WO2016086837A1

WO2016086837A1 - Disulfonic acid ester compound and application thereof, olefin polymerization catalyst component and olefin polymerization catalyst

Info

Publication number: WO2016086837A1
Application number: PCT/CN2015/096119
Authority: WO
Inventors: 尹宝作; 义建军; 孙天旭; 崔伟松; 袁苑; 张明革; 李红明; 崔亮
Original assignee: 中国石油天然气股份有限公司
Priority date: 2014-12-05
Filing date: 2015-12-01
Publication date: 2016-06-09
Also published as: WO2016086836A1

Abstract

Disclosed are a disulfonic acid ester compound of general formula I, olefin polymerization catalyst component prepared by using the disulfonic acid ester compound, a composite support of magnesium halide and silicon dioxide, a conventional internal electron donor compound and a titanium halide compound as raw materials of a reaction, such that two internal electron donor compounds are used, thus ensuring both the activity of a catalyst and the tacticity of a polymer prepared thereby. Also disclosed are an olefin polymerization catalyst comprising the component and application thereof.

Description

Dibasic sulfonate compound and application thereof and olefin polymerization catalyst component and olefin polymerization catalyst

Technical field

The present invention relates to a disulfonate compound and use thereof, and an olefin polymerization catalyst component prepared by using the disulfonate compound, and an olefin polymerization catalyst comprising the catalyst component and The application of the catalyst belongs to the technical field of olefin polymerization catalysts.

Background technique

It is well known that Ziegler-Natta catalysts for the polymerization of olefins, in particular alpha-olefins having three or more carbon atoms, generally comprise a main catalyst and a cocatalyst. The main catalyst is mostly a solid titanium catalyst prepared by reacting a titanium compound, a magnesium compound and an internal electron donor as a basic raw material. Olefin polymers having higher yields and higher stereoregularity can be prepared by using such a main catalyst. It is generally believed in the industry that magnesium compounds act as carriers (for example, MgCl _{2 ,} etc.) mainly as a skeleton; the morphology of the carrier directly determines the morphology of the particles of the main catalyst and the olefin polymer; titanium compounds (such as TiCl _{4 ,} etc.) mainly To form the active center; while the internal electron donor mainly plays the role of improving catalytic activity and stereotactic ability, and affects the hydrogen modulating sensitivity of the main catalyst and other aspects of performance, and with the development of internal electron donor compounds This has led to the continuous upgrading of olefin polymerization catalysts.

Heretofore, various internal electron donor compounds have been disclosed, mainly including polycarboxylic acids, monocarboxylic acid esters or polycarboxylic acid esters, acid anhydrides, ketones, monoethers or polyethers, alcohols, amines, and the like, and derivatives thereof. Among them, common ones are: aromatic carboxylic acid ester internal electron donors, such as ethyl benzoate, di-n-butyl phthalate, diisobutyl phthalate, etc. (see CN85100997A, US4784983, EP0045977, etc.) ; an aliphatic dicarboxylic acid ester internal electron donor, commonly including malonate compounds, succinate compounds, glutarate compounds, etc. (see CN1236732A, CN1236733A, CN1236734A, CN1292800A, WO0063261, WO9856830 , WO9856834, WO0157099, WO0163231 and WO0055215, etc.; diether internal electron donors, generally 1,3-diether compounds containing two ether groups, such as 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane and 9,9-bis(methoxymethyl)anthracene (see EP0361493, EP0361494, EP0728724) , EP0728769, US4971937, US2004014597, US2003027715, CN1042547A, CN1143651A, CN1141285A and WO03076480, etc.; ethyl cyanate internal electron donor (see CN1242780A, etc.); maleate internal electron donor; diketone internal donor Electron body, generally a 1,3-diketone compound, such as 2, 2, 4, 6, 6-five a group of 3-,5-heptanedione and 2,2,6,6-tetramethyl-4-ethyl-3,5-heptanedione (see CN1105671A, CN1054139A, etc.); Body (CN1087918A) and other types of Compound.

For example, EP 0 361 494, CN 1 141 285 A discloses ZN catalysts containing diether internal electron donors which have outstanding characteristics such as high activity, hydrogen sensitivity and high stereotactic ability. The catalyst is a MgCl ₂ /SiO ₂ spherical composite support prepared by spray drying, and is prepared by using a diether compound as an internal electron donor. Although the catalyst exhibits high catalytic propylene polymerization activity, sensitive hydrogen modulation property and high stereospecific ability, the obtained propylene homopolymer has a narrow molecular weight distribution, which brings inconvenience to the post-processing process; The bulk density of propylene polymers is low and is not convenient for practical industrial production.

In general, the aromatic carboxylic acid ester compound disclosed above, a 1,3-diether compound containing two ether groups, and an aliphatic dicarboxylic acid ester compound are used as internal electron donors. Catalysts for olefin polymerization have certain drawbacks in practical applications. For example, a catalyst prepared by using an aromatic carboxylic acid ester to an electron donor has a low activity, and the molecular weight distribution of the obtained polymer is also narrow; a catalyst prepared by using a 1,3-diether donor electron donor has a high activity and a catalyst. Hydrogen sensitivity is also good, but the molecular weight distribution of the obtained olefin polymer is narrow, which is not conducive to the development of different grades of olefin polymer; while the catalyst prepared by using the recently disclosed aliphatic dicarboxylic acid ester to electrons can be used. The molecular weight distribution of the obtained propylene polymer is significantly broadened, but the activity of the catalyst is still low, and the isotacticity of the obtained olefin polymer is low when no external electron donor is used.

Catalysts prepared using different internal electron donor compounds have different characteristics, some have higher activity, some have better hydrogen regulation properties, and some catalysts have polyolefins with wider molecular weight distribution. In order to obtain a catalyst with excellent comprehensive performance, two or more (including two) internal electron donors have been attempted to prepare a catalyst, and the related contents are disclosed in WO9957160, WO0230998, WO03002617, JP2001139621, JP2002249507, CN1242780A, CN1268957A, and CN1524886A. In the literature.

For example, CN 1524886 A discloses a composite support for olefin polymerization, in particular propylene polymerization or copolymerization catalysts, and a catalyst component and catalyst using the composite support. The catalyst component (ie, the main catalyst) is prepared by first contacting the magnesium halide with one or more of a fatty alcohol, an aromatic alcohol, an organic epoxy compound, an organophosphorus compound, and the like as an internal electron donor. To form a solution; then, the solution is mixed with silica gel having an average particle diameter of less than 30 μm, and spray-dried to obtain spherical composite carrier particles; then the carrier is loaded with a titanium compound and a conventional internal electron donor such as an aliphatic group. A dicarboxylic acid ester or an aromatic dicarboxylic acid ester, particularly a phthalate compound, gives the catalyst component. The polypropylene resin prepared by using the catalyst component has a high isotacticity, but the catalyst activity is not satisfactory.

As can be seen from the above, in order to obtain an olefin polymerization catalyst having excellent comprehensive performance, a novel internal electron donor compound is still to be developed.

Summary of the invention

In order to solve the above technical problems, an object of the present invention is to provide a disulfonic acid ester compound and use thereof. The disulfonic acid ester compound can be used as an internal electron donor for the preparation of an olefin polymerization catalyst component, and can have an excellent overall performance of the obtained hydrocarbon polymerization catalyst component.

Another object of the present invention is to provide an olefin polymerization catalyst component prepared by using the disulfonic acid ester compound.

It is also an object of the present invention to provide an olefin polymerization catalyst comprising the catalyst component and the use of the catalyst.

In order to achieve the above object, the present invention first provides a disulfonate compound having the following formula I,

Where n is an integer and n≥0;

R ₁ and R _{2 are the} same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are the} same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 cycloalkane. a group consisting of a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are} not all hydrogen and/or a halogen atom.

In the above disulfonate compound, preferably, the alkyl group, ring in the group selected from the group consisting of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ Any one or more of the carbon atoms and/or hydrogen atoms in the alkyl group, the aryl group, the arylalkyl group, the alkaryl group, the alkene group and the fused ring aryl group are substituted by a halogen atom. More preferably, any one or several hydrogen atoms on any one or several of the aryl, alkaryl and aralkyl groups selected from the group of R ₁ and R ₂ are replaced by a halogen atom .

In the above disulfonate compound, preferably, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ contain at least one hetero atom selected from nitrogen, oxygen, sulfur, A group of silicon, phosphorus, and halogen atoms.

In the above disulfonate compound, preferably, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ (and a carbon attached to these substituents) form a ring (ring form) Diversified, may be any of R _{3 -} R ₈ into a ring, can be a three-membered ring, four-membered ring, five-membered ring, six-membered ring, fused ring, etc.), forming a cycloalkyl-substituted diol a sulfonate or aryl substituted diphenol sulfonate, and a sulfonate in which one oxygen in the ester group is attached to the aryl group (phenol) and the other oxygen is linked to the alkyl group (alcohol). It should be noted that R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may not be ring-formed.

In the above disulfonate compound, preferably, several of the carbons bonded to R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ may be double-bonded.

In the above disulfonate compound, preferably, R ₁ and R ₂ (same or different) are respectively selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Composition of tert-butyl, n-pentyl, cyclopentyl, cyclohexyl, phenyl, alkylphenyl, halophenyl, haloalkylphenyl, fluorenyl, benzyl, phenylethyl and fused ring aryl Group. More preferably, R ₁ and R ₂ (same or different) are each selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylbenzene a group consisting of a halo, a halophenyl group, and a haloalkylphenyl group. Wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl, decyl, benzyl, phenyl b The aryl group and the fused ring aryl group are a group substituted or unsubstituted by a halogen atom.

In the above disulfonic acid ester compound, preferably, at least one of R ₁ and R ₂ is a group containing a benzene ring. More preferably, the benzene ring-containing group is a phenyl group or a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. Particularly preferably, R ₁ and R ₂ are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. Wherein, when n = 1, R ₁ and R ₂ (same or different) are preferably selected from the group consisting of phenyl, halophenyl, methylphenyl and halomethylphenyl, respectively.

In the above disulfonate compound, preferably, at least one of R ₃ and R ₄ is selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. a group consisting of a base, a tert-butyl group, a phenyl group, an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halogenated phenyl group; at least one of R ₅ and R ₆ is selected from the group consisting of hydrogen , halogen atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl substituted phenyl) And a group consisting of halophenyl groups. Wherein the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom. More preferably, R ₃ and R _{4 are} not all phenyl groups, and R ₅ and R _{6 are} not all phenyl groups.

More preferably, R ₃ and R ₄ (same or different) are each selected from the group consisting of hydrogen, a halogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a benzene group. a group consisting of an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halogenated phenyl group; R ₅ and R ₆ (identical or different) are each selected from hydrogen, a halogen atom, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halogenated A group consisting of phenyl groups. Wherein the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom. Particularly preferably, R ₃ and R _{4 are} not all phenyl groups, and R ₅ and R _{6 are} not all phenyl groups.

Particularly preferably, one of R ₃ and R ₄ is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkyl a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group; one of R ₅ and R ₆ is hydrogen and the other is selected from the group consisting of methyl, ethyl, and n-propyl a group consisting of isopropyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl; Wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl and alkylphenyl groups are substituted or unsubstituted groups by a halogen atom; and R ₃ and The group which is not hydrogen in R ₄ and the group which is not hydrogen in R ₅ and R ₆ are not all phenyl groups.

In the above disulfonate compound, preferably, at least one of R ₇ and R ₈ is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary. A group consisting of a butyl group, a phenyl group, an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halogenated phenyl group. More preferably, R ₇ and R ₈ (same or different) are each selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkane A group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group. Wherein the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom. Particularly preferably, R ₇ and R _{8 are} not all phenyl groups.

In the above disulfonate compound, preferably, at least one of R ₇ and R ₈ is a group containing a benzene ring. More preferably, the benzene ring-containing group is a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. Particularly preferably, R ₇ and R ₈ are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom.

Among the above disulfonate compounds, preferably, n = 0, 1, 2, 3, 4 or 5.

According to a particular embodiment of the invention, when n = 0, then the disulfonate compound has the following general formula II:

According to a particular embodiment of the invention, when n = 1, then the disulfonate compound has the following general formula III:

According to a particular embodiment of the invention, when n=2, the disulfonate compound has the following general formula IV:

In the above disulfonate compound, preferably, when n = 1, at least one of R ₃ , R ₄ , R ₅ and R ₆ is hydrogen.

In the above disulfonate compound, preferably, when n=1, at least one of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is a halogen atom, but R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are} not all hydrogen and/or a halogen atom; and at least one of the groups of the groups R ₃ and R ₄ , R ₅ and R ₆ is hydrogen, but R ₃ , R ₄ , R ₅ and R _{6 are} not all hydrogen.

In the above disulfonate compound, preferably, when n = 1, and _{three of} R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, the other is a halogen-substituted or unsubstituted methyl group. , ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.

In the above disulfonate compound, preferably, when n=1, and only one of the groups of the groups R ₃ and R ₄ , R ₅ and R ₆ is hydrogen, the other two groups The group is not all halogen. More preferably, when R ₃ and R ₄ , R ₅ and R _{6 are the} same group other than hydrogen, and only one of R ₇ and R ₈ is hydrogen, then another of R ₇ and R ₈ A group other than hydrogen is different from a group other than hydrogen in R ₃ , R ₄ , R ₅ and R ₆ .

In the above disulfonate compound, preferably, when n=1, and only one group of each of the two groups of R ₃ and R ₄ , R ₅ and R ₆ is selected from linear and branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 thick a group consisting of a cyclic aryl group (more preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, phenyl and substituted or unsubstituted) a group consisting of an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group), and when they are the same, R ₇ and R _{8 are} not all hydrogen, and one of R ₇ and R ₈ is In the case of hydrogen, the other is selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, and a C7-C20 alkaryl group. a group consisting of a C2-C20 olefin group and a C6-C20 fused ring aryl group (more preferably selected from a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group substituted or unsubstituted by a halogen atom) Base, isobutyl, tert-butyl, phenyl and alkylphenyl (preferably C1-C20 alkyl substituted phenyl) The group formed). Wherein the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkaryl group, the alkene group and the fused ring aryl group are a group in which a halogen atom is substituted or unsubstituted.

In the above disulfonate compound, preferably, when n=2, at least two of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are not Hydrogen and/or halogen atoms.

In the above disulfonate compound, preferably, when n = 2, at least one of R ₃ and R ₄ is hydrogen or a halogen atom, and at least one of R ₅ and R ₆ is hydrogen or a halogen atom. And R ₇ , R ₈ , R ₉ and R _{10 are} not all hydrogen. More preferably, only one of R ₃ and R ₄ is hydrogen or a halogen atom, and only one of R ₅ and R ₆ is hydrogen or a halogen atom, and R ₇ , R ₈ , R ₉ and R _{10 are} not all hydrogen.

In the above disulfonate compound, preferably, when n = 2, and only one of R ₃ and R ₄ is hydrogen or a halogen atom, only one of R ₅ and R ₆ is hydrogen or a halogen atom, and R _{7. When} R ₈ , R ₉ and R ₁₀ are both hydrogen, the groups other than hydrogen or a halogen atom among R ₃ , R ₄ , R ₅ and R ₆ are not all methyl groups.

In the above disulfonate compound, more preferably, when n = 2, R ₁ and R ₂ are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. a group; and one of R ₃ and R ₄ is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkane a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group; one of R ₅ and R ₆ is hydrogen and the other is selected from the group consisting of methyl, ethyl, and a group consisting of propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl And R ₇ , R ₈ , R ₉ and R ₁₀ (identical or different) are respectively selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, A group consisting of a phenyl group, an alkylphenyl group (preferably a C1-C20 alkyl-substituted phenyl group), and a halogenated phenyl group. Wherein the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.

In the above disulfonate compound, preferably, when n≥3, one of R ₃ and R ₄ is hydrogen, the other is methyl, and one of R ₅ and R ₆ is hydrogen, and One is a methyl group, and when R ₇ and R _{8 are} all hydrogen or hydrogen and methyl respectively, at least one of R ₁ and R ₂ is a halogen atom and/or an alkyl group (preferably a C1-C20 alkyl group). Substituted phenyl.

In the above disulfonate compound, preferably, when n=3, at least two of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are not hydrogen, and R ₃ , Several groups of R ₄ , R ₅ , R ₆ , R ₇ and R ₈ respectively bonded to different carbon atoms form a fused ring; more preferably, and at least one of R ₁ and R ₂ is selected from a halogen atom Or a group consisting of an unsubstituted aryl group and an alkaryl group; particularly preferably, both of R ₁ and R ₂ are selected from the group consisting of an aryl group and an alkylaryl group substituted or unsubstituted with a halogen atom.

In the above disulfonate compound, preferably, when n=4, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are not ring-formed, and at least R ₁ and R ₂ are There is a group consisting of an aryl group and an alkylaryl group which are substituted or unsubstituted by a halogen atom; more preferably, R ₁ and R ₂ are each selected from an aryl group and an alkylaryl group which are substituted or unsubstituted by a halogen atom. Group.

In the above disulfonate compound, preferably, when n≥3, R ₁ and R ₂ are each selected from the group consisting of a phenyl group, a phenyl group substituted by a C1-C20 alkyl group and/or a halogen atom. a group; and one of R ₃ and R ₄ is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkyl a group consisting of a phenyl group (preferably a C1-C20 alkyl-substituted phenyl group) and a halophenyl group; one of R ₅ and R ₆ is hydrogen and the other is selected from the group consisting of methyl, ethyl, and n-propyl a group consisting of isopropyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl; And the group which is not hydrogen in R ₃ and R ₄ and the group which is not hydrogen in R ₅ and R ₆ are not all phenyl; R ₇ and R ₈ (identical or different) are respectively selected from hydrogen, methyl, Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl (preferably C1-C20 alkyl-substituted phenyl) and halophenyl a group consisting of, and R ₇ and R _{8 are} not all phenyl; more preferably, and n = 3 or 4. Wherein the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are groups which are substituted or unsubstituted by a halogen atom.

In the above disulfonate compound, preferably, when n≥5, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are not ring-formed.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula V:

Wherein X is carbon or nitrogen, and Y is carbon or nitrogen;

When X is nitrogen, then the substituent R ₆ ' is absent; when Y is nitrogen, the substituent R ₅ ' is absent; when both X and Y are nitrogen, there are no substituents R ₅ ' and R ₆ ';

R ₃ ', R ₄ ', R ₅ ' and R ₆ ' are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula VI:

Wherein A and B are each selected from the group consisting of carbon, nitrogen, oxygen and sulfur;

When A is nitrogen, then there is no substituent R ₅ ”; when B is oxygen or sulfur, then there are no substituents R ₃ ′′ and R ₄ ”; when B is nitrogen, there is no substituent R ₃ ” ;

R ₃ ", R ₄ ", R ₅ " and R ₆ " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula VII:

Wherein R ₁ and R _{2 are the} same or different and are respectively selected from a linear and branched alkyl group derived from C1 to C10, a cycloalkyl group of C3-C20, an aryl group of C6-C20, an aralkyl group of C7-C20, a group consisting of alkyl alkaryl groups of C7-C20;

R ₃ , R ₄ , R ₅ and R _{6 are the} same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-. A group consisting of an aralkyl group of C10 and an alkylaryl group of C7-C10.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula VIII:

Wherein R ₁ and R _{2 are the} same or different and are respectively selected from a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, a fused ring aryl group of C6-C20, optionally hydrogen in the phenyl ring of the aryl group, the alkylaryl group or the aralkyl group The ground is replaced or unsubstituted by a halogen atom;

R _{11 -} R ₁₆ are each hydrogen or methyl.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula IX:

R ₃ , R ₄ , R ₅ and R _{6 are the} same or different and are respectively selected from hydrogen, a halogen atom, a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, and a C6-C20 aromatic group. a group consisting of a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R ₁₁ '-R ₁₈ 'is hydrogen or methyl, respectively.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula X:

Wherein R ₁ and R _{2 are the} same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R ₃ , R ₄ , R ₅ , R ₆ , R ₁₁ ′′ and R ₁₂ ′′ are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 group. a group consisting of a cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R ₃ , R ₄ , R ₅ , R ₆ , R ₁₁ ′′ and R ₁₂ ′′ are not all hydrogen and/or a halogen atom.

According to a particular embodiment of the invention, preferably the disulfonate compound of formula I comprises a compound of formula XI:

R ₃ , R ₄ , R ₅ and R _{6 are the} same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 group. a group consisting of an aryl group, an C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group; more preferably, R ₃ , R ₄ , R ₅ and R ₆ contain at least one hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, silicon, phosphorus and a halogen atom, and in R ₃ , R ₄ , R ₅ and R ₆ Several are looped or not looped together;

R ₁ ", R ₂ ", R ₃ " and R ₄ " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6 group. a group of -C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 fused ring aryl, and R ₁ ", R ₂ Several of ", R ₃ " and R ₄ " form or not form a fused ring structure.

Specifically, the disulfonate compound represented by Formula I of the present invention includes, but is not limited to, the following:

1,2-butanediol ditosylate, 2,3-butanediol ditosylate, catechol di-p-toluenesulfonate, dimethyl 2,5-dicarboxylate-3,4 -dihydroxydi-p-toluenesulfonate, 1,3-butanediol ditosylate, 2,4-pentanediol di-tert-butylbenzenesulfonate, 2,4-pentanediol di-m-chloride Benzene sulfonate, 2,4-pentanediol di-bromobenzenesulfonate, 2,4-pentanediol di-p-chlorobenzenesulfonate, 2,4-pentanediol di-p-toluenesulfonate, 2 , 4-pentanediol diphenyl sulfonate, 2,4-pentanediol di-p-butylbenzene sulfonate, 6-heptene-2,4-heptanediol diphenyl sulfonate, 3,5- Heptanediol diphenyl sulfonate, 3,5-heptanediol di-p-chlorobenzenesulfonate, 2,6-dimethyl-3,5-heptanediol diphenyl sulfonate, 2,6-di Methyl-3,5-heptanediol di-p-toluenesulfonate, 2,6-dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate, 6-methyl-2,4-heptane Glycol diphenyl sulfonate, 6-methyl-2,4-heptanediol di-toluene sulfonate, 6-methyl-2,4-heptanediol di-p-toluene sulfonate, 6-methyl -2,4-heptanediol di-p-chlorobenzenesulfonate, 6-methyl-2,4-heptanediol dipylyl sulfonate, 3-methyl-2,4-pentanediol Chlorobenzenesulfonate, 3-methyl-2,4- Di-di-toluenesulfonate, 3-butyl-2,4-pentanediol di-p-toluenesulfonate, 3-methyl-2,4-pentanediol di-tert-butylbenzenesulfonate, 3,3-Dimethyl-2,4-pentanediol diphenyl sulfonate, 3-ethyl-2,4-pentanediol diphenyl sulfonate, 3-butyl-2,4-pentane Alcohol diphenyl sulfonate, 3-allyl-2,4-pentanediol diphenyl sulfonate, 4-methyl-3,5-heptanediol diphenyl sulfonate, 2-ethyl-1 , 3-hexanediol diphenyl sulfonate, 2-ethyl-1,3-hexanediol xylene sulfonate, 2,2,4-trimethyl-1,3-pentanediol diphenyl sulfonate Acid ester, 4-methyl-3,5-octanediol diphenyl sulfonate, 5-methyl-4,6-nonanediol diphenyl sulfonate, 1,3-diphenyl-2-methyl 1,3-1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-1,3-propanediol di-n-propyl sulfonate, 1,3-diphenyl-2-methyl-1,3 - Propylene glycol di-n-propyl sulfonate, 1,3-diphenyl-2-methyl-1,3-propanediol diethyl sulfonate, 1,3-diphenyl-2,2-dimethyl -1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol di-n-propyl sulfonate, 1-phenyl-2-methyl -1,3-butanediol diphenyl sulfonate, 1-phenyl-2-methyl-1,3-butanediol dipivalyl sulfonate, 6- Alkene-2,4-heptanediol dipivalyl sulfonate, 2,2,4,6,6-pentamethyl-3,5-hexanediol diphenyl sulfonate, 1,3-di-tert Butyl-2 ethyl-1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-1,3-propanediol diacetate, 1-furan-2-methyl-1,3-butyl Diol diphenyl sulfonate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl sulfonate, 2-isopropyl-2 isopentyl-1,3-propanediol di-p-chlorobenzene Sulfonate, 2-isopropyl-2isopentyl-1,3-propanediol di-chlorobenzenesulfonate, 2-isopropyl-2isopentyl-1,3-propanediol di-p-methoxybenzene Sulfonate, 2-isopropyl-2isopentyl-1,3-propanediol di-n-propyl sulfonate, 2,2-diisobutyl-1,3-propanediol diphenyl sulfonate, 2-iso Propyl-2-isopentyl-1,3-propanediol dibenzenesulfonate, 1,8-naphthalenediol di-p-toluenesulfonate, 9,9-bis(phenylsulfonylmethyl)phosphonium, 9 , 9-bis(p-methylbenzenesulfonylmethyl) Indole, 1,1-bis(p-toluenesulfonylmethyl)cyclohexane, 2,3-diethyl-1,4-butanediol di-p-toluenesulfonate, 2,5-dimethyl- 2,5-hexanediol di-p-toluenesulfonate, 3,6-dimethyl-3,6-dioctanol di-p-toluenesulfonate, cis-2-butene-1,4-diol II P-toluenesulfonate, 1,5-diphenyl-1,5-pentanediol di-p-toluenesulfonate, 1,4-hexanediol di-p-toluenesulfonyl ester, 1,5-hexane Alcohol di-p-toluenesulfonate, 2,2'-biphenyldimethanol di-p-toluenesulfonate, and the like.

The above-mentioned disulfonic acid ester compound provided by the present invention can be obtained by the following method: a diol compound, a diphenol compound or a monophenol monool compound (that is, one hydroxyl group to be esterified is linked to an aryl group, and the other hydroxyl group is The alkyl-linked compound) is esterified with a sulfonic acid or a sulfonyl chloride to give the disulfonate compound.

The disulfonate compounds of the present invention can be prepared by a variety of methods. According to a specific embodiment of the present invention, the method for preparing the above-mentioned disulfonic acid ester compound comprises the steps of: a hydrocarbyl sulfonic acid (RSO ₃ H, wherein R is R ₁ or R ₂ in the above formula I) or a hydrocarbyl sulfonate An acid chloride (RSO ₃ Cl, wherein R is R ₁ or R ₂ in the above formula I) is esterified with a diol compound, a diphenol compound or a monophenol monool compound having the formula XII to give the Disulfonate compound,

Where n is an integer and n≥0;

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R _{8 are} not all hydrogen and/or halogen.

The preferred ranges of R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are as described above and will not be described herein.

In the above preparation method, the diol compound, the diphenol compound or the monophenol monool compound having the formula XII can be produced according to the preparation method in the prior art, as in the case of CN1041752A, pages 5-6, CN1141285A. A method for producing the disclosed diol compound and a method for synthesizing 9,9-(bishydroxymethyl)anthracene (Acta Chemica Scandina-vica 21, pp. 718-720). The entire contents of the above-mentioned three documents are hereby incorporated by reference herein.

In the above preparation method, the specific steps of the esterification reaction and the parameters such as temperature and time are mainly changed with different reactants, and those skilled in the art can carry out the conventional steps of esterification reaction, temperature and time, etc. Regulation.

In the above preparation method, when n = 0, the diol compound, the diphenol compound or the monophenol monool The compound has the general formula XIII:

In the above preparation method, when n=1, the diol compound, the diphenol compound or the monophenol monool compound has the following formula XIV:

In the above preparation method, when n = 2, the diol compound, the diphenol compound or the monophenol monool compound has the following formula XV:

The present invention also provides the use of the above disulfonic acid ester compound in the preparation of an olefin polymerization catalyst component.

The disulfonate compound of the present invention is applied to the preparation of the olefin polymerization catalyst component to obtain a catalyst component excellent in overall performance. The use of the catalyst component as a main catalyst for catalyzing the polymerization of olefins has high catalytic activity and sensitivity to hydrogen modulation, and a polymer having high stereospecificity and a broad molecular weight distribution can also be obtained.

The above olefin polymerization catalyst component can be produced by a method in the prior art, such as the following methods.

One of the methods is: grinding the anhydrous magnesium dichloride and the disulfonic acid ester compound of the present invention under the activation condition of magnesium dichloride; and grinding the mixture at 80-135 ° C with excess TiCl ₄ The reaction is carried out once or several times for each reaction time of 0.5 to 4 hours; then the solid mixture after the reaction is washed with a hydrocarbon solvent (washing is required after each reaction) until it is free of chloride ions, and an olefin polymerization catalyst component is obtained.

Another method is: grinding magnesium dichloride, a titanium compound and a disulfonate compound of the present invention in an anhydrous state to obtain a ground mixture; and then using, for example, 1,2-dichloroethane, chlorobenzene, The halogenated hydrocarbon such as dichloromethane is reacted with the milled mixture at a temperature of from 40 ° C to the boiling point of the halogenated hydrocarbon for 1-4 hours; then the solid mixture after the reaction is washed with an inert hydrocarbon solvent such as hexane. An olefin polymerization catalyst component is obtained.

Still another method is: pre-activation of magnesium dichloride by a known method, and then reacting with pre-activated magnesium dichloride at 80-135 ° C using an excess of TiCl ₄ solution containing the disulfonate compound of the present invention or Several times, the solid mixture after the reaction is washed with an inert hydrocarbon solvent such as hexane to remove unreacted TiCl ₄ to obtain an olefin polymerization catalyst component.

Still another method is to prepare an olefin polymerization catalyst by reacting a magnesium alkoxide or a chloroalcoholate with an excess TiCl ₄ solution containing the disulfonic acid ester compound of the present invention at 80 to 135 °C. A preferred embodiment of the method is to use a titanium compound of the formula TiZ _m (OQ) _4-m (wherein Q is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom, m = 1-4, preferably TiCl ₄ ) and an adduct of the formula MgCl ₂ ·pTOH (wherein p is an integer of 0.1-6, preferably 2-4, and T is a hydrocarbon group having 1-20 carbon atoms) at 80-130 ° C The reaction is carried out for 0.5 to 2 hours to prepare an olefin polymerization catalyst. Wherein, the adduct of the formula MgCl ₂ ·pTOH can be suitably formed into a spherical shape by mixing an alcohol and magnesium chloride in the presence of an inert hydrocarbon solvent which is not miscible with the adduct, so that the emulsion rapidly quenches. Thereby, the adduct is cured in the form of spherical particles. Examples of spherical MgCl ₂ ·pTOH adducts prepared in accordance with this method can be found in USP 4,399,054 and USP 4,469,648. The MgCl ₂ ·pTOH adduct obtained by this method can be directly reacted with the titanium compound, or it can be subjected to a thermally controlled dealcoholization (at 80-130 ° C) to obtain a new adduct, wherein The number of moles of alcohol is generally less than 4, preferably from 2 to 3.5. The reaction with the titanium compound can be carried out by suspending the MgCl ₂ ·pTOH adduct (dealcoholated or unde-alcoholized) in cold TiCl ₄ (generally below 0 ° C). Wherein TiCl ₄ is used as the titanium compound, and other titanium compounds may be used instead of TiCl ₄ , and the reaction with TiCl ₄ may be carried out once or several times. The disulfonic acid ester compound of the present invention may be added to TiCl ₄ to carry out the reaction, and one or several reactions may be carried out. After the reaction, the solid mixture is washed to obtain an olefin polymerization catalyst component.

Still another method is: using a solution of an aromatic hydrocarbon (for example, toluene, xylene, etc.) of TiCl ₄ containing the disulfonate compound of the present invention at 80 to 130 ° C with, for example, a dialkoxymagnesium or a diaryloxy group. A magnesium alkoxide compound such as magnesium is reacted for a reaction time of 0.5 to 4 hours, and may be reacted once or several times, after which the solid mixture after the reaction is washed to obtain an olefin polymerization catalyst component.

In another aspect, the present invention provides an olefin polymerization catalyst component prepared by using the above-described disulfonic acid ester compound, which comprises the reaction product of the following raw materials:

Raw material (1) composite carrier: which forms a solution by contacting a magnesium halide with one or several compounds capable of dissolving magnesium halide, and then mixing the solution with silica having an average particle diameter of less than 10 μm, and preparing by spray drying ;

Starting material (2) electron donor a: at least one compound selected from the group consisting of the above-mentioned disulfonic acid ester compounds;

Starting material (3) electron donor b: at least one selected from the group consisting of aliphatic mono- and dicarboxylic acid ester compounds, aromatic mono- and dicarboxylic acid ester compounds, and diether compounds represented by formula XVI The composition of the group Object:

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{6 are the} same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6 a group consisting of an aryl group of C10, an aralkyl group of C7-C10, an alkylaryl group of C7-C10; R ⁷ and R ^{8 are the} same or different and are respectively selected from linear and branched alkane from C1 to C10; a group consisting of a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, and a C7-C20 alkaryl group;

Raw material (4) titanium halide: at least one compound selected from the group consisting of titanium compounds represented by the general formula Ti(OQ) _4-m Z _m , wherein Q is selected from the group consisting of C1-C14 aliphatic hydrocarbon groups Group, several Qs may be the same or different, Z is selected from the group consisting of F, Cl and Br, several Z may be the same or different, and m is an integer from 1 to 4;

Wherein, the total amount of the electron donor a and the electron donor b is 0.01 to 1 mole per mole of the magnesium halide in the composite carrier, and the molar ratio of the electron donor a to the electron donor b is 0.1 to 10, the titanium compound It is 1-100 moles.

In the above olefin polymerization catalyst component, preferably, the electron donor b is selected from the group consisting of a benzoate compound, a phthalate compound, a malonate compound, a succinate compound, and a pentane compound. A group consisting of an acid ester compound, a pivalate compound, and a diether compound represented by the formula XVI.

The malonate compound is represented by the formula XVII:

Wherein R ^{1 '} and R ^{2 ' are the} same or different and are each selected from the group consisting of methyl and ethyl; R ^{3 '} and R ^{4 ' are the} same or different and are each selected from a C1-C20 hydrocarbon group and a hydrocarbon oxygen group. A group consisting of bases.

The glutarate compound is represented by the formula XVIII:

Wherein R ^1" and R ^{2" are the} same or different and are each selected from the group consisting of hydrocarbyl groups; R ^{3" -} R ^{8" are the} same or different and are each selected from the group consisting of hydrogen, C1-C20 hydrocarbyl groups. R ^{3" -} R ^8" is preferably a hydrocarbon group which is substituted by a halogen atom and which has two substituents on the same carbon atom bonded to form a ring.

The succinate compound is represented by the formula XVX:

Wherein R ^1"' and R ^{2"' are the} same or different and are each selected from the group consisting of a C1-C20 hydrocarbon group (which may contain a hetero atom); R ^3"' -R ^{6"' are the} same or different, respectively a group consisting of hydrogen, C1-C20 hydrocarbon groups (which may contain heteroatoms); preferably, R ^3"' -R ^{6"' is} not all hydrogen, and R ^3"' -R ^6"' is not The group of hydrogen is selected from the group consisting of a C1-C20 hydrocarbon group which may contain a hetero atom.

In the above olefin polymerization catalyst component, preferably, the magnesium halide used in the composite carrier has a general formula of Mg(OJ) _2-v G _v , wherein J is selected from a linear chain of C ₁ - C ₁₄ , a group consisting of branched and cyclic alkyl groups, several J may be the same or different, G is selected from the group consisting of F, Cl and Br, several G may be the same or different, v is 0, 1 or 2. Specifically, the magnesium halide includes, but is not limited to, magnesium dichloride, magnesium dibromide, magnesium phenoxide chloride, magnesium isopropoxide chloride, magnesium butoxide chloride, magnesium diethoxylate, and the like. The magnesium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

In the above olefin polymerization catalyst component, preferably, the compound for dissolving the magnesium halide is selected from the group consisting of halogenated fatty alcohols, halogenated aromatic alcohols, aliphatic ethers, cyclic ethers, aliphatic ketones, fatty acid alkyl esters, aromatic acids. a group consisting of alkyl esters. Particularly suitable are halogenated C1-C8 saturated fatty alcohols; lower alkyl esters of C1-C4 saturated aliphatic carboxylic acids; C7-C8 aromatic mono- and polycarboxylic acid lower alkyl esters; C2-C8, Preferred are C4-C5 fatty ethers; C4-C5 aliphatic ethers; C4-C5 cycloaliphatic ethers; preferably C4 monoethers or diethers; and C3-C6, preferably C4-C5 Aliphatic ketone. "Lower alkyl" as used herein refers to a C1-C6 alkyl group.

In the above olefin polymerization catalyst component, more preferably, the compound for dissolving the magnesium halide comprises at least one group selected from the group consisting of halogenated C1-C8 fatty alcohols, C7-C10 aromatic alcohols. compound of. Particularly preferably, the compound is at least one of a halogenated C1-C8 fatty alcohol and a C7-C10 aromatic alcohol, or a halogenated C1-C8 fatty alcohol and/or a C7-C10 aromatic alcohol and a C1-C6 Fatty ether, C3-C5 cyclic ether, fat or A mixture of C1-C6 alkyl esters of aromatic carboxylic acids.

Among the above olefin polymerization catalyst components, examples of the compound for dissolving the magnesium halide include, but are not limited to, methanol, ethanol, isopropanol, n-butanol, isobutanol, isoamyl alcohol, n-octanol, and isooctyl Alcohol, ethylene glycol, propylene glycol, chlorohydrin, trichloroethanol, diethyl ether, dibutyl ether, methyl formate, ethyl acetate, butyl acetate, hexyl ether, tetrahydrofuran (THF), acetone, methyl isobutyl ketone, benzene Ethyl formate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, etc., preferably ethanol, isopropanol, n-butanol, trichloroethanol, tetrahydrofuran, benzoic acid Ethyl ester, diethyl phthalate.

In the above olefin polymerization catalyst component, preferably, the compound for dissolving the magnesium halide further includes a system containing an organic epoxy compound selected from the group consisting of C2-C8 fat, and/or an organic phosphorus compound. A group consisting of a family of epoxides and diepoxides, halogenated aliphatic epoxides, and diepoxides and glycidyl ethers. For example: ethylene oxide, propylene oxide, butylene oxide, vinyl ethylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether. The organophosphorus compound is selected from the group consisting of C1-C10 hydrocarbyl esters of orthophosphoric acid and phosphorous acid and halohydrocarbyl esters. For example: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, triphenyl methyl phosphite .

In the above olefin polymerization catalyst component, the compound for dissolving the magnesium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

Usually, from 3 to 50 moles, preferably from 6 to 30 moles, of the compound for dissolving the magnesium halide is required per mole of the magnesium halide, so that the magnesium halide is contacted with the compound to form a homogeneous solution.

The preparation of such a solution can be carried out in the presence of an inert solvent which does not form an adduct with the magnesium halide. Preferably, the inert solvent is selected from the group consisting of C5-C12 alkane, C1-C6 halogenated hydrocarbon and C6-C12 aromatic hydrocarbon, such as hexane, heptane, dichloromethane, toluene, xylene, B. Benzene, etc. The inert solvent may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

In the above olefin polymerization catalyst component, the silica is generally selected from silica having an average particle diameter of less than 10 μm, also referred to as fumed silica, to facilitate spray molding to obtain a composite carrier of smaller particles. The specific surface area of such silica is generally 200 ± 50 m ² /g. Preferably, the silica has an average particle size of less than 1 μm.

In the above olefin polymerization catalyst component, the solution is mixed with silica to obtain a slurry suitable for spraying. Generally, silica is added in an amount of from 10 to 200 g per liter of the solution.

In the above olefin polymerization catalyst component, the spray drying may be carried out by the following steps: a slurry obtained by mixing a solution with silica and a dry dry gas are spray-dried by a spray dryer to obtain a spherical composite carrier solid. Particles.

In the above olefin polymerization catalyst component, preferably, the composite carrier has an average diameter of 5 to 60 μm, more preferably 10 to 40 μm, particularly preferably 12 to 30 μm, which is capable of making the composite carrier more suitable. For the preparation of a catalyst for propylene polymerization.

In the above olefin polymerization catalyst component, preferably, the titanium halide may be selected from titanium tetrahalide, particularly titanium tetrachloride, trichlorobutoxy and trichlorophenoxy titanium; tetraalkoxy titanium, particularly It is titanium tetrabutoxide, titanium tetraethoxide, and the like. The titanium halide may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

In the above olefin polymerization catalyst component, preferably, the total amount of the electron donor a and the electron donor b is 0.05 to 0.5 mole per mole of the magnesium halide in the composite carrier; the electron donor a and the electron donor b The molar ratio is 0.2-5.

The olefin polymerization catalyst component of the present invention can be produced by various published production methods. In the preparation process, the electron donor a and the electron donor b may be treated before or after the reaction of the composite carrier with the titanium compound. The electron donor a and the electron donor b can be used together in a variety of ways, can be added under the same or different steps or conditions, preferably in the same steps and conditions.

Specifically, the olefin polymerization catalyst component of the present invention can be produced by the following method:

(1) Preparation of magnesium halide solution

The magnesium halide solution can be prepared according to some of the disclosed methods, such as the magnesium halide dissolution system disclosed in US Pat. No. 4,478,983 and US Pat.

Preferably, the magnesium halide solution is prepared as follows:

In a stirred reactor, an alcohol or a mixture of two or more alcohols may be added, or an ether or an ester may be further added, and then anhydrous magnesium halide is added, and the magnesium halide is dissolved by heating; wherein the alcohol and the magnesium halide are The molar ratio is (3-50): 1, and the molar ratio of the ether or ester to the magnesium halide is (0-20):1. The above magnesium halide may also be dissolved in an inert solvent in an amount of 0-20 mL/g based on the mass of the magnesium halide;

(2) Preparation of spherical Mg(OJ) _2-v G _v /SiO ₂ composite carrier

Adding fumed silica gel to the above magnesium halide solution, the amount of silica gel is 0.1-2 g per gram of magnesium halide, and the silica gel used is fumed silica having an average particle diameter of less than 10 μm; then stirring at 10-100 ° C 0.5-3h, the slurry is prepared; then the slurry is spray-dried together with the inert dry gas by a spray dryer to obtain a spherical Mg(OJ) _2-v G _v /SiO ₂ composite carrier having an average particle size of 5-60 μm; The inlet air temperature during spray drying is controlled at 80-300 ° C, and the outlet gas temperature is controlled at 50-200 ° C; in general, the composition of the composite carrier is:

Mg(OJ) _2-v G _v : 20%-60% by weight,

SiO ₂ : 10% - 60% by weight,

Alcohol: 5%-40% by weight,

Ether: 0%-20% by weight,

Solvent: <5% by weight;

(3) Preparation of olefin polymerization catalyst components

The above composite carrier is suspended in a mixture of a titanium halide and an inert solvent (preferably hexane) (the amount of titanium halide is 5-10 mL/g by mass of the composite carrier, and the volume ratio of the inert solvent to the titanium halide is 0-2) Medium, slowly warming to 80-100 ° C, after which the liquid is filtered off for a period of time; adding an excess of titanium halide (the amount of titanium halide is 12-16 mL / g based on the mass of the composite carrier), 1-3h Internally, the temperature is slowly raised to 100-120 ° C, and the electron donor a and the electron donor b are simultaneously added during the temperature increase, and the total amount of the electron donor a and the electron donor b is calculated per mole of the magnesium halide in the composite carrier. 0.01-1 mole, the molar ratio of electron donor a to electron donor b is 0.1-10; after 1-2 hours of reaction, it can be filtered; then a certain amount of titanium halide can be added, maintained at 120 ° C for 1-2 h, and then filtered (final The step of adding a titanium halide may be omitted; washing the solid product with an inert solvent such as hexane or the like, and then drying the solid product under vacuum at 30 to 50 ° C to obtain an olefin polymerization catalyst of the present invention.

The olefin polymerization catalyst component of the invention is used in combination with a composite carrier and two internal electron donor compounds, thereby ensuring high activity, high stereospecificity and high hydrogen modulating sensitivity of the obtained catalyst, and at the same time, can be prepared by using the catalyst. The polymer has a high bulk density and a broad molecular weight distribution, which is advantageous for industrial production and post-polymer processing.

The present invention also provides an olefin polymerization catalyst comprising the following components:

Component (1) the above olefin polymerization catalyst component;

Component (2) an alkyl aluminum compound.

In the above catalyst, the olefin polymerization catalyst component of the present invention may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

In the above catalyst, preferably, the alkyl aluminum compound has a formula represented by AlL _w D _3-w , wherein L is selected from hydrogen, a C1-C20 alkyl group, a C1-C20 aryl group, and C1- A group consisting of aralkyl groups of C20, several L may be the same or different, D is a halogen atom, preferably selected from chlorine and bromine, and several D may be the same or different, w = 1, 2 or 3. The alkyl aluminum compound is preferably triethyl aluminum and/or triisobutyl aluminum. The alkyl aluminum compounds may be used singly or in combination of several kinds, and when used in combination, may be mixed in any ratio.

According to a specific embodiment of the present invention, preferably, the catalyst further comprises an organosilicon compound of the formula (3) of the formula T ¹ _u Si(OT ² ) _4-u as an external electron donor component, wherein T ¹ Selected from the group consisting of hydrogen, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group and a halogenated alkyl group, several T ^{1 's} may be the same or different; T ^{2 is} selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group and a halogenated alkyl group. For the group formed, several T ² may be the same or different; T ¹ and T ^{2 are the} same or different; u is an integer of 0-3. The organosilicon compound may be used singly or in combination of several kinds, and when used in combination, it may be mixed in any ratio.

In the above catalyst, preferably, the ratio between the component (1) and the component (2) is 1: (5-1000), preferably 1: (20-500) in terms of a molar ratio of titanium: aluminum. .

In the above catalyst, preferably, the ratio between the component (1) and the component (3) is 1: (5-500) in terms of a molar ratio of titanium: silicon.

In the above catalyst, preferably, the ratio between the component (2) and the component (3) is from 0.1 to 500, more preferably from 1 to 300, particularly preferably from 3 to 100, in terms of a molar ratio of aluminum: silicon. .

The present invention also provides the use of the above olefin polymerization catalyst in the polymerization of olefins.

In the above application, preferably, the olefin polymerization reaction is a CH ₂ =CHG olefin polymerization reaction, wherein G is selected from the group consisting of hydrogen, a C1-C20 alkyl group, and a C1-C20 aryl group; more preferably G is selected from the group consisting of hydrogen, a C1-C6 alkyl group, and a C1-C6 aryl group.

In the above applications, the polymerization of the olefin can be carried out according to known methods, such as in the liquid phase of a liquid monomer or a solution of a monomer in an inert solvent, or in a gas phase, or by a combined polymerization process in a gas phase. Take action. The polymerization temperature is usually from 0 to 150 ° C, preferably from 60 to 100 ° C. The polymerization pressure is normal pressure or higher.

The present invention provides a dibasic acid ester compound having a specific structure which is used as an internal electron donor for the preparation of an olefin polymerization catalyst component (i.e., a main catalyst), and a catalyst component excellent in overall performance can be obtained. When the catalyst component is used for the polymerization of propylene, a satisfactory polymerization yield can be obtained; and the obtained polymer has high stereospecificity, and even when an external electron donor is not used, a higher isotacticity can be obtained. The polymer; at the same time, the catalyst component is also very sensitive to hydrogen modulation; and the molecular weight distribution of the obtained polymer is wide, which is favorable for the development of different grades of polymers. Further, the catalyst component can give less gel content when used for copolymerization of olefins, particularly ethylene-propylene copolymerization, and thus has better copolymerization properties.

In addition, the present invention utilizes the above-mentioned disulfonic acid ester compound having a special structure in combination with a conventional internal electron donor compound, and is combined with a composite carrier to prepare an olefin polymerization catalyst having high activity, high stereospecificity and high hydrogen sensitivity sensitivity. The catalyst is compounded with a catalyst such as an alkyl aluminum compound to make the prepared polymer have a higher bulk density and a broader molecular weight distribution, which is advantageous for industrial production and post-polymer processing; and the activity of the catalyst It has a certain balance with the stereoregularity of the polymer (especially polypropylene resin), that is, the high activity catalyst can be obtained, and the higher stereoregularity of the polymer can be ensured. The industrial application of catalysts is very important.

detailed description

The detailed description of the technical features, the advantages and the advantages of the present invention will be understood by the following detailed description of the invention.

testing method

1. Melt index: use

The MI-4 melt indexer was used for the measurement, and the test method was in accordance with GB/T3682-2000.

2. Measurement of nuclear magnetic resonance: Measurement was carried out by using a Bruker-400 nuclear magnetic resonance apparatus ¹ H-NMR (400 MHz, solvent CDCl ₃ , TMS as an internal standard, and a measurement temperature of 300 K).

3. Polymer molecular weight distribution MWD (MWD=Mw/Mn): The measurement was carried out at 150 ° C using trichlorobenzene as a solvent (standard: PS, flow rate: 1.0 ml/min).

4. The isotacticity of the polymer is determined by heptane extraction (boiling heptane extraction for 6 hours): 2 g of the dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours. The ratio of the weight (g) of the polymer obtained by drying the remaining polymer sample to constant weight is 2, which is isotactic.

Example 1

This example provides 1,2-butanediol ditosylate which is prepared by the following method:

1,2-butanediol (2.50 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-toluenesulfonyl chloride (10.60 g) was added in four portions, and at 0. After reacting at ° C for 4 hours, the reaction was continued to room temperature for 6 hours, and then water was added to the reaction system until the inorganic phase was transparent; the organic phase was separated, and the inorganic phase was extracted with diethyl ether, and the extracted diethyl ether solution was combined with the organic phase. The organic phase combined with the extracted diethyl ether solution was washed and dried over anhydrous sodium sulfate. After concentrated, the product was isolated to afford 4.37 g. The results of nuclear magnetic resonance measurement of the product were: δ 1.0-1.1 (3H), 1.7-1.9 (2H), 2.3-2.6 (6H), 4.4-4.6 (2H), 5.4-5.5 (1H), 7.2-8.0 ( 8H), it was confirmed that 1,2-butanediol ditosylate was obtained in the present example.

Example 2

This example provides 2,3-butanediol xylene sulfonate, which is prepared in substantially the same manner as the preparation method in Example 1, except that the raw material 1,2-butanediol in Example 1 is used. It was replaced with 2,3-butanediol in the same amount as in Example 1, to give the product 4.69 g. The results of nuclear magnetic resonance measurement of the product were: δ1.4-1.6 (6H), 2.3-2.6 (6H), 5.3-5.5 (2H), 7.2-8.0 (8H), and it was confirmed that the preparation of this example obtained 2, 3 - Butanediol ditosylate.

Example 3

This example provides catechol di-p-toluenesulfonate, which is prepared by the following method:

2.75 g of catechol was added to 50 mL of tetrahydrofuran, and 12.10 mL of pyridine was added thereto with stirring. After stirring, 11.66 g of p-toluenesulfonyl chloride was slowly added, and the mixture was stirred at room temperature for 1 hour, and then heated to reflux to keep the reaction 4 The resulting salt was dissolved in 70 mL of deionized water, then extracted with toluene, and the organic phase was separated. The organic phase was washed three times with saturated brine, dried over anhydrous sodium sulfate, and then evaporated and then recrystallised. Get The product was 4.02 g. The results of nuclear magnetic resonance measurement of the product were: δ1.0-1.1 (6H), 2.3-2.6 (6H), 4.4-4.6 (4H), 7.3-7.6 (8H), and it was confirmed that phthalic acid was obtained in the present example. Phenol di-p-toluenesulfonate.

Example 4

This example provides dimethyl 2,5-dicarboxylate-3,4-dihydroxydi-p-toluenesulfonate, which is prepared by the following method:

6.50 g of 3,4-dihydroxythiophene-2,5-dicarboxylic acid dimethyl ester was added to 80 mL of tetrahydrofuran, and 12.10 mL of pyridine was added thereto with stirring. After stirring, 11.66 g of p-toluenesulfonyl chloride was slowly added, and the mixture was stirred at room temperature. 1 hour, then heated to reflux, the reaction was kept for 4 hours; 70 mL of deionized water was added to dissolve the resulting salt, and then extracted with toluene, the organic phase was separated, and the organic phase was washed three times with saturated brine, then anhydrous sodium sulfate After drying, the solvent was removed, washed and recrystallized to give the product 6.80 g. The results of nuclear magnetic resonance measurement of the product were: δ2.3-2.6 (6H), 7.3-7.6 (8H), 7.9-8.2 (4H), and it was confirmed that dimethyl 2,5-dicarboxylate was prepared in this example- 3,4-dihydroxydi-p-toluenesulfonate.

Example 5-8

Examples 5-8 each provide an olefin polymerization catalyst component which is prepared according to the preparation method as described below:

In a reactor that was replaced by high-purity nitrogen, 4.80 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added in sequence; the temperature was raised to 50 ° C under stirring, and the reaction was kept for 2.5 hours until the solid was completely completed. Dissolved; add 1.40g of phthalic anhydride, continue the heat preservation reaction for 1 hour; cool the solution to below -25 °C, add 125 ml of TiCl ₄ in 1 hour; then slowly raise the temperature to 80 ° C, gradually precipitate solids during the heating process Then, the glycol sulfonate compound or the diphenol sulfonate compound prepared in Example 1-4 was separately added to 6 mmol, and the reaction was kept for 1 hour; after filtration, 70 mL of toluene was added and washed twice to obtain a solid precipitate; Then, 60 mL of toluene and 40 mL of TiCl ₄ were added, and the mixture was heated to 100 ° C for 2 hours. After the filtrate was drained, 60 mL of toluene and 40 mL of TiCl _{4 were} added, and the mixture was reacted at 100 ° C for 2 hours to remove the filtrate; 60 mL of toluene was added, and the mixture was washed three times in a boiling state. Further, 60 mL of hexane was added, washed three times in a boiling state, and then 60 mL of hexane was added, and after washing twice at normal temperature, the olefin polymerization catalyst component of Example 5-8 was obtained.

Example 9

This example provides 1,3-butanediol xylene sulfonate, which is prepared by the following method:

To the reactor were added 1,3-butanediol (2.50 g), pyridine (8.80 g) and tetrahydrofuran (70 mL), and after mixing uniformly, p-toluenesulfonyl chloride (10.60 g) was added in four portions under stirring. And reacting at 0 ° C for 4 hours, then raising to room temperature to continue the reaction for 6 hours, and then adding water to the reaction system until the inorganic phase is transparent; separating the organic phase, extracting the inorganic phase with diethyl ether, and then extracting the ether solution and organic after extraction Combined, washed with water and combined with extraction The organic phase of the ethereal solution was dried over anhydrous sodium sulfate and then evaporated. The results of nuclear magnetic resonance measurement of the product were: δ1.0-1.1 (6H), 2.3-2.6 (6H), 4.4-4.6 (2H), 7.2-8.0 (8H), and it was confirmed that the preparation of this example gave 1,3 - Butanediol ditosylate.

Example 10

This example provides 2,4-pentanediol di-p-toluenesulfonate, which is prepared by the following method:

2,4-pentanediol (2.92 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-toluenesulfonyl chloride (10.60 g) was added in four portions under stirring. And reacting at 0 ° C for 4 hours, then raising to room temperature to continue the reaction for 6 hours, and then adding water to the reaction system until the inorganic phase is transparent; separating the organic phase, extracting the inorganic phase with diethyl ether, and then extracting the ether solution and organic after extraction The phases were combined; the organic phase combined with the extracted diethyl ether solution was washed with water and dried over anhydrous sodium sulfate. The results of nuclear magnetic resonance measurement of the product are: δ1.1-1.3 (6H), 1.6-2.1 (2H), 2.4-2.5 (6H), 4.5-4.7 (2H), 7.2-8.0 (8H), and the present embodiment can be determined. For example, 2,4-pentanediol di-p-toluenesulfonate was obtained.

Example 11

This example provides 2,4-pentanediol diphenyl sulfonate, which is prepared by the following method:

2,4-pentanediol (2.92 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, benzenesulfonyl chloride (10.60 g) was added in four portions under stirring, and After reacting at 0 ° C for 4 hours, the reaction was continued to room temperature for 6 hours, and then water was added to the reaction system until the inorganic phase was transparent; the organic phase was separated, and the inorganic phase was extracted with diethyl ether, and then the extracted diethyl ether solution was combined with the organic phase. The organic phase combined with the extracted diethyl ether solution was washed with water and dried over anhydrous sodium sulfate. After concentrated, the product was isolated to afford 4.79 g of product. The results of nuclear magnetic resonance measurement of the product were: δ1.1-1.3 (6H), 1.6-2.1 (2H), 4.5-4.7 (2H), 7.5-8.0 (10H), and it was confirmed that the preparation of this example obtained 2, 4 - pentanediol diphenyl sulfonate.

Example 12

This example provides 3,5-heptanediol diphenyl sulfonate, which is prepared by the following method:

3,5-Heptanediol (3.45 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, benzenesulfonyl chloride (10.60 g) was added in four portions under stirring, and After reacting at 0 ° C for 4 hours, the reaction was continued to room temperature for 6 hours, and then water was added to the reaction system until the inorganic phase was transparent; the organic phase was separated, and the inorganic phase was extracted with diethyl ether, and then the extracted diethyl ether solution was combined with the organic phase. The organic phase combined with the extracted diethyl ether solution was washed with water and dried over anhydrous sodium sulfate. After concentrated, the product was isolated to afford 4.79 g of product. The results of nuclear magnetic resonance measurement of the product are: δ0.7-0.8 (6H), 1.4-1.7 (4H), 1.8-2.1 (2H), 4.4-4.6 (2H), 7.5-8.0 (10H), and the present embodiment can be determined. For example, 3,5-heptanediol diphenyl sulfonate was obtained.

Example 13

This example provides 2,4-pentanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:

2,4-pentanediol (2.92 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-chlorobenzenesulfonyl chloride (11.53 g) was added in four portions under stirring. And reacting at 0 ° C for 4 hours, then increasing to room temperature to continue the reaction for 6 hours, and then adding water to the reaction system until the inorganic phase is transparent; separating the organic phase, extracting the inorganic phase with diethyl ether, and then extracting the ether solution and the organic phase after extraction The organic phase combined with the extracted diethyl ether solution was washed with water and dried over anhydrous sodium sulfate. After concentrated, the product was isolated to give 4.79 g of product. The results of nuclear magnetic resonance measurement of the product were: δ1.1-1.3 (6H), 1.6-2.1 (2H), 4.5-4.7 (2H), 7.5-8.0 (8H), and it was confirmed that the preparation of the present example obtained 2, 4 - pentanediol di-p-chlorobenzenesulfonate.

Example 14

This example provides 3,5-heptanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:

3,5-Heptanediol (3.45 g), pyridine (8.80 g) and tetrahydrofuran (70 mL) were added to the reactor, and after mixing uniformly, p-chlorobenzenesulfonyl chloride (11.53 g) was added in four portions under stirring. And reacting at 0 ° C for 4 hours, then increasing to room temperature to continue the reaction for 6 hours, and then adding water to the reaction system until the inorganic phase is transparent; separating the organic phase, extracting the inorganic phase with diethyl ether, and then extracting the ether solution and the organic phase after extraction The organic phase combined with the extracted diethyl ether solution was washed with water and dried over anhydrous sodium sulfate. After concentrated, the product was isolated to give 4.79 g of product. The results of nuclear magnetic resonance measurement of the product are: δ0.7-0.8 (6H), 1.4-1.7 (4H), 1.8-2.1 (2H), 4.4-4.6 (2H), 7.5-8.0 (8H), and the present embodiment can be determined. For example, 3,5-heptanediol di-p-chlorobenzenesulfonate was obtained.

Example 15

This example provides 2,6-dimethyl-3,5-heptanediol diphenyl sulfonate, which is prepared by the following method:

(1) Preparation of 2,6-dimethyl-3,5-heptanediol

A mixture of 2,6-dimethyl-3,5-heptanedione 7.1 g and 15 mL of methanol was added dropwise at 0-10 ° C to a mixture of 1.25 g of sodium borohydride, 0.025 g of sodium hydroxide and 25 mL of water. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and then the solvent was removed, and the mixture was continuously extracted with 20 mL of ethyl acetate for 10 hours; after the solvent was removed, the mixture was again distilled under reduced pressure, and the fraction was collected to obtain a colorless liquid 2,6-dimethyl-3,5. - heptanediol; 90% yield; IR spectra at 3400 cm ^-1 has a strong absorption peak, while no absorption peak at about ^-1, 1700 cm prove that the reduction reaction to completion;

(2) Preparation of 2,6-dimethyl-3,5-heptanediol diphenyl sulfonate

Adding 0.03 mol of 2,6-dimethyl-3,5-heptanediol prepared in the step (1) to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then adding 0.075 mol of benzenesulfonyl chloride under stirring, the reaction After the reaction was completed, 20 mL of a saturated aqueous sodium chloride solution was added, and the mixture was extracted with ethyl acetate. The results of nuclear magnetic resonance measurement of the product were: δ0.9-1.0 (12H), 1.9-2.0 (4H), 5.1-5.2 (2H), 7.2-8.0 (10H), and it was confirmed that the preparation of this example obtained 2,6 -Dimethyl-3,5-heptanediol II Phenyl sulfonate.

Example 16

This example provides 2,6-dimethyl-3,5-heptanediol di-p-toluenesulfonate, which is prepared by the following method:

(1) Preparation of 2,6-dimethyl-3,5-heptanediol

A mixture of 2,6-dimethyl-3,5-heptanedione 7.1 g and 15 mL of methanol was added dropwise at 0-10 ° C to a mixture of 1.25 g of sodium borohydride, 0.025 g of sodium hydroxide and 25 mL of water. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and then the solvent was removed, and the mixture was continuously extracted with 20 mL of ethyl acetate for 10 hours; after the solvent was removed, the mixture was again distilled under reduced pressure, and the fraction was collected to obtain a colorless liquid 2,6-dimethyl-3,5. - heptanediol; yield 90%; IR spectra at 3400 cm ^-1 has a strong absorption peak, while no absorption peak at about ^-1, 1700 cm prove that the reduction reaction to completion;

(2) Preparation of 2,6-dimethyl-3,5-heptanediol di-p-toluenesulfonate

0.03 mol of 2,6-dimethyl-3,5-heptanediol prepared in the step (1) was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of p-toluenesulfonyl chloride was added under stirring. After the reaction was completed for 4 hours, 20 mL of a saturated aqueous sodium chloride solution was added, and the mixture was extracted with ethyl acetate. The results of nuclear magnetic resonance measurement of the product are: δ0.9-1.0 (12H), 1.9-2.0 (4H), 2.4-2.5 (6H), 5.1-5.2 (2H), 7.2-8.0 (10H), and the present embodiment can be determined. For example, 2,6-dimethyl-3,5-heptanediol di-p-toluenesulfonate was obtained.

Example 17

This example provides 2,6-dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:

(1) Preparation of 2,6-dimethyl-3,5-heptanediol

(2) Preparation of 2,6-dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate

0.03 mol of 2,6-dimethyl-3,5-heptane obtained in the step (1) was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of p-chlorobenzenesulfonyl chloride was added with stirring. After the reaction was completed, 20 mL of a saturated aqueous sodium chloride solution was added, and the mixture was extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. The results of nuclear magnetic resonance measurement of the product were: δ0.9-1.0 (12H), 1.9-2.0 (4H), 5.1-5.2 (2H), 7.2-8.0 (10H), and it was confirmed that the preparation of this example obtained 2,6 - Dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate.

Example 18

This example provides 3-methyl-2,4-pentanediol di-p-chlorobenzenesulfonate, which is prepared by the following method:

0.03 mol of 3-methyl-2,4-pentanediol was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of p-chlorobenzenesulfonyl chloride was added under stirring for 4 hours; after the reaction was over, it was added. The mixture was extracted with ethyl acetate, dried over anhydrous magnesium sulfate and evaporated. The results of nuclear magnetic resonance measurement of the product are: δ1.0-1.1 (3H), 1.3-1.4 (6H), 1.9-2.1 (1H), 5.1-5.3 (2H), 7.2-8.0 (6H), and the present embodiment can be determined. For example, 3-methyl-2,4-pentanediol di-p-chlorobenzenesulfonate was obtained.

Example 19

This example provides 3-methyl-2,4-pentanediol di-p-toluenesulfonate, which is prepared by the following method:

0.03 mol of 3-methyl-2,4-pentanediol was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of p-toluenesulfonyl chloride was added under stirring for 4 hours; after the reaction was over, 20 mL was added. The mixture was diluted with brine and dried over anhydrous magnesium sulfate. The results of nuclear magnetic resonance measurement of the product were: δ 1.0-1.1 (3H), 1.3-1.4 (6H), 1.9-2.1 (1H), 2.3-2.4 (6H), 5.1-5.3 (2H), 7.2-8.0 ( 6H), it was confirmed that 3-methyl-2,4-pentanediol di-p-toluenesulfonate was obtained in the present example.

Example 20

This example provides 2-ethyl-1,3-hexanediol xylene sulfonate which is prepared by the following method:

0.03 mol of 2-ethyl-1,3-hexanediol was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of benzenesulfonyl chloride was added under stirring for 4 hours; after the reaction was completed, 20 mL of saturation was added. The mixture was extracted with EtOAc, dried over anhydrous magnesium sulfate and evaporated. The results of nuclear magnetic resonance measurement of the product were: δ 1.0-1.1 (3H), 1.3-1.4 (6H), 1.9-2.1 (1H), 2.3-2.4 (6H), 5.1-5.3 (2H), 7.2-8.0 ( 6H), it was confirmed that 2-ethyl-1,3-hexanediol ditosylate was obtained in the present example.

Example 21

This example provides 2,2,4-trimethyl-1,3-pentanediol diphenyl sulfonate, which is prepared by the following method:

0.03 mol of 2,2,4-trimethyl-1,3-pentanediol was added to a mixture of 30 mL of tetrahydrofuran and 0.09 mol of pyridine, and then 0.075 mol of benzenesulfonyl chloride was added under stirring for 4 hours; the reaction was completed. Thereafter, 20 mL of a saturated aqueous sodium chloride solution was added, and the mixture was extracted with ethyl acetate and dried over anhydrous magnesium sulfate. The results of nuclear magnetic resonance measurement of the product were: δ1.01-1.07 (6H), 1.1 (6H), 4.1-4.2 (6H), 5.1-5.3 (2H), 7.2-8.0 (10H), and the preparation of this example was confirmed. 2,2,4-Trimethyl-1,3-pentanediol diphenyl sulfonate was obtained.

Example 22

This example provides 6-heptene-2,4-heptanediol diphenyl sulfonate, which is prepared by the following method:

Under anhydrous and oxygen-free and nitrogen-protected conditions, 6-heptene-2,4-heptanediol was added to the reactor in 0.02 mol, pyridine 0.06 mol, and then 0.05 mol of benzenesulfonyl chloride was slowly added dropwise. After the end of the reaction, the reaction was carried out for 8 hours; after the reaction was completed, the reaction mixture was filtered, and the solid fraction was washed three times with anhydrous diethyl ether; then the organic phase was washed with brine, and then dried over anhydrous magnesium sulfate. After chromatography separation, the product was obtained. The results of nuclear magnetic resonance measurement of the product were: δ1.6-1.7 (2H), 2.1-2.2 (2H), 4.7-4.8 (2H), 5.1-5.2 (2H), 5.5-5.6 (2H), 7.2-8.0 ( 10H), it was confirmed that 6-heptene-2,4-heptanediol diphenylsulfonate was obtained in the present example.

Example 23

This example provides 1,8-dinaphthol di-p-toluenesulfonate, which is prepared by the following method:

Add 4 g of 1,8-dinaphthol to 60 mL of tetrahydrofuran, add 12.10 mL of pyridine with stirring, stir well, then slowly add 11.66 g of p-toluenesulfonyl chloride, stir at room temperature for 1 hour, then heat to reflux, keep warm The reaction was carried out for 4 hours; 70 mL of deionized water was added to dissolve the resulting salt, which was then extracted with toluene, and the organic phase was separated. The organic phase was washed three times with saturated brine and dried over anhydrous sodium sulfate. The product was obtained 4.64 g. The results of nuclear magnetic resonance measurement of the product were: δ2.3-2.6 (6H), 7.3-7.8 (14H), and it was confirmed that 1,8-dinaphthol di-p-toluenesulfonate was obtained in the present example.

Example 24

This example provides 9,9-bis(p-toluenesulfonylmethyl)fluorene, which is prepared in substantially the same manner as in the preparation method of Example 10, except that the raw material 2 in Example 10 is used. The 4-pentanediol was replaced with 9,9-bishydroxyindole in the same molar amount as in Example 10. The results of nuclear magnetic resonance measurement of the product were: δ2.3-2.6 (6H), 7.2-7.8 (16H), and it was confirmed that 9,9-bis(p-toluenesulfonylmethyl)anthracene was obtained in the present example.

Example 25

This example provides cis-1,2-bis(p-toluenesulfonylmethyl)cyclohexane, which is prepared in substantially the same manner as the preparation method in Example 9, except that the same will be given in Example 9. The raw material 1,3-butanediol was replaced with cis-1,2-cyclohexanediol in the same molar amount as in Example 9. The results of nuclear magnetic resonance measurement of the product were: δ1.2-1.5 (10H), 2.3-2.6 (6H), 3.5-3.7 (4H), 7.2-7.8 (8H), and it was confirmed that the preparation of this example gave 1,1- Bis(p-toluenesulfonylmethyl)cyclohexane.

Example 26-29

Examples 26-29 respectively provide an olefin polymerization catalyst component which is prepared according to the preparation method as follows:

In a reactor that was replaced by high-purity nitrogen, 4.80 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added in sequence; the temperature was raised to 50 ° C under stirring, and the reaction was kept for 2.5 hours until the solid was completely completed. Dissolved; add 1.40g of phthalic anhydride, continue the heat preservation reaction for 1 hour; cool the solution to below -25 °C, add 125 ml of TiCl ₄ in 1 hour; then slowly raise the temperature to 80 ° C, gradually precipitate solids during the heating process Then, 6 mmol of the disulfonate compound prepared in Example 9-12 was separately added, and the reaction was kept for 1 hour; after filtration, 70 mL of toluene was added and washed twice to obtain a solid precipitate; then, toluene 60 mL, TiCl ₄ 40 mL was added. The temperature was raised to 100 ° C for 2 hours. After the filtrate was drained, 60 mL of toluene and 40 mL of TiCl _{4 were} added. The reaction was carried out at 100 ° C for 2 hours to remove the filtrate. 60 mL of toluene was added, washed three times in a boiling state, and then added with 60 mL of hexane. The state was washed three times, and then 60 mL of hexane was added, and after washing twice at normal temperature, the olefin polymerization catalyst component of Examples 26 to 29 was obtained.

Example 30

This example provides 2,3-diethyl-1,4-butanediol di-p-toluenesulfonate, which is prepared by the following method:

6.45 g of 2,3-diethyl-1,4-butanediol was mixed with 100 mL of tetrahydrofuran, and then 17.20 g of p-toluenesulfonyl chloride and 14 g of pyridine were added, followed by heating to reflux, and the reaction was kept for 4 hours; Then, the organic phase was separated, and the organic phase was washed, dried and concentrated to give 8.76 g of product. The results of nuclear magnetic resonance measurement of the product were: δ1.0-1.5 (10H), 2.1-2.3 (2H), 2.3-2.6 (6H), 7.2-7.9 (8H), and it was confirmed that the preparation of this example gave 2,3 -Diethyl-1,4-butanediol di-p-toluenesulfonate.

Example 31

This example provides 2,5-dimethyl-2,5-hexanediol di-p-toluenesulfonate, which is prepared in substantially the same manner as in the preparation method of Example 30, except that Example 30 will be used. The raw material 2,3-diethyl-1,4-butanediol was replaced with 2,5-dimethyl-2,5-hexanediol in the same molar amount as in Example 1, to give the product 7.92. g. The results of nuclear magnetic resonance measurement of the product were: δ1.5-1.7 (12H), 2.1-2.3 (4H), 2.3-2.6 (6H), 7.2-7.9 (8H), and it was confirmed that the preparation of this example gave 2,5. - Dimethyl-2,5-hexanediol di-p-toluenesulfonate.

Example 32

This example provides 3,6-dimethyl-3,6-dioctanol di-p-toluenesulfonate, which is prepared in substantially the same manner as in the preparation method of Example 30, except that Example 30 will be used. The raw material 2,3-diethyl-1,4-butanediol was replaced by 3,6-dimethyl-3,6-dioctanol in the same molar amount as in Example 1, to obtain the product 8.34. g. The results of nuclear magnetic resonance measurement of the product were: δ0.9-1.0 (6H), 1.5-1.6 (6H), 1.9-2.0 (4H), 2.0-2.1 (4H), 2.3-2.6 (6H), 7.2-7.9 ( 8H), it was confirmed that 3,6-dimethyl-3,6-dioctanol di-p-toluenesulfonate was obtained in the present example.

Example 33

This example provides cis-2-butene-1,4-diol di-p-toluenesulfonate, which is prepared in substantially the same manner as the preparation method in Example 1, except that the raw material in Example 30 is used. Replace 2,3-diethyl-1,4-butanediol with cis 2-butene-1,4-diol was added in the same amount as in Example 1 to give the product 9.78 g. The results of nuclear magnetic resonance measurement of the product were: δ2.3-2.6 (6H), 3.8-4.2 (4H), 5.3-5.8 (2H), 7.2-7.9 (8H), and it was confirmed that cis-2 was prepared in this example. - Butene-1,4-diol di-p-toluenesulfonate.

Example 34-37

Examples 34-37 respectively provide an olefin polymerization catalyst component which is prepared according to the preparation method as follows:

In a reactor that was replaced by high-purity nitrogen, 4.80 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added in sequence; the temperature was raised to 50 ° C under stirring, and the reaction was kept for 2.5 hours until the solid was completely completed. Dissolved; add 1.40g of phthalic anhydride, continue the heat preservation reaction for 1 hour; cool the solution to below -25 °C, add 125 ml of TiCl ₄ in 1 hour; then slowly raise the temperature to 80 ° C, gradually precipitate solids during the heating process Then, 6 mmol of the glycol sulfonate compound prepared in Examples 30-33 was separately added, and the reaction was kept for 1 hour; after filtration, 70 mL of toluene was added and washed twice to obtain a solid precipitate; then, toluene 60 mL, TiCl _{4 was} added. 40mL, the temperature was raised to 100 ° C for 2 hours, after draining the filtrate, add 60 mL of toluene, 40 mL of TiCl ₄ , react at 100 ° C for 2 hours, drain the filtrate; add 60 mL of toluene, wash three times in boiling state, then add 60 mL of hexane, The mixture was washed three times in a boiling state, and then 60 mL of hexane was added thereto, and after washing twice at normal temperature, the olefin polymerization catalyst component of Examples 34 to 37 was obtained.

Example 38

This example provides 1,5-diphenyl-1,5-pentanediol di-p-toluenesulfonate, which is prepared by the following method:

Reduction of 1,5-diphenyl-1,5-pentanedione with lithium aluminum hydride to 1,5-diphenyl-1,5-pentanediol; 0.03 mol of 1,5-diphenyl-1 5-pentanediol was added to 30 mL of tetrahydrofuran, and 0.09 mol of pyridine was added. 0.075 mol of p-toluenesulfonyl chloride was added in portions while stirring, and then heated to reflux, and the reaction was kept for 4 hours; after cooling, it was washed with 20 mL of saturated brine. It was extracted with ethyl acetate, dried over anhydrous sodium sulfate and evaporated. The results of nuclear magnetic resonance measurement of the product are: δ1.3-1.5 (2H), 1.9-2.1 (4H), 2.3-2.6 (6H), 5.9-6.0 (2H), 7.2-8.0 (8H), and the present embodiment can be determined. For example, 1,5-diphenyl-1,5-pentanediol di-p-toluenesulfonate was obtained.

Example 39

The present embodiment provides 1,4-hexanediol di-p-toluenesulfonyl ester, which is prepared in the same manner as in the preparation method of Example 1, except that the raw material 1,5-diphenyl in Example 1 is used. The benzyl-1,5-pentanediol was replaced with 1,4-hexanediol in the same molar amount as in Example 1, and the step of reducing the ketone to an alcohol was omitted to obtain a product. The results of nuclear magnetic resonance measurement of the product are: δ1.1-1.2 (8H), 1.8-1.9 (2H), 2.3-2.6 (6H), 4.2-4.3 (4H), 7.2-7.8 (8H), and the present embodiment can be determined. For example, 1,4-hexanediol di-p-toluenesulfonyl ester was obtained.

Example 40

This example provides 1,5-hexanediol di-p-toluenesulfonate, which is prepared in the same manner as the preparation method in Example 1, except that the raw material 1,5-diphenyl in Example 1 is used. The benzyl-1,5-pentanediol was replaced with 1,5-hexanediol in the same amount as in Example 1, and the step of reducing the ketone to the alcohol was omitted to obtain a product. The results of nuclear magnetic resonance measurement of the product were: δ1.3-1.4 (3H), 1.5-1.6 (2H), 1.6-1.7 (2H), 1.7-1.8 (2H), 2.3-2.6 (6H), 4.3-4.4 ( 2H), 5.2-5.3 (1H), 7.2-7.8 (8H), it was confirmed that 1,5-hexanediol di-p-toluenesulfonate was obtained in this example.

Example 41

The present embodiment provides 2,2'-biphenyldiethanol di-p-toluenesulfonate, which is prepared in the same manner as in the first embodiment, except that the raw material in the first embodiment is 1,5- Diphenyl-1,5-pentanediol was replaced with 2,2'-biphenyldimethanol in the same molar amount as in Example 1, and the step of reducing the ketone to the alcohol was omitted to obtain the product. The results of nuclear magnetic resonance measurement of the product were: δ 1.0-1.1 (6H), 2.2-2.3 (4H), 2.3-2.6 (6H), 4.8-4.9 (4H), 5.2-5.3 (1H), 7.2-7.8 ( 16H), it was confirmed that 2,2'-biphenyldiethanol di-p-toluenesulfonate was obtained in the present example.

Example 42-45

Examples 42-45 provide an olefin polymerization catalyst component, respectively, which is prepared according to the preparation method described below:

In a reactor that was replaced by high-purity nitrogen, 4.80 g of magnesium chloride, 95 mL of toluene, 4 mL of epichlorohydrin, and 12.5 mL of tributyl phosphate were added in sequence; the temperature was raised to 50 ° C under stirring, and the reaction was kept for 2.5 hours until the solid was completely completed. Dissolved; add 1.40g of phthalic anhydride, continue the heat preservation reaction for 1 hour; cool the solution to below -25 °C, add 125 ml of TiCl ₄ in 1 hour; then slowly raise the temperature to 80 ° C, gradually precipitate solids during the heating process Then, 6 mmol of the glycol sulfonate compound prepared in Examples 38-41 was separately added, and the reaction was kept for 1 hour; after filtration, 70 mL of toluene was added and washed twice to obtain a solid precipitate; then, toluene 60 mL, TiCl _{4 was} added. 40mL, the temperature was raised to 100 ° C for 2 hours, after draining the filtrate, add 60 mL of toluene, 40 mL of TiCl ₄ , react at 100 ° C for 2 hours, drain the filtrate; add 60 mL of toluene, wash three times in boiling state, then add 60 mL of hexane, The mixture was washed three times in a boiling state, then 60 mL of hexane was added, and after washing twice at normal temperature, the olefin polymerization catalyst component of Examples 42 to 45 was obtained.

Comparative example 1

This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation methods of Examples 5-8, 26-29, 34-37 and 42-45, except that the disulfide is disulfide. The acid ester compound (internal electron donor) is replaced by ethylene glycol di-p-toluenesulfonate.

Comparative example 2

This comparative example provides an olefin polymerization catalyst component, which is prepared in the same manner as in Examples 5-8, 26-29, 34-37. The preparation method is basically the same as in 42-45 except that the disulfonate compound (internal electron donor) is replaced with ethyl benzoate.

Comparative example 3

This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation methods of Examples 5-8, 26-29, 34-37 and 42-45, except that the disulfide is disulfide. The acid ester compound (internal electron donor) is replaced with di-n-butyl phthalate.

Propylene polymerization test

The solid catalyst components of the above Examples 5-8, 26-29, 34-37 and 42-45 and Comparative Examples 1-3 were used to catalyze the polymerization of propylene. The propylene polymerization was carried out by disposing a 5 L stainless steel autoclave having a volume of 5 rpm with a gas propylene, and then adding AlEt ₃ 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 thereto. Further, 8-10 mg (preferably 10 mg) of the solid catalyst component prepared in the above Examples 5-8, 26-29, 34-37 and 42-45 and Comparative Examples 1-3 and 1.2 L of hydrogen were added, respectively. 2.3 L of liquid propylene was introduced, and the temperature was raised to 70 ° C. After the reaction was kept for 1 hour, the temperature was lowered and pressure was released to obtain a polypropylene (PP) powder. Among them, the solid catalyst component prepared in Examples 5-8, 26-29, 34-37, 42-45 or Comparative Example 1-3, AlEt ₃ and CHMMS constitute an olefin polymerization catalyst, which collectively catalyzes the polymerization of propylene.

Calculating the catalyst activity, the catalyst activity is calculated by the amount of the obtained polypropylene / the amount of the solid catalyst component added, and the obtained polypropylene powder is subjected to isotacticity, melt index and molecular weight distribution test, and the test method is as described above. The results are shown in Table 1.

Table 1

As can be seen from Table 1, the catalytic activity of the olefin polymerization catalyst component prepared in Examples 5-8, 26-29, 34-37 and 42-45 is higher, and the stereospecific orientation of the polymer prepared by using the catalyst component is obtained. Higher properties and wider molecular weight distribution are beneficial for processing applications.

Example 46

This example provides an olefin polymerization catalyst component which is prepared by the following method:

1. The preparation of the spherical MgCl ₂ /SiO ₂ composite carrier is carried out in two steps:

(1) Preparation of spray-dried mother liquor: 200 mL of dehydrated ethanol was added to a stirred 400 mL reactor which was sufficiently substituted with N ₂ ; 20 g of anhydrous magnesium chloride was added while stirring at room temperature to control the rate of magnesium chloride addition. , the temperature of the system is kept below 40 ° C; after the addition of magnesium chloride, the temperature of the mixed system is raised to 70 ° C, and the temperature is kept at this temperature for 4 h to obtain a uniform magnesium chloride ethanol solution; 12.5 g of TS-particle size of 0.1 μm is added. 610 fuming silica gel, stirring for 1 h, to obtain a mother liquor for spray drying;

(2) Preparation of MgCl ₂ /SiO ₂ spherical carrier by spray drying: preparing a composite carrier by using a spray dryer; introducing the obtained mother liquor into a two-fluid nozzle through a pipe by a peristaltic pump, atomizing into a drying chamber; controlling the liquid and the spray gas N _{2 The} flow rate is 8Ml/min and 1400L/h respectively, the spray gas temperature is room temperature; the inlet temperature of the instrument is 190 °C, the outlet temperature of the instrument is stable at about 105 °C; the spherical MgCl ₂ /SiO ₂ is collected at the lower outlet of the cyclone separator. Composite carrier particles; chemical composition analysis results show that: Mg 14.2wt%, Cl 35.4wt%, C ₂ H ₅ OH 41.4wt%, D50 is 45.8μm;

2. Synthesis of solid catalyst components:

9 g of the above carrier was taken, and slowly added to 100 mL of TiCl ₄ precooled to 0 ° C, and the temperature was raised to 40 ° C in 1 h, and 3 g of 1,8-dinaphthol dip-toluenesulfonate was added, and then the temperature was raised to 0.5 h. After maintaining at 100 ° C for 2 h, the liquid phase was filtered off, and the solid was washed five times with hexane at 60 ° C, and dried under vacuum to obtain a solid catalyst component.

Example 47

The present embodiment provides an olefin polymerization catalyst component, which is prepared in substantially the same manner as the preparation method in Example 46, except that the addition of 1,8-dinaphthol di-p-toluenesulfonate is simultaneously Dibutyl phthalate was added in an amount of 1.24 g.

Example 48

The present embodiment provides an olefin polymerization catalyst component, a preparation method thereof and a preparation method in the embodiment 46 Basically the same, the only difference is that 1,8-dinaphthol di-p-toluenesulfonate is replaced with 9,9-bis(p-toluenesulfonylmethyl)phosphonium, which is used in an amount of 3.20 g. 9,9-bis(methoxymethyl)anthracene was added in an amount of 1.16 g.

Comparative example 4

The present comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol dip-toluenesulfonate is replaced with 1, 3-butanediol ditosylate, which was used in an amount of 2.74 g.

Comparative example 5

This comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol di-p-toluenesulfonate is replaced with o-benzene. Dibutyl diformate was used in an amount of 2.29 g.

Comparative example 6

The present comparative example provides an olefin polymerization catalyst component which is prepared in substantially the same manner as in the preparation method of Example 46 except that 1,8-dinaphthol dip-toluenesulfonate is replaced with 9 , 9-bis(methoxymethyl)anthracene, used in an amount of 1.75 g.

Propylene polymerization test

The solid catalyst component prepared in the above Examples 46-48 and Comparative Examples 4-6 was used to catalyze the polymerization of propylene. The propylene polymerization was carried out by disposing a 5 L stainless steel autoclave having a volume of 5 rpm with a gas propylene, and then adding AlEt ₃ 2.5 mmol, methylcyclohexyldimethoxysilane (CHMMS) 0.1 thereto. Ethyl, 8-10 mg (preferably 10 mg) of the olefin polymerization catalyst component prepared in the above Examples 46-48 and Comparative Examples 4-6, and 1.2 L of hydrogen, respectively, followed by a liquid propylene 2.3 L, and then heated to 70 After the reaction was carried out for 1 hour at ° C, the temperature was lowered and the pressure was released to obtain a polypropylene (PP) powder. The results are shown in Table 2.

Table 2

It can be seen from Table 2 that when the disulfonate compound of the present invention is used alone or in combination as an internal electron donor, a polymer product having a high stereoregularity and a broad molecular weight distribution can be obtained, which is advantageous. Product development and processing applications.

Claims

a disulfonate compound having the following general formula I,

Where n is an integer and n≥0;

R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;

R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 cycloalkane. a group consisting of a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not all hydrogen and/or a halogen atom.
The disulfonate compound according to claim 1, wherein the alkyl group in the group selected from the group consisting of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Any one or more of the carbon atoms and/or hydrogen atoms of the cycloalkyl, aryl, aralkyl, alkaryl, alkene and fused ring aryl groups are substituted by a halogen atom.
The disulfonate compound according to claim 1, wherein R 3 , R 4 , R 5 , R 6 , R 7 and R 8 contain at least one hetero atom selected from nitrogen, oxygen, a group of sulfur, silicon, phosphorus, and halogen atoms.
The disulfonate compound according to claim 1, wherein R 1 and R 2 are each selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, a group consisting of n-pentyl, cyclopentyl, cyclohexyl, phenyl, alkylphenyl, halophenyl, haloalkylphenyl, anthracenyl, benzyl, phenylethyl and fused ring aryl; Wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclopentyl, cyclohexyl, decyl, benzyl, phenyl b The aryl group and the fused ring aryl group are a group substituted or unsubstituted by a halogen atom.
The disulfonate compound according to claim 1, wherein one of R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, and iso a group consisting of butyl, tert-butyl, phenyl, alkylphenyl and halophenyl; one of R 5 and R 6 is hydrogen and the other is selected from methyl, ethyl, n-propyl, a group consisting of isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl and halophenyl; wherein the methyl, ethyl, n-propyl, isopropyl a group, n-butyl group, isobutyl group, tert-butyl group and alkylphenyl group are a group substituted or unsubstituted by a halogen atom; and a group other than hydrogen in R 3 and R 4 and R 5 and R 6 The groups other than hydrogen are not all phenyl groups.
The disulfonate compound according to claim 1, wherein at least one of R 7 and R 8 is selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl. a group consisting of t-butyl, phenyl, alkylphenyl and halophenyl; wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert The butyl group and the alkylphenyl group are a group substituted or unsubstituted by a halogen atom; and R 7 and R 8 are not all a phenyl group.
The disulfonate compound according to claim 1, wherein n = 0, 1, 2, 3, 4 or 5.
The disulfonate compound according to claim 1, wherein when n = 0, the disulfonate compound has the following formula II:

When n=1, then the disulfonate compound has the following formula III:

When n=2, then the disulfonate compound has the following general formula IV:
The disulfonate compound according to claim 1 or 8, wherein, when n = 1, at least one of R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is a halogen atom, but R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not all hydrogen and/or a halogen atom; and each of the two groups of R 3 and R 4 , R 5 and R 6 has at least one group. It is hydrogen, but R 3 , R 4 , R 5 and R 6 are not all hydrogen.
The disulfonate compound according to claim 1 or 8, wherein when n = 1, and three of R 3 , R 4 , R 5 and R 6 are hydrogen, the other is a halogen atom substituted or not Substituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl or phenyl.
The disulfonate compound according to claim 1 or 8, wherein when n = 1, and only one of the groups of the groups R 3 and R 4 , R 5 and R 6 is hydrogen, The other two groups are not all halogen; and when R 3 and R 4 , R 5 and R 6 are the same group other than hydrogen, and only one of R 7 and R 8 is hydrogen, then R Another group other than hydrogen in 7 and R 8 is different from a group other than hydrogen in R 3 , R 4 , R 5 and R 6 .
The disulfonate compound according to claim 1 or 8, wherein, when n = 1, and only one of each of the groups of R 3 and R 4 , R 5 and R 6 is selected from a linear chain And branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6 a group of -C20 fused ring aryl groups, and when they are the same, R 7 and R 8 are not all hydrogen, and one of R 7 and R 8 is hydrogen and the other is selected from linear and branched C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 A group consisting of fused ring aryl groups; wherein the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkaryl group, alkene group and fused ring aryl group are a halogen-substituted or unsubstituted group.
The disulfonate compound according to claim 1 or 8, wherein when n = 2, only one of R 3 and R 4 is hydrogen or a halogen atom, and only one of R 5 and R 6 is hydrogen or halogen. Atom, and R 7 , R 8 , R 9 and R 10 are not all hydrogen.
The disulfonate compound according to claim 1 or 8, wherein when n = 2, and only one of R 3 and R 4 is hydrogen or a halogen atom, only one of R 5 and R 6 is hydrogen or halogen. When an atom and R 7 , R 8 , R 9 and R 10 are both hydrogen, the groups other than hydrogen or a halogen atom among R 3 , R 4 , R 5 and R 6 are not all methyl groups.
The disulfonate compound according to claim 1 or 8, wherein, when n = 2, R 1 and R 2 are each selected from benzene substituted by a phenyl group, a C1-C20 alkyl group and/or a halogen atom. a group consisting of: and one of R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, benzene a group consisting of alkyl, alkylphenyl and halophenyl; one of R 5 and R 6 is hydrogen and the other is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, a group consisting of isobutyl, tert-butyl, phenyl, alkylphenyl and halophenyl; and R 7 , R 8 , R 9 and R 10 are each selected from hydrogen, methyl, ethyl, and a group consisting of propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl and halophenyl; wherein the methyl, ethyl, n-propyl group Isopropyl, n-butyl, isobutyl, tert-butyl and alkylphenyl are groups which are substituted or unsubstituted by a halogen atom.
The disulfonate compound according to claim 1, wherein, when n ? 3, one of R 3 and R 4 is hydrogen, the other is methyl, and one of R 5 and R 6 is hydrogen And the other is a methyl group, and when R 7 and R 8 are all hydrogen or hydrogen and methyl respectively, at least one of R 1 and R 2 is a phenyl group substituted by a halogen atom and/or an alkyl group.
The disulfonate compound according to claim 1, wherein, when n = 3, at least two of R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not hydrogen, and R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are respectively attached to several groups on different carbon atoms to form a fused ring; and R 1 and R 2 are each selected from a substituted or unsubstituted aryl group. a group consisting of a base and an alkylaryl group.
The disulfonate compound according to claim 1, wherein when n = 4, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not ring-formed, and R 1 and R 2 are Each is selected from the group consisting of an aryl group and an alkylaryl group substituted or unsubstituted with a halogen atom.
The disulfonate compound according to claim 1, wherein, when n ? 3, R 1 and R 2 are each selected from a phenyl group substituted by a phenyl group, a C1-C20 alkyl group and/or a halogen atom; a group consisting of; and one of R 3 and R 4 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, a group consisting of an alkylphenyl group and a halophenyl group; one of R 5 and R 6 is hydrogen and the other is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl a group consisting of a base, a tert-butyl group, a phenyl group, an alkylphenyl group, and a halogenated phenyl group; and a group other than hydrogen in R 3 and R 4 and a group other than hydrogen in R 5 and R 6 Not all phenyl; R 7 and R 8 are each selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, alkylphenyl and halo a group consisting of phenyl groups, and R 7 and R 8 are not all phenyl; wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, and The alkylphenyl group is a group substituted or unsubstituted by a halogen atom.
The disulfonate compound according to claim 1, wherein when n ? 5, R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are not ring-formed.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound represented by the formula V:

Wherein X is carbon or nitrogen, and Y is carbon or nitrogen;

When X is nitrogen, then the substituent R 6 ' is absent; when Y is nitrogen, the substituent R 5 ' is absent; when both X and Y are nitrogen, there are no substituents R 5 ' and R 6 ';

R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;

R 3 ', R 4 ', R 5 ' and R 6 ' are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound represented by the formula VI:

Wherein A and B are each selected from the group consisting of carbon, nitrogen, oxygen and sulfur;

When A is nitrogen, then there is no substituent R 5 ”; when B is oxygen or sulfur, then there are no substituents R 3 ′′ and R 4 ”; when B is nitrogen, there is no substituent R 3 ” ;

R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20;

R 3 ", R 4 ", R 5 " and R 6 " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, A group consisting of an aryl group of C6-C20, an aralkyl group of C7-C20, an alkaryl group of C7-C20, an alkene group of C2-C20, and a fused ring aryl group of C6-C20.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound of the formula VII:

Wherein R 1 and R 2 are the same or different and are respectively selected from a linear and branched alkyl group derived from C1 to C10, a cycloalkyl group of C3-C20, an aryl group of C6-C20, an aralkyl group of C7-C20, a group consisting of alkyl alkaryl groups of C7-C20;

R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6-C10 aryl, C7-. A group consisting of an aralkyl group of C10 and an alkylaryl group of C7-C10.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound of the formula VIII:

Wherein R 1 and R 2 are the same or different and are respectively selected from a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, a fused ring aryl group of C6-C20, optionally hydrogen in the phenyl ring of the aryl group, the alkylaryl group or the aralkyl group The ground is replaced or unsubstituted by a halogen atom;

R 11 - R 16 are each hydrogen or methyl.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound of the formula IX:

Wherein R 1 and R 2 are the same or different and are respectively selected from a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of an alkylaryl group of C7-C20, an alkene group of C2-C20, a fused ring aryl group of C6-C20, optionally hydrogen in the phenyl ring of the aryl group, the alkylaryl group or the aralkyl group The ground is replaced or unsubstituted by a halogen atom;

R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear or branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, and a C6-C20 aromatic group. a group consisting of a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R 11 '-R 18 'is hydrogen or methyl, respectively.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound represented by the formula X:

Wherein R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R 3 , R 4 , R 5 , R 6 , R 11 ′′ and R 12 ′′ are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, and a C3-C20 group. a group consisting of a cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R 3 , R 4 , R 5 , R 6 , R 11 ′′ and R 12 ′′ are not all hydrogen and/or a halogen atom.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises a compound of the formula XI:

Wherein R 1 and R 2 are the same or different and are respectively selected from a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group. a group consisting of a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group;

R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 group. a group consisting of an aryl group, an C7-C20 aralkyl group, a C7-C20 alkaryl group, a C2-C20 alkene group, and a C6-C20 fused ring aryl group; and R 3 , R 4 , R 5 and Several of R 6 are looped or not looped to each other;

R 1 ", R 2 ", R 3 " and R 4 " are the same or different and are respectively selected from hydrogen, a halogen atom, a linear and branched C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6 group. a group of -C20 aryl, C7-C20 aralkyl, C7-C20 alkaryl, C2-C20 alkene and C6-C20 fused ring aryl, and R 1 ", R 2 Several of ", R 3 " and R 4 " form or not form a fused ring structure.
The disulfonate compound according to claim 1, wherein the disulfonate compound represented by the formula I comprises: 1,2-butanediol ditosylate, 2,3-butyl Glycol-toluenesulfonate, catechol di-p-toluenesulfonate, dimethyl 2,5-dicarboxylate-3,4-dihydroxydi-p-toluenesulfonate, 1,3-butanediol Tosylate, 2,4-pentanediol di-tert-butylbenzenesulfonate, 2,4-pentanediol di-chlorobenzenesulfonate, 2,4-pentanediol di-bromobenzenesulfonic acid Ester, 2,4-pentanediol di-p-chlorobenzenesulfonate, 2,4-pentanediol di-p-toluenesulfonate, 2,4-pentanediol diphenylsulfonate, 2,4-pentane Di-tert-butylbenzenesulfonate, 6-heptene-2,4-heptanediol diphenylsulfonate, 3,5-heptanediol diphenylsulfonate, 3,5-heptanediol Chlorobenzenesulfonate, 2,6-dimethyl-3,5-heptanediol diphenylsulfonate, 2,6-dimethyl-3,5-heptanediol di-p-toluenesulfonate, 2 ,6-Dimethyl-3,5-heptanediol di-p-chlorobenzenesulfonate, 6-methyl-2,4-heptanediol diphenylsulfonate, 6-methyl-2,4-heptane Diol tosylate, 6-methyl-2,4-heptanediol di-p-toluenesulfonate, 6-methyl-2,4-heptanediol di-chloride Sulfonate, 6-methyl-2,4-heptanediol dipivalyl sulfonate, 3-methyl-2,4-pentanediol di-p-chlorobenzenesulfonate, 3-methyl-2 , 4-pentanediol di-p-toluenesulfonate, 3-butyl-2,4-pentanediol di-p-toluenesulfonate, 3-methyl-2,4-pentanediol di-p-tert-butylbenzene Sulfonate, 3,3-dimethyl-2,4-pentanediol diphenyl sulfonate, 3-ethyl-2,4-pentanediol diphenyl sulfonate, 3-butyl-2, 4-pentanediol diphenyl sulfonate, 3-allyl-2,4-pentanediol diphenyl sulfonate, 4-methyl-3,5-heptanediol diphenyl sulfonate, 2- Ethyl-1,3-hexanediol diphenyl sulfonate, 2-ethyl-1,3-hexanediol xylene sulfonate, 2,2,4-trimethyl-1,3-pentane Alcoholic acid diphenyl sulfonate, 4-methyl-3,5-octanediol diphenyl sulfonate, 5-methyl-4,6-nonanediol diphenyl sulfonate, 1,3-diphenyl -2-methyl-1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-1,3-propanediol di-n-propyl sulfonate, 1,3-diphenyl-2-methyl -1,3-propanediol di-n-propyl sulfonate, 1,3-diphenyl-2-methyl-1,3-propanediol diethyl sulfonate, 1,3-diphenyl-2,2 - dimethyl-1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol di-n-propyl Sulfonate, 1-phenyl-2-methyl-1,3-butanediol diphenyl sulfonate, 1-phenyl-2-methyl-1,3-butanediol dipentyl sulfonic acid Ester, 6-heptene-2,4-heptanediol dipivalyl sulfonate, 2,2,4,6,6-pentamethyl-3,5-hexanediol diphenyl sulfonate, 1 , 3-di-tert-butyl-2ethyl-1,3-propanediol diphenyl sulfonate, 1,3-diphenyl-1,3-propanediol diacetate, 1-furan-2-methyl- 1,3-butanediol diphenyl sulfonate, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl sulfonate, 2-isopropyl-2 isopentyl-1,3- Propylene glycol di-p-chlorobenzenesulfonate, 2-isopropyl-2-isopentyl-1,3-propanediol di-chlorobenzenesulfonate, 2-isopropyl-2-isopentyl-1,3-propanediol P-methoxybenzenesulfonate, 2-isopropyl-2isopentyl-1,3-propanediol di-n-propanesulfonate, 2,2-diisobutyl-1,3-propanediol dibenzenesulfonic acid Ester, 2-isopropyl-2-isopentyl-1,3-propanediol diphenyl sulfonate, 1,8-naphthalenediol di-p-toluenesulfonate, 9,9-bis(benzenesulfonate) Base, 9,9-bis (p-toluenesulfonic acid) Methyl) hydrazine, 1,1-bis(p-toluenesulfonylmethyl)cyclohexane, 2,3-diethyl-1,4-butanediol di-p-toluenesulfonate, 2,5- Dimethyl-2,5-hexanediol di-p-toluenesulfonate, 3,6-dimethyl-3,6-dioctanol di-p-toluenesulfonate, cis-2-butene-1,4 -diol di-p-toluenesulfonate, 1,5-diphenyl-1,5-pentanediol di-p-toluenesulfonate, 1,4-hexanediol di-p-toluenesulfonyl ester, 1, 5-hexanediol di-p-toluenesulfonate, 2,2'-biphenyldiethanol di-p-toluenesulfonate.
Use of the metasulfonate compound according to any one of claims 1 to 28 for the preparation of an olefin polymerization catalyst component.
An olefin polymerization catalyst component prepared by using the disulfonic acid ester compound according to any one of claims 1 to 28, which comprises a reaction product of the following raw materials:

Raw material (1) composite carrier: which forms a solution by contacting a magnesium halide with one or several compounds capable of dissolving magnesium halide, and then mixing the solution with silica having an average particle diameter of less than 10 μm, and preparing by spray drying ;

Starting material (2) electron donor a: at least one compound selected from the group consisting of the above-mentioned disulfonic acid ester compounds;

Starting material (3) electron donor b: at least one selected from the group consisting of aliphatic mono- and dicarboxylic acid ester compounds, aromatic mono- and dicarboxylic acid ester compounds, and diether compounds represented by formula XVI Composition of the group of compounds:

Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and are respectively selected from hydrogen, C1-C10 linear and branched alkyl, C3-C10 cycloalkyl, C6- a group consisting of an aryl group of C10, an aralkyl group of C7-C10, and an alkylaryl group of C7-C10; R 7 and R 8 are the same or different and are each selected from a linear and branched alkyl group derived from C1 to C10. a group consisting of a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C7-C20 aralkyl group, and a C7-C20 alkaryl group;

Raw material (4) titanium halide: at least one compound selected from the group consisting of titanium compounds represented by the general formula Ti(OQ) 4-m Z m , wherein Q is selected from the group consisting of C1-C14 aliphatic hydrocarbon groups Group, several Qs may be the same or different, Z is selected from the group consisting of F, Cl and Br, several Z may be the same or different, and m is an integer from 1 to 4;

Wherein, the total amount of the electron donor a and the electron donor b is 0.01 to 1 mole per mole of the magnesium halide in the composite carrier, and the molar ratio of the electron donor a to the electron donor b is 0.1 to 10, the titanium compound It is 1-100 moles.
The olefin polymerization catalyst component according to claim 30, wherein the electron donor b is selected from the group consisting of a benzoate compound, a phthalate compound, a malonic ester compound, a succinate compound, E A group consisting of a diester compound, a pivalate compound, and a diether compound represented by the formula XVI.
The olefin polymerization catalyst component according to claim 30, wherein the composite carrier has an average diameter of from 5 to 60 μm.
The olefin polymerization catalyst component according to claim 30, wherein the total amount of the electron donor a and the electron donor b is 0.05 to 0.5 mol per mol of the magnesium halide in the composite support; the electron donor a and the electron donor The molar ratio of the body b is 0.2-5.
An olefin polymerization catalyst comprising the following components:

Component (1) The olefin polymerization catalyst component according to any one of claims 30 to 33;

Component (2) an alkyl aluminum compound.
The olefin polymerization catalyst according to claim 34, wherein the alkyl aluminum compound has a formula of AlL w D 3-w , wherein L is selected from the group consisting of hydrogen, a C1-C20 alkyl group, a C1-C20 aryl group, A group consisting of C1-C20 aralkyl groups, D is a halogen atom, w=1, 2 or 3.
The olefin polymerization catalyst according to claim 34, which further comprises an organosilicon compound of the formula (3) of the formula T 1 u Si(OT 2 ) 4-u , wherein T 1 is selected from hydrogen, a halogen atom, a group consisting of an alkyl group, a cycloalkyl group, an aryl group, and a halogenated alkyl group; T 2 is selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and a halogenated alkyl group; T 1 and T 2 are the same or different; An integer of 0-3.
The olefin polymerization catalyst according to claim 34 or 36, wherein the ratio between the component (1) and the component (2) is 1: (5-1000) in terms of a molar ratio of titanium: aluminum; 1) The ratio between the components (3) is 1: (5-500) in terms of a molar ratio of titanium: silicon.
Use of the olefin polymerization catalyst of any of claims 34-37 in the polymerization of olefins.
The use according to claim 38, wherein the olefin polymerization reaction is a CH 2 =CHG olefin polymerization reaction, wherein G is selected from the group consisting of hydrogen, a C1-C20 alkyl group, and a C1-C20 aryl group.