyl chloride, and the like.

The titanium compound according to the present invention 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 (II),

Ti(OR”) _4-k X _k formula (II)

In formula (II): r' is C ₁ -C ₂₀ X is F, cl or Br; k is an integer of 0 to 4.

According to a preferred embodiment of the invention, in formula (II): r' is C ₁ -C ₁₀ Is an alkane of (2)A base.

According to a preferred embodiment of the invention, in formula (II): r' is C ₁ -C ₅ Is a hydrocarbon group.

According to a preferred embodiment of the invention, for example, in formula (II): 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 (II): x is Cl.

According to a preferred embodiment of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium tributoxide monochloride, titanium dibutoxide dichloride, titanium tributoxide monochloride, titanium triethoxide monochloride, titanium diethoxide dichloride, titanium monoethoxide trichloride and titanium trichloride.

According to a preferred embodiment of the invention, the titanium compound is titanium tetrachloride.

According to some embodiments of the present invention, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).

According to the invention, the aluminum alkyl compound is of the formula AlR ₃ Compounds of formula (I) wherein R is C ₁ -C ₂₀ Alkyl or halo C ₁ -C ₂₀ An alkyl group.

According to a preferred embodiment of the invention, in the general formula AlR ₃ Wherein R is C ₁ -C ₈ Alkyl or halo C ₁ -C ₈ An alkyl group.

According to a preferred embodiment of the present invention, the alkylaluminum compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monohydride, aluminum (n-C) ₆ H ₁₃ ) ₃ And Al (n-C) ₈ H ₁₇ ) ₃ One or more of the following.

According to a preferred embodiment of the present invention, the alkyl aluminum compound is triethylaluminum and/or triisobutylaluminum.

According to an embodiment of the present invention, in the catalyst system, the molar ratio of the catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum is 1: (5-5000).

According to a preferred embodiment of the present invention, in said catalyst system, the molar ratio of the catalyst component, calculated as titanium element, to the alkylaluminum compound, calculated as aluminum, is 1: (20-2000).

According to an embodiment of the invention, in the catalyst system, the molar ratio of the external electron donor to the alkylaluminum compound, calculated as aluminum, is 1: (0.1-500).

According to a preferred embodiment of the present invention, in the catalyst system, the molar ratio of the external electron donor to the alkylaluminum compound, calculated as aluminum, is 1: (1-200).

In a third aspect, the present invention provides a prepolymerized catalyst composition for olefin polymerization comprising a prepolymer obtained by prepolymerizing the catalyst system according to the second aspect with an olefin.

According to some embodiments of the invention, the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin prepolymer per g of solid catalyst component.

According to some preferred embodiments of the invention, the prepolymer has a prepolymerization multiple of 0.2 to 500g of olefin prepolymer per g of solid catalyst component.

According to some preferred embodiments of the invention, the prepolymer has a pre-polymerization multiple of 0.5 to 20g of olefin prepolymer per g of solid catalyst component.

According to the invention, a "prepolymerized catalyst" refers to a catalyst which has undergone a polymerization step at a lower degree of conversion. In the present invention, the same alpha-olefin as the olefin used for polymerization can be used for the prepolymerization.

According to some preferred embodiments of the invention, the olefin that is prepolymerized is propylene.

According to some preferred embodiments of the present invention, propylene or a mixture thereof with one or more alpha-olefins in a molar amount of up to 20% is used for the prepolymerization.

According to some embodiments of the invention, the temperature of the prepolymerization is from-20 to 80℃and the polymerization pressure is preferably from 0 to 5MPa.

According to some preferred embodiments of the invention, the temperature of the prepolymerization is 0-50 ℃.

According to some embodiments of the invention, the pre-polymerization is performed in liquid or in gas phase.

According to some embodiments of the invention, the pre-polymerization step may be performed in-line as part of a continuous polymerization process or separately in a batch operation.

According to some preferred embodiments of the present invention, to prepare 0.1 to 1000g of olefin prepolymer per g of polymer of solid catalyst component, the prepolymerization of the catalyst according to the invention with olefin is carried out independently in a batch operation, the polymerization pressure being 0 to 5MPa.

In a fourth aspect, the present invention provides a process for the polymerization of olefins, wherein the olefins are polymerized in the presence of the catalyst system according to the second aspect and/or the prepolymerized catalyst composition according to the third aspect, the olefins having the general formula CH ₂ =chr, wherein R is hydrogen or C ₁ -C ₆ Alkyl, said olefin polymerization may be a homo-polymerization of a single said olefin or a co-polymerization of a plurality of said olefins.

According to some preferred embodiments of the 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 a fifth aspect, the present invention provides the use of a catalyst system according to the second aspect and/or a pre-polymerisation catalyst composition according to the third aspect in an olefin polymerisation reaction.

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

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

According to the invention, the catalyst system of the invention can be added directly to the reactor for use in the polymerization process or can be added to the reactor after the catalyst system has been prepolymerized with the olefin to obtain a prepolymerized catalyst composition.

According to the present invention, the olefin polymerization may be carried out according to a known polymerization method, in a liquid phase or a gas phase, or in a combination of liquid and gas phase polymerization stages, or by a conventional technique such as a slurry method, a gas phase fluidized bed, or the like.

According to some preferred embodiments of the invention, the polymerization conditions include a temperature of 0 to 150℃for a time of 0.2 to 5 hours and a pressure of 0.01 to 10MPa.

According to some preferred embodiments of the invention, the polymerization conditions include a temperature of 50 to 90 ℃, a time of 0.3 to 2 hours, and a pressure of 0.02 to 5MPa.

According to the invention, the polymerization may be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X10, based on the titanium element in the solid catalyst component ^-5 -5×10 ^-5 Moles/liter.

According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent may be 0.2X10, based on the titanium element in the solid catalyst component ^-5 -2×10 ^-5 Moles/liter.

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

In the present invention, alkyl refers to straight chain alkyl or branched alkyl, 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-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 alkenyl groups 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.

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

Examples of halogens in the present invention include, but are not limited to, fluorine, chlorine, bromine, and iodine.

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

In the present invention, aralkyl refers to an alkyl group having an aryl substituent, 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, alkylaryl refers to an aryl group having an alkyl substituent with a carbon number of 7 to 20, examples of which 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.

Examples of fused ring aryl groups in the present invention may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl.

In the present invention, the hetero atom means an atom commonly 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.

Preparation examples, examples and comparative examples

Preparation example 1

A mixed solution of 3, 4-dimethoxybenzyl alcohol (5 g)/dichloromethane (20 mL) was added dropwise to a dichloromethane (200 mL) solution of trifluoroacetic acid (25 mL), and the reaction was continued under an ice bath for 4 hours after completion of the dropwise addition. The reaction solution was neutralized with sodium hydroxide solution, the organic phase was separated and completely drained. The resultant product was washed with water and an organic solvent several times, and recrystallized from chloroform (80 mL)/benzene (30 mL) to obtain 2.5g of compound a.

In example 1 and comparative example 1, propylene polymerization was carried out using NDQ catalyst obtained from medium petrochemical alda catalyst company.

This example is illustrative of the catalyst system provided by the present invention and its use.

Polymerization reaction a:

in a 48-channel parallel pressure reactor (PPR, reaction volume 20 ml), purging with nitrogen at high temperature, cooling to room temperature; replacing the reactor with propylene at normal temperature, and charging propylene with a certain pressure and a certain amount of hydrogen; charging propylene gas to about 1MPa, and adding 5ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminum (as elemental aluminum): external electron donors in table 1: sequentially adding triethylaluminum, an external electron donor and a heptane solution of the NDQ catalyst (calculated by titanium element) in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into a reactor; the temperature was raised to 70℃and the reaction was carried out for 1 hour.

The isotactic index of the polymer was measured and the results are shown in Table 1.

Polymer isotactic index: reference standard GB/T2412-2008.

TABLE 1

Examples	External electron donor	Hydrogenation amount (mNL)	Isotactic index (%)
				Example 1	Compound A	4	96.5
Comparative example 1	Without adding	4	95.8

As can be seen from Table 1, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the catalyst system using the compound shown in the formula A and the derivative thereof as the external electron donor can improve the isotactic index of the polymer, and can be applied to the production of polypropylene products.

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

1. polymerization activity of the catalyst: the amount of polymer obtained (in kg) over a period of time divided by the amount of catalyst added (in g).

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

3. Polymer isotactic index: reference standard GB/T2412-2008.

4. Ethylene content: fourier infrared spectrometer VERTEX70 measurement.

Preparation example 2

This preparation example is used to illustrate the preparation of magnesium compounds.

Mixing anhydrous magnesium chloride and ethanol according to the molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alkoxide melt, stirring at high speed in dispersion medium white oil and silicone oil, then placing into cooled hexane to form spherical magnesium chloride alkoxide particles, washing and drying to obtain the spherical carrier.

Preparation example 3

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

In a 300ml glass reaction bottle with stirring fully replaced by high-purity nitrogen, adding 100ml titanium tetrachloride, cooling to-20 ℃, adding 8g of spherical magnesium chloride alkoxide prepared in preparation example 2, slowly heating to 110 ℃, adding 6mmol of 2-isopropyl-2-isopentyl-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 vacuum drying to obtain a titanium-containing solid catalyst component Z1.

Preparation example 4

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

In a 300ml glass reaction flask with stirring, which is fully replaced by high-purity nitrogen, 100ml of titanium tetrachloride is added, the mixture is cooled to-20 ℃, 8g of spherical magnesium chloride alkoxide prepared in preparation example 2 is added, the temperature is slowly raised to 110 ℃, 3mmol of 2, 4-pentanediol dibenzoate and 3mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane are added as internal electron donors in the process of temperature rise, after the temperature is kept constant at 110 ℃ for 0.5h, liquid is filtered, the titanium tetrachloride is added for two times, then hexane is used for washing five times, and the titanium-containing solid catalyst component Z2 is obtained after vacuum drying.

Preparation example 5

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

6.0g of magnesium chloride, 119ml of toluene, 5ml of epichlorohydrin and 15.6ml of tributyl phosphate (TBP) are sequentially added into a reactor which is fully replaced by high-purity nitrogen, the temperature is raised to 50 ℃ under stirring, and the temperature is maintained for 2.5 hours, so that the solid is completely dissolved; addingPhthalic anhydride 1.7g was added and continued for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl in 1 hour ₄ Slowly heating 70ml to 80 ℃, and gradually precipitating solid matters in the heating process; 6mmol of 3-methyl-2, 4-pentanediol dibenzoate was added as an internal electron donor, the temperature was maintained for 1 hour, and after filtration, 80ml of toluene was added and washed twice to obtain a solid precipitate. 60ml of toluene and TiCl are then added ₄ 40ml, heating to 100deg.C, treating for 2 hr, removing filtrate, adding 60ml toluene and TiCl ₄ 40ml, heating to 100deg.C, treating for 2 hr, and removing filtrate; 60ml of toluene is added, washing is carried out three times under boiling state, 60ml of hexane is added, washing is carried out twice under boiling state, 60ml of hexane is added, and washing is carried out twice under normal temperature, thus obtaining the solid catalyst component Z3.

Preparation example 6

This preparation example is used to illustrate the preparation of magnesium alkoxides:

after a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10L of ethanol, 300mL of 2-ethylhexanol, 11.2g of iodine, 8g of magnesium chloride and 640g of magnesium powder were added to the reactor. Stirring while heating the system to 75 ℃ for reflux reaction until no more hydrogen is discharged. Stopping the reaction, washing with 3L ethanol, filtering and drying to obtain the alkoxy magnesium.

Preparation example 7

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

10g of the magnesium alkoxide compound of preparation 6, 50mL of toluene, 3mmol of diethyl 2, 3-diisopropylsuccinate and 3mmol of 3, 5-heptanediol dibenzoate were taken and prepared into a suspension. Adding 40mL of toluene and 60mL of titanium tetrachloride into a 300mL reaction kettle repeatedly replaced by high-purity nitrogen, heating to 80 ℃, adding the prepared suspension into the kettle, keeping the temperature for 1 hour, slowly heating to 110 ℃, keeping the temperature for 2 hours, adding 78mL of toluene and 52mL of titanium tetrachloride into the mixture after filter pressing, and stirring the mixture at 110 ℃ for 1 hour, thus treating for 3 times. Washing with hexane for 4 times, each time 150mL, press-filtering, and drying to obtain a solid catalyst component Z4.

Preparation example 8

A mixed solution of 3, 4-diethoxybenzyl alcohol (5.8 g)/dichloromethane (20 mL) was added dropwise to a dichloromethane (200 mL) solution of trifluoroacetic acid (25 mL), and the reaction was continued under an ice bath for 4 hours after the completion of the dropwise addition. The reaction solution was neutralized with sodium hydroxide solution, the organic phase was separated and completely drained. The resultant product was washed with water and an organic solvent several times, and recrystallized from chloroform (80 mL)/benzene (30 mL) to obtain 1.5g of compound B.

Polymerization reaction B:

in a 48-channel parallel pressure reactor (PPR, reaction volume 20 ml), purging with nitrogen at high temperature, cooling to room temperature; replacing the reactor with propylene at normal temperature, and charging propylene with a certain pressure and a certain amount of hydrogen; charging propylene gas to about 1MPa, and adding 5ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminum (as elemental aluminum): external electron donors in table 1: the solid catalyst component prepared in preparation examples 3, 4, 5 or 7 (calculated as titanium element) is added with triethylaluminum, the external electron donor in table 1 and the heptane solution of the solid catalyst component prepared in preparation examples 3, 4, 5 or 7 in turn according to the molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into a reactor; the temperature was raised to 70℃and the reaction was carried out for 1 hour.

Discharging, weighing the polymer by using a weighing device of the PPR, and calculating to obtain the activity of the catalyst; the isotactic index and weight average molecular weight of the polymer were also measured, and the results are shown in Table 2.

Polymerization C:

in a 48-channel parallel pressure reactor (PPR, reaction volume 20 ml), purging with nitrogen at high temperature, cooling to room temperature; replacing the reactor with hydrogen at normal temperature; charging propylene gas to about 1MPa, and adding 5ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminum (as elemental aluminum): external electron donors in table 1: the solid catalyst component prepared in preparation example 3 or 4 (calculated as titanium element) was added with triethylaluminum, the external electron donor in table 1, and the heptane solution of the solid catalyst component prepared in preparation example 3 or 4 in the molar ratio of 250:10:1 in order to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into a reactor; the temperature was raised to 70℃and the reaction was carried out for 40 minutes. The reactor was vented, the system was replaced with ethylene-propylene mixture, and the pressure was controlled at 80℃for 20 minutes at 0.7 MPa.

Discharging, weighing the polymer by using a weighing device of the PPR, and calculating to obtain the activity of the catalyst; the ethylene content of the polymer was also measured, and the results are shown in Table 3.

TABLE 2

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Note that: C-Donor: cyclohexyl methyl dimethoxy silane;

compound 1 molar ratio is compound a: C-donor=1:1;

compound 2 molar ratio is compound a: C-donor=1:9;

compound 3 molar ratio is compound B: C-donor=1:1.

TABLE 3 Table 3

Note that: C-Donor: cyclohexyl methyl dimethoxy silane;

compound 1 molar ratio is compound a: C-donor=1:1;

compound 2 molar ratio is compound a: C-donor=1:9.

As can be seen from Table 2, the catalyst system provided by the invention has better stereospecificity, catalytic activity and hydrogen regulation sensitivity when being used for olefin polymerization, especially propylene polymerization. Compared with the catalyst taking C-Donor as an external electron Donor, the catalyst system containing the twelve-membered ring compound shown in the formula A has the advantages of improved hydrogen regulation sensitivity, obviously improved polymerization activity and improved polymer isotactic index. According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is particularly suitable for preparing a polypropylene product with high stereoregularity and low ash content, and the melt index of the product can be regulated and controlled within a wider range by adjusting the hydrogenation amount.

As can be seen from Table 3, when the catalyst system provided by the invention is used for olefin copolymerization, especially ethylene-propylene copolymerization, compared with the catalyst system in which C-Donor is used as an external electron Donor, the ethylene content of the copolymer obtained by the catalyst system in which the external electron Donor contains the twelve-membered ring compound shown in the formula A is equivalent, and the polymerization activity is improved. According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is also suitable for a copolymerization system, and is beneficial to improving the copolymerization productivity.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (15)

1. The use of a compound of formula A as an external electron donor in a catalyst system for the polymerization of olefins,

a is a kind of

In the formula A, the components of the compound,

M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ 、M ₁₅ is R _a O-，M ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ 、M ₁₆ Is a hydrogen gas which is used as a hydrogen gas,

when two adjacent groups on the benzene ring are R _a O-, optionally, two adjacent groups may form a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof ，

Wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

2. Use according to claim 1, characterized in that M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ 、M ₁₅ Each independently selected from C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

3. The use according to claim 1, wherein in formula a, R _a Selected from C ₁ -C ₆ Alkyl, C ₃ -C ₆ Cycloalkyl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl, wherein any of said alkyl, cycloalkyl, aralkyl, heterocycloalkyl may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkyl ammoniaA group, an aldehyde group and a carboxyl group.

4. The use according to claim 1, wherein in formula a, R ₁ To R ₈ Each independently selected from hydrogen, C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

5. A catalyst system for the polymerization of olefins comprising:

1) A solid catalyst component containing magnesium, titanium, halogen and an internal electron donor;

2) An alkyl aluminum compound; and

3) An external electron donor;

wherein the external electron donor comprises a compound represented by formula A,

a is a kind of

In the formula A, the components of the compound,

M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ 、M ₁₅ is R _a O-，M ₁ 、M ₄ 、M ₅ 、M ₈ 、M ₉ 、M ₁₂ 、M ₁₃ 、M ₁₆ Is a hydrogen gas which is used as a hydrogen gas,

when two adjacent groups on the benzene ring are R _a O-in which two adjacent radicals optionally form a ring with each otherThe rings are selected from the group consisting of saturated or unsaturated monocyclic rings, saturated or unsaturated polycyclic rings, and combinations thereof,

wherein R is _a Selected from C ₁ -C ₁₀ Alkyl, C ₃ -C ₈ Cycloalkyl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl;

R ₁ to R ₈ The same or different are each independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, C ₂ -C ₁₀ Alkenyl, C ₂ -C ₁₀ Alkynyl, C ₃ -C ₈ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₂₀ Aralkyl, 4-12 membered heterocycloalkyl and C ₅ -C ₂₀ A heteroaryl group, which is a group,

any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₁₀ Alkylamino, bis-C ₁ -C ₁₀ Alkylamino, aldehyde, carboxyl and heteroatom.

6. The catalyst system of claim 5, wherein M ₂ 、M ₃ 、M ₆ 、M ₇ 、M ₁₀ 、M ₁₁ 、M ₁₄ 、M ₁₅ Each independently selected from C ₁ -C ₆ Alkoxy and halogen substituted C ₁ -C ₆ An alkoxy group.

7. The catalyst system of claim 5 wherein in formula A, R _a Selected from C ₁ -C ₆ Alkyl, C ₃ -C ₆ Cycloalkyl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl, wherein any of said alkyl, cycloalkyl, aralkyl, heterocycloalkyl may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyanoNitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, and carboxyl.

8. The catalyst system of claim 5 wherein in formula A, R ₁ To R ₈ Each independently selected from hydrogen, C ₁ -C ₆ Alkyl, C ₂ -C ₆ Alkenyl, C ₂ -C ₆ Alkynyl, C ₃ -C ₆ Cycloalkyl, C ₆ -C ₁₀ Aryl, C ₇ -C ₁₀ Aralkyl, 4-6 membered heterocycloalkyl and C ₅ -C ₁₀ Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C ₁ -C ₆ Alkylamino, bis-C ₁ -C ₆ Alkylamino, aldehyde, carboxyl and heteroatom.

9. The catalyst system of any one of claims 5-8, wherein the molar ratio of the external electron donor to the aluminum alkyl compound, calculated as aluminum, is 1: (0.1-500); and/or the molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum is 1: (5-5000); and/or the weight ratio of titanium element, magnesium element and internal electron donor in the solid catalyst component is 1: (5-25): (2-15).

10. The catalyst system of claim 9, wherein the molar ratio of the external electron donor to the aluminum alkyl compound, calculated as aluminum, is 1: (1-200); and/or the molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum is 1: (20-2000).

11. The catalyst system according to any one of claims 5-8 and 10, wherein the internal electron donor is selected from at least one of diethers, alkoxides, aromatic carboxylates, succinates and ketones.

12. A prepolymerized catalyst composition for olefin polymerization comprising a prepolymer obtained by prepolymerizing the catalyst system according to any one of claims 5-11 with an olefin.

13. A process for the polymerization of olefins having the general formula CH, said olefins being polymerized in the presence of a catalyst system according to any of claims 5-11 and/or a prepolymerized catalyst composition according to claim 12 ₂ =chr, wherein R is hydrogen or C ₁ -C ₆ An alkyl group; the olefin polymerization may be a homo-polymerization of a single said olefin or a co-polymerization of a plurality of said olefins.

14. The method of claim 13, wherein the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, or 1-hexene.

15. Use of the catalyst system according to any one of claims 5-11 and/or the prepolymerized catalyst composition according to claim 12 in olefin polymerization reactions.