RU2779192C2 - Catalytic component for olefin polymerization, its production method, and catalyst including it - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalytic component of a Ziegler-Natt catalyst for olefin polymerization, its production method, a catalyst including it, a prepolymerized catalyst, and a method for olefin polymerization. The catalytic component includes magnesium, titanium, halogen, an inner electron-donor compound, and an auxiliary precipitating additive, which contains an additive a of the formula (I), including isomer of the general formula (I-a) and/or (I-b). The content of the auxiliary precipitating additive a is less than 1.0 wt.% per the total weight of the catalytic component. The method for the production of the catalytic component includes stages of: 1) dissolution of a magnesium compound in a system of solvents to form a solution containing the magnesium compound; 2) precipitation of particles of magnesium-containing solid substances from the solution containing the magnesium compound in the presence of the auxiliary precipitating additive, which contains at least one auxiliary precipitating additive a of the formula (I), which contains isomers (I-a) and/or (I-b), in amount of more than 80 wt.% per the total weight of the auxiliary precipitating additive a; 3) application of an active component based on titanium to particles of magnesium-containing solid substances to form a solid catalytic component.

EFFECT: extremely low content of a residual auxiliary precipitating additive in the resulting solid catalytic component, as a result of which hindering impact of the auxiliary precipitating additive on an inner electron donor is eliminated; increase in the activity.

17 cl, 4 tbl, 18 ex

Description

Cross-reference to related applications

This application claims the priority and benefit of Chinese Patent Applications Nos. 201810489139.5, 201810489207.8 and 201810489282.4, filed May 21, 2018, which are incorporated herein by reference in their entirety.

Technical field

The present invention belongs to the field of catalysts and, in particular, relates to a catalyst component for the polymerization of olefins, a method for producing a catalyst component and a catalyst containing it.

State of the art

Solid catalyst components containing magnesium, titanium, halogen and an electron donor as main ingredients, i.e., Ziegler-Natta catalysts, well known in the art, can be used for the polymerization of α-olefins, especially for the polymerization of α-olefins having 3 or more carbon atoms, while providing a higher yield and give polymers having higher stereoregularity. One of the methods for their preparation includes the following steps: first, the preparation of magnesium dichloride in a homogeneous solution, and then the precipitation of a solid and the application of a titanium-containing active component. In such a process, in the solids precipitation step, solids with a uniform particle size and good morphology can usually be obtained only when a precipitating aid is present, the precipitating aid usually being an organic acid anhydride, an organic acid, a ketone, an ether, an ester. ether, etc., and sometimes it is considered an internal electron-donating compound. See, for example, documents CN 101864009, CN 106317274, CN 106317275, CN 101906177, CN 102276765, CN 103012625, CN 103012626, CN 103012627 and CN 106608933.

It is believed that when a precipitant is used in the preparation of a solid catalyst component, the resulting solid catalyst component will contain some precipitant, and the precipitant may affect the performance of the solid catalyst component. However, little attention has been paid in the prior art to the effect of the type of precipitant additive and its content in the solid catalyst component on the performance of the solid catalyst component.

In addition, various internal electron donor compounds have been disclosed in the literature that are capable of imparting desired properties to a Ziegler-Natta catalyst. For example, document CN 1020448 discloses internal electron donor compounds of the 1,3-diester type. Catalyst components containing a 1,3-diether type internal electron donor compound have high activity and good hydrogen modulation sensitivity when used for olefin polymerization, and the molecular weight distribution of the obtained olefin polymers is very narrow. As another example, documents CN 102311513 and CN 102603931 disclose the use of diethyl 2-cyanosuccinate as an internal electron donor compound. The obtained polyolefin catalyst is insensitive to hydrogen modulation, has good stereospecificity, and the polypropylene obtained using the catalyst has a very broad molecular weight distribution.

However, the prior art does not provide guidance on how to reduce the interference of the precipitating aid in the operation of the internal electron donor compound.

There is still a need in the art for an improved Ziegler-Natta catalyst exhibiting many desirable properties and methods for making the same.

The essence of the invention

In order to solve the problems encountered in the prior art, the inventors of the present invention have made extensive and in-depth studies. As a result, it was unexpectedly found that when a diol ester in which the content of isomers of a certain configuration (i.e., R,R-configuration and/or S,S-configuration isomers) is greater than 80% is used as a precipitating aid when producing a solid catalyst component, solid particles with good morphology can be deposited, and the content of the residual precipitant additive in the obtained solid catalyst component is extremely low, thereby eliminating the interfering effect of the precipitant additive on the internal electron donor. The present invention has been made on this basis.

Thus, the object of the present invention is to provide a catalyst component for the polymerization of olefins, containing magnesium, titanium, halogen, an internal electron donor compound and an auxiliary precipitating additive, and the auxiliary precipitating additive contains at least one auxiliary precipitating additive a represented by the formula (I ), and the auxiliary precipitating additive a contains an isomer represented by formula (I-a) and/or formula (I-b):

where the substituents R ₁ and R ₂ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted ; the substituents R ₃ and R ₄ are each independently selected from the group consisting of C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl and C ₇ -C ₂₀ -aralkyl, or substituted or unsubstituted, and

where the content of the auxiliary precipitating additives and is lower than 1.0% of the mass. based on the mass of the catalytic component.

Another object of the present invention is to develop a method for producing the catalyst component described above.

Another object of the present invention is to provide an olefin polymerization catalyst comprising:

1) a catalyst component according to the invention;

2) alkyl aluminum compound; and

3) optionally an external electron donor compound.

Another object of the present invention is to provide a prepolymerized catalyst for the polymerization of olefins, comprising a prepolymer obtained by prepolymerization using the catalyst component/catalyst of the invention and an olefin.

Another object of the present invention is to provide a process for the polymerization of an olefin having the formula CH ₂ =CHR, where R is a hydrogen atom, C ₁ -C ₆ -alkyl or aryl, comprising the polymerization of an olefin in the presence of a catalyst or a prepolymerized catalyst in accordance with the present the invention to form a polyolefin polymer; and isolating the thus obtained polyolefin polymer.

Detailed description of the preferred embodiments of the invention

Definitions

As used herein, the term "substituted" or "substituted" means that one or more hydrogen atoms on the group in question is replaced by a halogen atom, a heteroatom, a C ₁ -C ₆ alkyl, or a C ₁ -C ₆ alkoxy group, or a carbon atom in the main chain is replaced by a heteroatom.

As used herein, the term "halogen" or "halogen atom" refers to at least one of fluorine, chlorine, bromine, and iodine.

As used herein, the term "heteroatom" refers to at least an atom selected from the group consisting of O, S, N, P, Si, and Ge.

The term "polymerization" as used herein is meant to include homopolymerization and copolymerization. The term "polymer" as used herein is intended to include homopolymer, copolymer, and terpolymer.

As used herein, the term "(solid) catalyst component" refers to the main catalyst or procatalyst component which, together with a conventional co-catalyst such as aluminum alkyl and an optional external electron donor, constitutes an olefin polymerization catalyst (also referred to in the art as catalytic system).

In a first aspect, the present invention provides an olefin polymerization catalyst component comprising magnesium, titanium, halogen, an precipitant aid and an internal electron donor compound, the precipitant aid comprising an precipitant aid a represented by formula (I) and the precipitant aid a comprising isomers represented by formula (I-a) and/or formula (I-b):

where the substituents R ₁ and R ₂ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted , preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, or substituted or unsubstituted, more preferably from the group including substituted or unsubstituted C ₁ -C ₄ - alkyl, and even more preferably from the group consisting of methyl, ethyl, n-propyl and isopropyl; the substituents R ₃ and R ₄ are each independently selected from the group consisting of C ₁ -C ₂₀ -alkyl, C ₃ -C ₂₀ -cycloalkyl, C ₆ -C ₂₀ -aryl and C ₇ -C ₂₀ -aralkyl, or substituted or unsubstituted, preferably from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl and C ₆ -C ₁₀ -aryl, or substituted or unsubstituted, more preferably from the group including C ₅ -C ₁₀ -alkyl, C ₅ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, either substituted or unsubstituted, and even more preferably from the group consisting of cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, p-ethylphenyl, p -n-propylphenyl, and p-n-butylphenyl.

Precipitating aid a shown by formula (I) and useful in the present invention are diol esters which contain two chiral carbon atoms. When the substituents R ₁ and R ₂ are different from each other and/or the substituents R ₃ and R ₄ are different from each other, the two chiral carbon atoms are different chiral carbon atoms, and the compounds represented by formula (I) include four isomers of R, R-configurations, S, S-configurations, R, S-configurations and S, R-configurations, shown by formulas (Ia), (Ib), (Ic) and (Id), respectively. When the substituents R ₁ and R ₂ are the same and the substituents R ₃ and R ₄ are the same, the two chiral carbons are identical chiral carbons, the R, S configuration and the S, R configuration become entirely the same configuration, and , therefore, the compounds represented by formula (I) have three isomers R, R-configuration, S, S-configuration and R, S-/S, R-configuration shown by formulas (Ia), (Ib) and (Ic) , respectively.

In some embodiments, examples of precipitant additive a represented by formula (I) include, but are not limited to, 2,4-pentylenedibenzoate, 2,4-pentylene-di-p-methylbenzoate, 2,4-pentylene-di-p -ethylbenzoate, 2,4-pentylene-di-p-n-propylbenzoate, 2,4-pentylene-di-p-n-butylbenzoate, 3,5-heptylene-dibenzoate, 3,5-heptylene-di-p-methylbenzoate , 3,5-heptylene-di-p-ethyl benzoate, 3,5-heptylene-di-p-n-propyl benzoate, 3,5-heptylene-di-p-n-butyl benzoate and mixtures thereof.

According to the present invention, a precipitating aid containing the precipitating aid a represented by formula (I) is used in the preparation of a catalyst component. The source material of the auxiliary precipitating additive and usually contains (R, R) - and/or (S, S) -isomers in an amount of more than 80 wt. -%, preferably more than 90 wt. -%, more preferably more than 95 wt.%. and even more preferably more than 98% of the mass. based on their total weight. Compared to the (R, S)- and (S, R)-configuration isomers, the (R, R)- and/or (S, S)-configuration isomers have a very different ability to bind to the catalyst component and are easily washed out, and, therefore, the co-precipitant a retained in the final catalyst component will contain a significantly reduced proportion of (R, R)- and (S, S)-isomers and a significantly increased proportion of (R, S)- and (S, R)-isomers compared with the starting material of the auxiliary precipitating additive a. Depending on the composition of the starting material of the auxiliary precipitating additive a used in the preparation of the catalytic component, the content of the (R, R)- and (S, S)-isomer and the content of the (R, S)- and (S, R)-isomer of the residual auxiliary precipitating additive and in the final catalytic component can vary over a wide range. However, it is preferable that the ratio of the content of (R, R)- and (S, S)-isomers to the content of (R, S)- and (S, R)-isomers of the residual auxiliary precipitating additive a in the final catalytic component is not less than 1 :10, preferably not less than 1:5, more preferably not less than 1:3, and even more preferably not less than 1:2. This can be achieved by selecting the starting material of the auxiliary precipitating additive a, having a high content of (R, R) - and (S, S) -isomers.

In some specific embodiments, for the purpose of the present invention, the starting material of the auxiliary precipitating additive used in the preparation of the catalytic component contains in an amount of more than 80% wt., preferably more than 90% wt., more preferably more than 95% wt. and even more preferably more than 98% of the mass. based on their total weight, at least one of the following isomeric combinations: (R, R)-2,4-pentylene-dibenzoate and (S, S)-2,4-pentylenedibenzoate, (R, R)- 2,4-pentylene-di-p-methylbenzoate and (S,S)-2,4-pentylene-di-p-methylbenzoate, (R,R)-2,4-pentylene-di-p-ethylbenzoate and (S , S)-2,4-pentylene-di-p-ethyl-benzoate, (R, R)-2,4-pentylene-di-p-n-propylbenzoate and (S, S)-2,4-pentylene- di-p-n-propyl benzoate, (R, R)-2,4-pentylene-di-p-n-butyl-benzoate and (S, S)-2,4-pentylene-di-p-n-butyl benzoate, (R, R)-3,5-heptylenedibenzoate and (S, S)-3,5-heptylenedibenzoate, (R, R)-3,5-heptylene-di-p-methylbenzoate and (S, S)-3, 5-heptylene-di-p-methyl-benzoate, (R,R)-3,5-heptylene-di-p-ethylbenzoate and (S,S)-3,5-heptylene-di-p-ethylbenzoate, (R , R)-3,5-heptylene-di-p-n-propyl-benzoate and (S, S)-3,5-heptylene-di-p-n-propyl-benzoate, (R, R)-3,5- heptylene di-p-n-butyl benzoate; and (S, S)-3,5-heptylene di-p-n-butyl benzoate.

Preferably, the starting material of the auxiliary precipitating additive a used in the preparation of the catalytic component contains more than 80% by weight, preferably more than 90% by weight, more preferably more than 95% by weight. and even more preferably more than 98% of the mass. based on their total weight, at least one of the following isomeric combinations: (R, R)-2,4-pentylenedibenzoate and (S, S)-2,4-pentylenedibenzoate, (R, R)-2.4 -pentylene-di-p-methyl-benzoate and (S,S)-2,4-pentylene-di-p-methylbenzoate, (R,R)-2,4-pentylene-di-p-ethylbenzoate and (S, S)-2,4-pentylene-di-p-ethylbenzoate, (R, R)-2,4-pentylene-di-p-n-propylbenzoate and (S, S)-2,4-pentylene-di-p -n-propylbenzoate, (R, R)-3,5-heptylenedibenzoate and (S, S)-3,5-heptylenedibenzoate, (R, R)-3,5-heptylene-di-p-methylbenzoate and (S, S)-3,5-heptylene-di-p-methylbenzoate, (R, R)-3,5-heptylene-di-p-ethyl-benzoate and (S, S)-3,5-heptylene-di-p -ethyl benzoate, (R, R)-3,5-heptylene-di-p-n-propyl-benzoate and (S, S)-3,5-heptylene-di-p-n-propyl-benzoate.

Most preferably, the starting material of the auxiliary precipitating additive a used in the preparation of the catalytic component contains, in an amount of more than 80% wt., preferably more than 90% wt., more preferably more than 95% wt. and even more preferably more than 98% of the mass. based on their total weight, at least one of the following isomeric combinations: (R, R)-2,4-pentylenedibenzoate and (S, S)-2,4-pentylenedibenzoate, (R, R)-2.4 -pentylene-di-p-methyl-benzoate and (S,S)-2,4-pentylene-di-p-methylbenzoate, (R,R)-2,4-pentylene-di-p-ethylbenzoate and (S, S)-2,4-pentylene-di-p-ethylbenzoate, (R, R)-3,5-heptylenedibenzoate and (S, S)-3,5-heptylenedibenzoate, (R, R)-3,5-heptylene -di-p-methylbenzoate and (S,S)-3,5-heptylene-di-p-methylbenzoate, (R,R)-3,5-heptylene-di-p-ethylbenzoate and (S,S)-3 ,5-heptylene-di-p-ethylbenzoate.

In some embodiments of the invention, the content of the auxiliary precipitating additives in the catalytic component is less than 1.0% wt., preferably less than 0.5% wt., more preferably less than 0.2% wt. and even more preferably less than 0.15% of the mass. based on the total weight of the catalytic component.

In some embodiments, the precipitant additive also optionally comprises a precipitant additive b represented by formula (II):

Ti(OR ₇ ) _n X _4-n (II),

where R ₇ is C ₁ -C ₁₀ alkyl or C ₃ -C ₁₀ cycloalkyl, X is halogen, and n is 1, 2, 3 or 4.

In some preferred embodiments, the precipitating aid b is at least one selected from tetramethyl titanate, tetraethyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-n-propyl titanate, and tetraisopropyl titanate, and is preferably tetraethyl titanate or tetra-n-butyl titanate.

In some embodiments, the precipitant in the catalytic component of the invention consists essentially of the precipitant auxiliaries described above a and the precipitant auxiliaries described above b.

In other embodiments, the implementation of the auxiliary precipitating additive in the catalyst component according to the invention consists essentially of the auxiliary precipitating additive described above a.

In some embodiments, the implementation of the catalytic component according to the invention does not contain other auxiliary precipitating additives in addition to the auxiliary precipitating additive described above a and the auxiliary precipitating additive described above b.

In accordance with the present invention, there is no particular limitation on the internal electron donor in the catalyst component, and any internal electron donor compound known in the art that imparts the desired properties to the catalyst component may be included in the catalyst component.

In some embodiments, the catalyst component of the invention contains at least one 2,2-dihydrocarbyl-1,3-propylene glycol dimethyl ether type compound represented by formula (III) as an internal electron donor:

where the substituents R ₅ and R ₆ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -alkaryl, or substituted or unsubstituted ; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, or substituted or unsubstituted; more preferably from the group consisting of substituted or unsubstituted C ₁ -C ₆ alkyl groups; and also preferably from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, cyclopentyl, cyclohexyl and phenyl. Substituents R ₅ and R ₆ are optionally linked to form a ring. Other ethers such as diethyl ether, dipropyl ether, methyl ethyl ether and the like are also contemplated.

Suitable examples of the 2,2-dihydrocarbyl-1,3-propylene glycol dimethyl ether type compound represented by formula (III) include, but are not limited to, 2,2-di-n-propyl-1,3-propylene glycol dimethyl ether, 2,2-diisopropyl-1,3-propylene glycol dimethyl ether, 2,2-di-n-butyl-1,3-propylene glycol dimethyl ether, 2,2-diisobutyl-1,3-propylene glycol dimethyl ether, dimethyl ether 2, 2-di-n-pentyl-1,3-propylene glycol, 2,2-diisopentyl-1,3-propylene glycol dimethyl ether, 2,2-di-n-hexyl-1,3-propylene glycol dimethyl ether, dimethyl ether 2, 2-diisohexyl-1,3-propylene glycol, 2-n-propyl-2-isopropyl-1,3-propylene glycol dimethyl ether, 2-n-propyl-2-n-butyl-1,3-propylene glycol dimethyl ether, dimethyl ether 2-n-propyl-2-isobutyl-1,3-propylene glycol, 2-n-propyl-2-n-pentyl-1,3-propylene glycol dimethyl ether, 2-n-propyl-2-isopentyl-1 dimethyl ether, 3-propylene glycol, 2-n-propyl-2-n-hexyl-1,3-propylene glycol dimethyl ether, 2-n-propyl-2-isohexyl dimethyl ether -1,3-propylene glycol, 2-isopropyl-2-n-butyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-n dimethyl ether -pentyl-1,3-propylene glycol, 2-isopropyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-n-hexyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2 dimethyl ether -isohexyl-1,3-propylene glycol, 2-n-butyl-2-isobutyl-1,3-propylene glycol dimethyl ether, 2-n-butyl-2-n-pentyl-1,3-propylene glycol dimethyl ether, dimethyl ether 2 -n-butyl-2-isopentyl-1,3-propylene glycol, 2-n-butyl-2-n-hexyl-1,3-propylene glycol dimethyl ether, 2-n-butyl-2-isohexyl-1,3 dimethyl ether -propylene glycol, 2-isobutyl-2-n-pentyl-1,3-propylene glycol dimethyl ether, 2-isobutyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-isobutyl-2-n-hexyl-1 dimethyl ether ,3-propylene glycol, 2-isobutyl-2-isohexyl-1,3-propylene glycol dimethyl ether, 2-n-pentyl-2-isopentyl-1,3-propylene glycol dimethyl ether, dimethyl 2-n-pentyl-2-n-hexyl-1,3-propylene glycol ether, 2-n-pentyl-2-isohexyl-1,3-propylene glycol dimethyl ether, 2-isopentyl-2-n-hexyl-1 dimethyl ether ,3-propylene glycol, 2-isopentyl-2-isohexyl-1,3-propylene glycol dimethyl ether and 2-n-hexyl-2-iso-hexyl-1,3-propylene glycol dimethyl ether.

In some preferred embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one compound selected from the group consisting of 2,2-di-isopropyl-1,3-propylene glycol dimethyl ether, 2,2- di-n-butyl-1,3-propylene glycol, dimethyl ether 2,2-diisobutyl-1,3-propylene glycol, dimethyl ether 2,2-di-n-pentyl-1,3-propylene glycol, dimethyl ether 2,2- diisopentyl-1,3-propylene glycol, 2-n-propyl-2-isopropyl-1,3-propylene glycol dimethyl ether, 2-n-propyl-2-isobutyl-1,3-propylene glycol dimethyl ether, 2-n-dimethyl ether propyl-2-isopentyl-1,3-propylene glycol, 2-isopropyl-2-n-butyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1,3-propylene glycol dimethyl ether, 2-dimethyl ether isopropyl-2-n-pentyl-1,3-propylene glycol, 2-isopropyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propylene glycol dimethyl ether, 2-dimethyl ether n-butyl-2-iso butyl-1,3-propylene glycol, 2-n-butyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-n-butyl-2-isohexyl-1,3-propylene glycol dimethyl ether, 2-isobutyl-dimethyl ether 2-n-pentyl-1,3-propylene glycol, 2-isobutyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-isobutyl-2-n-hexyl-1,3-propylene glycol dimethyl ether, 2-dimethyl ether isobutyl-2-isohexyl-1,3-propylene glycol; and 2-n-pentyl-2-isopentyl-1,3-propylene glycol dimethyl ether.

In some preferred embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one compound selected from the group consisting of 2,2'-diisopropyl-1,3-propylene glycol dimethyl ether, 2,2'- diisobutyl-1,3-propylene glycol, 2,2'-diisopentyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-isobutyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-n-pentyl dimethyl ether -1,3-propylene glycol, 2-isopropyl-2-isopentyl-1,3-propylene glycol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propylene glycol dimethyl ether, 2-isobutyl-2-n-pentyl dimethyl ether -1,3-propylene glycol, 2-isobutyl-2-isopentyl-1,3-propylene glycol dimethyl ether and 2-n-pentyl-2-isopentyl-1,3-propylene glycol dimethyl ether.

In some embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one compound of the diethyl 2-cyano-2,3-dihydrocarbyl succinate type represented by formula (III'):

where the substituents R ₅ and R ₆ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted ; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, or substituted or unsubstituted; more preferably from the group consisting of C ₁ -C ₆ -alkyl and phenyl, or substituted or unsubstituted; and even more preferably from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, cyclopentyl, cyclohexyl and phenyl. Suitable other ethers are also contemplated, such as dimethyl ether, dipropyl ether, methyl ethyl ether, and the like.

Suitable examples of the diethyl 2-cyano-2,3-dihydrocarbyl succinate type compound represented by formula (III') include, but are not limited to, diethyl 2-cyano-2,3-di-n-propyl succinate, diethyl 2-cyano -2,3-diisopropylsuccinate, diethyl-2-cyano-2,3-di-n-butylsuccinate, diethyl-2-cyano-2,3-diisobutyl-succinate, diethyl-2-cyano-2,3-di-n -pentylsuccinate, diethyl-2-cyano-2,3-diisopentylsuccinate, diethyl-2-cyano-2,3-dicyclopentylsuccinate, diethyl-2-cyano-2,3-di-n-hexylsuccinate, diethyl-2-cyano-2 ,3-diisohexylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-propylsuccinate, diethyl-2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl-2-cyano-2-isopropyl-3-isobutylsuccinate , diethyl 2-cyano-2-isopropyl-3-n-pentylsuccinate, diethyl-2-cyano-2-isopropyl-3-isopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl-2-cyano -2-n-butyl-3-n-propyl-succinate, diethyl-2-cyano-2-n-butyl-3-isopropylsuccinate, diethyl-2-cyano-2-n-butyl-3-isobutylsuccinate, diethyl-2 -cyano-2-n-butyl-3-n-pentylsuccinate, diethyl-2-cyano-2-n-butyl-3 -isopentyl succinate, diethyl 2-cyano-2-n-butyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-isobutyl-3-n-propyl succinate, diethyl 2-cyano-2-isobutyl-3-isopropyl succinate , diethyl 2-cyano-2-isobutyl-3-n-butylsuccinate, diethyl-2-cyano-2-isobutyl-3-n-pentylsuccinate, diethyl-2-cyano-2-isobutyl-3-iso-pentyl-succinate , diethyl 2-cyano-2-isobutyl-3-cyclopentyl succinate, diethyl 2-cyano-2-n-pentyl-3-n-propyl succinate, diethyl 2-cyano-2-n-pentyl-3-isopropyl succinate, diethyl -2-cyano-2-n-pentyl-3-n-butylsuccinate, diethyl-2-cyano-2-n-pentyl-3-isobutylsuccinate, diethyl-2-cyano-2-n-pentyl-3-isopentylsuccinate, diethyl -2-cyano-2-n-pentyl-3-cyclopentyl-succinate, diethyl-2-cyano-2-isopentyl-3-n-propyl-succinate, diethyl-2-cyano-2-isopentyl-3-isopropyl-succinate, diethyl -2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl-2-cyano-2-isopentyl-3-isobutylsuccinate, diethyl-2-cyano-2-isopentyl-3-n-pentylsuccinate, diethyl-2-cyano -2-isopentyl-3-cyclopentylsuccinate, diethyl-2-cyano-2-cyclopentyl-3-n-propyl-succinate, diethyl-2-cyano-2-cyclopentyl-3-i zoopropyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-butyl succinate, diethyl 2-cyano-2-cyclopentyl-3-isobutyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-pentyl succinate and diethyl 2-cyano-2-cyclopentyl-3-isopentylsuccinate.

In some preferred embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one compound selected from the group consisting of diethyl-2-cyano-2,3-diisopropyl-succinate, diethyl-2-cyano-2, 3-di-n-butylsuccinate, diethyl-2-cyano-2,3-diisobutylsuccinate, diethyl-2-cyano-2,3-di-n-pentylsuccinate, diethyl-2-cyano-2,3-diisopentylsuccinate, diethyl- 2-cyano-2-isopropyl-3-n-propylsuccinate, diethyl-2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl-2-cyano-2-isopropyl-3-isobutylsuccinate, diethyl-2-cyano- 2-isopropyl-3-n-pentylsuccinate, diethyl-2-cyano-2-isopropyl-3-isopentylsuccinate, diethyl-2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl-2-cyano-2-n-butyl- 3-isopropyl-succinate, diethyl-2-cyano-2-n-butyl-3-isobutyl-succinate, diethyl-2-cyano-2-n-butyl-3-n-pentylsuccinate, diethyl-2-cyano-2-isobutyl- 3-isopropylsuccinate, diethyl-2-cyano-2-isobutyl-3-n-butylsuccinate, diethyl-2-cyano-2-isobutyl-3-n-pentylsuccinate, diethyl-2-cyano-2-n-pentyl-3- from opyl succinate, diethyl 2-cyano-2-n-pentyl-3-n-butyl succinate, diethyl 2-cyano-2-n-pentyl-3-isobutyl succinate, diethyl 2-cyano-2-isopentyl-3-isopropyl succinate, diethyl 2-cyano-2-isopentyl-3-n-butylsuccinate, diethyl-2-cyano-2-isopentyl-3-isobutylsuccinate, diethyl-2-cyano-2-cyclopentyl-3-isopropyl-succinate, diethyl-2- cyano-2-cyclopentyl-3-n-butylsuccinate; and diethyl 2-cyano-2-cyclopentyl-3-isobutylsuccinate.

In some preferred embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one compound selected from the group consisting of diethyl-2-cyano-2,3-diisopropyl-succinate, diethyl-2-cyano-2, 3-di-n-butylsuccinate, diethyl-2-cyano-2,3-diisobutylsuccinate, diethyl-2-cyano-2,3-di-n-pentylsuccinate, diethyl-2-cyano-2,3-di-isopentylsuccinate, diethyl 2-cyano-2-isopropyl-3-n-butylsuccinate, diethyl-2-cyano-2-isopropyl-3-isobutylsuccinate, diethyl-2-cyano-2-isopropyl-3-n-pentylsuccinate, diethyl-2- cyano-2-isopropyl-3-isopentylsuccinate, diethyl-2-cyano-2-isopropyl-3-cyclopentylsuccinate, diethyl-2-cyano-2-n-butyl-3-isopropylsuccinate, diethyl-2-cyano-2-isobutyl- 3-isopropyl succinate, diethyl 2-cyano-2-n-pentyl-3-isopropyl succinate, diethyl 2-cyano-2-isopentyl-3-isopropyl succinate and diethyl 2-cyano-2-cyclopentyl-3-isopropyl succinate.

In some embodiments, the catalyst component of the invention contains, as an internal electron donor, at least one phthalate type compound represented by formula (III"):

where the substituents R ₇ and R ₈ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -alkaryl, or substituted or unsubstituted ; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, or substituted or unsubstituted; more preferably from the group consisting of substituted or unsubstituted C ₁ -C ₆ alkyl groups; and even more preferably from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and isopentyl.

Suitable examples of the phthalate-type compound represented by formula (III'') include, but are not limited to, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, and diisoamyl phthalate.

Preferably, the phthalate type compound represented by formula (III'') is selected from the group consisting of diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate and di-n-pentyl phthalate. Most preferably, the phthalate-type compound represented by formula (III'') is selected from the group consisting of diethyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate and di-isobutyl phthalate.

In the catalytic component according to the invention, the titanium content is in the range from 1.0 to 8.0% of the mass. and preferably from 1.6 to 6.0% wt.; the magnesium content is in the range from 10.0 to 70.0% of the mass. and preferably from 15.0 to 40.0% wt.; the halogen content is in the range from 20.0 to 90.0% of the mass. and preferably from 30.0 to 85.0% wt.; the content of the internal electron donor compounds is in the range from 2.0 to 30.0% of the mass. and preferably from 3.0 to 20.0% of the mass. based on the total weight of the catalytic component.

In some embodiments, the catalyst component of the invention comprises the reaction product of a magnesium compound, a titanium compound, at least one internal electron donor compound, and an auxiliary precipitant, at least containing at least one precipitant additive a, represented by formula (I ). Titanium compounds, magnesium compounds, and internal electron donor compounds that can be used to prepare Ziegler-Natta catalyst components by the dissolution-precipitation process are well known to those skilled in the art, and they can be used in conventional amounts used in the art to obtain catalyst component of the present invention. Some examples of titanium compounds and magnesium compounds are described below.

In some embodiments of the invention, relative to one mol of magnesium compound, the amount of used auxiliary precipitating additive a may be in the range from 0.005 to 0.3 mol and preferably from 0.01 to 0.05 mol; the mole ratio of co-precipitant a to internal electron donor compound may be in the range of 0.05:1 to less than 0.8:1, and preferably 0.1:1 to 0.7:1.

In some embodiments, the precipitating aid used in the preparation of the catalyst component further comprises the precipitating aid b described above, and the amount of precipitating aid b used is in the range of 0.01 to 5 mol, and preferably 0.5 to 3 mole relative to one mole of the auxiliary precipitating additive a.

In a second aspect, the present invention provides a method for producing an olefin polymerization catalyst component in accordance with the present invention. In principle, any method known in the art that can be used to prepare a Ziegler-Natta catalyst using a solution-precipitation process can be used to prepare the catalyst components of the present invention, provided that the precipitant containing the precipitant additive a, described above, is introduced into the reaction system before the precipitation of solid particles.

Thus, the present invention provides a process for producing an olefin polymerization catalyst component comprising the steps of:

1) dissolving a magnesium compound in a solvent system to obtain a solution containing a magnesium compound;

2) precipitation of particles of magnesium-containing solids from a solution containing a magnesium compound in the presence of an auxiliary precipitating additive, where the auxiliary precipitating additive contains at least one auxiliary precipitating additive a represented by formula (I):

where the substituents R ₁ and R ₂ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl or C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted ; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, or C ₇ -C ₂₀ aralkyl, or substituted or unsubstituted;

where the auxiliary precipitating additive a represented by formula (I) contains the isomers represented by formula (I-a) and/or formula (I-b) in an amount of more than 80 wt%, preferably more than 90 wt%, more preferably more than 95 % wt. and even more preferably more than 98% of the mass. based on the total weight of the auxiliary precipitating additive a represented by formula (I); and

3) applying the titanium-based active component to magnesium-containing solid particles to form a solid catalyst component.

The first exemplary process that can be used to prepare the olefin polymerization catalyst component of the present invention includes the following steps:

(1) reacting a magnesium compound with an alcohol compound, optionally in the presence of an inert hydrocarbon solvent, to obtain a homogeneous solution of the (magnesium compound)-alcohol adduct;

(2) reacting the (magnesium compound)-alcohol adduct solution from step (1) with the first titanium compound in the presence of a precipitant to obtain a mixture containing a solid precipitate, wherein the precipitant contains at least one precipitant a represented by formula (I):

where the substituents R ₁ and R ₂ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted ; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and C ₇ -C ₂₀ aralkyl, or substituted or unsubstituted;

where the auxiliary precipitating additive a represented by formula (I) contains the isomers represented by formula (I-a) and/or formula (I-b) in an amount of more than 80 wt%, preferably more than 90 wt%, more preferably more than 95 % wt. and even more preferably more than 98% of the mass. based on the total mass of the auxiliary precipitating additive a represented by formula (I):

(3) contacting the mixture from step (2) with a first internal electron donor compound to form a slurry;

(4) subjecting the slurry from step (3) to a (solid)/liquid separation to obtain a first solid intermediate, and contacting the resulting first solid intermediate with a second titanium compound and optionally a second internal electron donor compound to form a mixture;

(5) subjecting the mixture from step (4) to a (solid)/liquid separation to obtain a second solid intermediate, and treating the second solid intermediate with a third titanium compound to form a solid catalyst component; and

(6) isolation of the solid catalyst component.

The first, second and third titanium compounds used in the first method may be the same or different, and the first and second internal electron donors may be the same or different.

In a specific embodiment, the first method includes the following steps: (1) carrying out a first reaction of contacting a magnesium compound and an alcohol compound in an inert hydrocarbon solvent to obtain a homogeneous solution of an adduct (magnesium compound)-alcohol; (2) carrying out a second reaction of contacting the homogeneous solution from step (1) and the first titanium compound in the presence of an auxiliary precipitating additive to obtain a mixture containing a solid precipitate; (3) carrying out a third reaction of contacting the mixture from step (2) and the first internal electron donor compound to obtain a suspension; (4) subjecting the slurry from step (3) to a (solid)/liquid separation, carrying out a fourth reaction of contacting the obtained solid intermediate with a second titanium compound and a second internal electron donor compound, and then carrying out a (solid)/liquid separation to obtain a solid intermediate ; (5) carrying out a fifth reaction of contacting the solid intermediate from step (4) with a third titanium compound, followed by a (solid)/liquid separation and subjecting the resulting solid product to washing with an inert solvent and drying to obtain a finished solid catalyst component.

The alcohol compound used in the first method may be one or more compounds selected from linear or branched C ₁ -C ₁₀ aliphatic alcohol, C ₃ -C ₁₂ alicyclic alcohol, C ₆ -C ₂₀ aryl alcohol and C ₇ -C ₂₀ -aralkyl alcohol. Examples of the alcohol compound include, but are not limited to, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, isopentanol, n-hexanol, isohexanol, 2-ethylhexanol, benzyl alcohol, phenylethanol, cyclopentanol , methylcyclopentanol, cyclohexanol and mixtures thereof, preferably 2-ethylhexanol.

In the first method, with respect to one mol of magnesium, the amount of alcohol compound used is in the range of 2 to 4 mol and preferably 2.5 to 3.5 mol, and the total amount of titanium compounds used in steps (2), (4) and (5 ), is in the range from 1 to 40 mol and preferably from 1.5 to 35 mol.

The process conditions used in the first method include: in step (1), the reaction/first contacting reaction temperature is in the range of 30 to 150°C and preferably 60 to 140°C, and the reaction time is in the range of 0.5 to 10 hours and preferably from 0.5 to 6 hours; in step (2), the reaction/second contacting reaction temperature is in the range of -40 to 0°C and preferably -30 to -20°C, and the reaction time is in the range of 3 to 5 hours and preferably 3.5 to 4.5 hour; in step (3), the reaction temperature/third contacting reaction is in the range of 20 to 120°C and preferably 70 to 110°C, and the reaction time is in the range of 0.5 to 6 hours and preferably 1 to 4 hours; in step (4), the reaction temperature/quadruple contacting reaction is in the range of 50 to 150°C and preferably 80 to 120°C, and the reaction time is in the range of 1 to 6 hours and preferably 2.5 to 4.5 hour; in step (5), the treatment/reaction temperature of the fifth contact is in the range of 50 to 150°C and preferably 80 to 120°C, and the time is in the range of 1 to 6 hours and preferably 2.5 to 4.5 hours .

More detailed information on the above method can be found in document CN 106317275, the full description of which is incorporated herein by reference.

A second exemplary process that can be used to prepare the olefin polymerization catalyst component of the present invention includes the following steps:

(1) contacting a magnesium compound with an organic epoxy compound and an organophosphorus compound, optionally in the presence of an inert hydrocarbon solvent, to form a homogeneous solution of the magnesium compound;

(2) reacting the solution of the magnesium compound from step (1) with the first titanium compound and the first internal electron donor compound in the presence of a precipitating aid to obtain a slurry containing a solid precipitate, wherein the precipitating aid contains at least one precipitating aid a represented by formula (I):

where the substituents R ₁ and R ₂ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted or unsubstituted ; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl, and C ₇ -C ₂₀ aralkyl, or substituted or unsubstituted;

where the auxiliary precipitating additive a represented by formula (I) contains the isomers represented by formula (I-a) and/or formula (I-b) in an amount of more than 80 wt%, preferably more than 90 wt%, more preferably more than 95 % wt. and even more preferably more than 98% of the mass. based on the total mass of the auxiliary precipitating additive a represented by formula (I):

(3) subjecting the slurry from step (2) to a (solid)/liquid separation to obtain a first solid intermediate and contacting the first solid intermediate with a second titanium compound and optionally a second internal electron donor compound to form a mixture;

(4) subjecting the mixture from step (3) to a (solid)/liquid separation to obtain a second solid intermediate;

(5) treating the second solid intermediate with a third titanium compound 1-4 times to form a solid catalyst component; and

(6) isolation of the solid catalyst component.

The first, second and third titanium compounds used in the second method may be the same or different, and the first and second internal electron donors may be the same or different.

In a specific embodiment, the second method includes the following steps: (1) carrying out a first reaction of contacting a magnesium compound with an organic epoxy compound and an organophosphorus compound in an inert hydrocarbon solvent to obtain a homogeneous solution of the magnesium compound; (2) carrying out a second reaction of contacting the homogeneous solution from step (1) with the first titanium compound and the first internal electron donor compound in the presence of an auxiliary precipitating additive to obtain a suspension containing a solid precipitate; (3) subjecting the solid-containing slurry from step (2) to a (solid)/liquid separation to obtain a solid intermediate A, and carrying out a third reaction of contacting the solid intermediate A with a second titanium compound and a second internal electron donor compound, followed by separation ( solid)/liquid to give a solid intermediate B; (4) carrying out a fourth reaction of contacting solid intermediate B from step (3) with a third titanium compound, followed by (solid)/liquid separation to obtain solid intermediate C; treating the solid intermediate C with a third titanium compound 1-3 times, followed by a (solid)/liquid separation and subjecting the resulting solid product to washing with an inert solvent and drying to obtain a finished solid catalyst component.

The organic epoxy compound used in the second method may be at least one selected from epoxyethane, epoxypropane, epoxybutane, vinylepoxyethane, butadiene dioxide, epoxychloropropane, methyl glycidyl ether and diglycidyl ether, and is preferably epoxychloropropane.

The organophosphorus compound used in the second method may be at least a compound selected from hydrocarbyl esters or halogenated hydrocarbyl esters of phosphoric or phosphorous acid, preferably at least a compound selected from trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate , trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite, and is more preferably tributyl phosphate.

In the second method, with respect to one mol of magnesium, the amount of organic epoxy compound used is in the range of 0.2 to 10 mol and preferably 0.5 to 4.0 mol; the amount of organophosphorus compound used is in the range of 0.1 to 3.0 mol and preferably 0.3 to 1.5 mol; and the total amount of titanium compounds used is in the range of 3 to 40 mol and preferably 5 to 35 mol.

The process conditions used in the second method include: in step (1), the reaction/first contacting reaction temperature is in the range of 0 to 80°C and preferably 10 to 60°C, and the reaction time is in the range of 0.5 to 10 hours and preferably from 0.5 to 6 hours; in step (2), the reaction/second contacting reaction temperature is in the range of -40 to 0°C and preferably -30 to -20°C, and the reaction time is in the range of 3 to 5 hours and preferably 3.5 to 4.5 hour; in step (3), the reaction/third contacting reaction temperature is in the range of 50 to 150°C and preferably 80 to 120°C, and the reaction time is in the range of 1 to 6 hours and preferably 2.5 to 4.5 hour; in step (5), the treatment/quaternary contacting reaction temperature is in the range of 50 to 150°C, and preferably 80 to 120°C, and the time is in the range of 1 to 6 hours, preferably 2.5 to 4.5 hour.

More detailed information on the method described above can be found in document CN 101864009, the full description of which is incorporated herein by reference.

Any internal electron donor compound known in the art that can impart the desired properties to the polyolefin catalyst component can be used in the processes of the present invention as an internal electron donor or first and/or second internal electron donor. In some embodiments of the methods of the present invention, at least one compound represented by formula (III), formula (III'), or formula (III") is used, which are described above as the first and/or second internal electron donor. The first and second internal electron donors may be the same or different.

In the above first and second production methods, the molar ratio of the first internal electron donor compound to the second internal electron donor compound may be (0.1-10):1, preferably (0.2-5):1, and more preferably (0.2-1 ):one.

Examples of the magnesium compound that can be used in the first and second production methods described above include one or more of the compounds represented by formula (IV), hydrates represented by formula (V), and alcohol adducts represented by formula (VI):

MgR ₈ R ₉ (IV)

MgR ₈ R ₉ qH ₂ O (V)

MgR ₈ R ₉ pR ₀ OH (VI)

where the substituents R ₈ and R ₉ are each independently selected from the group consisting of halogen, C ₁ -C ₅ -hydrocarbyl, C ₁ -C ₅ -hydrocarbyl-oxy group, C ₁ -C ₅ -halohydrocarbyl and C ₁ -C ₅ - halohydrocarbyloxy group; preferably the substituents R ₈ and R ₉ are each independently fluorine, chlorine, bromine or iodine, preferably chlorine or bromine,

where in the formula (V) q has a value from 0.1 to 6.0 and preferably from 2.0 to 3.5;

where in the formula (VI) substituent R ₀ represents C ₁ -C ₁₈ -hydrocarbyl, preferably C ₁ -C ₅ -alkyl; and p is from 0.1 to 6.0 and preferably from 2.0 to 3.5.

In some preferred embodiments, the magnesium compound is at least a compound selected from magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride.

In some more preferred embodiments, the magnesium compound is anhydrous magnesium dichloride.

The inert hydrocarbon solvent may be any hydrocarbon solvent commonly used in the art that does not chemically react with the magnesium compound, such as at least one of alkanes, cycloalkanes and aromatics, preferably at least one of the numbers of decane, benzene, toluene and xylene, and more preferably toluene.

The titanium compound useful in the methods of the present invention includes at least a compound represented by formula (VII):

TiX _m (OR ₁₀ ) _4-m (VII),

where Deputy R ₁₀ represents C ₁ -C ₂₀ -hydrocarbyl, preferably C ₁ -C ₅ -alkyl; X is chlorine, bromine, or iodine; and m is 1, 2, 3, or 4.

In some preferred embodiments, the titanium compound is at least one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetraalkoxytitanium, alkoxytitanium trihalide, dialkoxytitanium dihalide, and trialkoxytitanium halide.

In some more preferred embodiments, the titanium compound is titanium tetrachloride.

In a third aspect, the present invention provides an olefin polymerization catalyst comprising:

1) a catalyst component as described in the first aspect of the present invention;

2) alkyl aluminum compound; and

3) optionally an external electron donor compound.

Preferably the molar ratio of component 1) to component 2) in terms of (titanium:aluminum) is (5-5000):1, preferably (20-1000):1 and more preferably (50-500):1.

The alkylaluminum compound of component 2) may be one or more different alkylaluminum compounds which can be used as a cocatalyst in Ziegler-Natta type catalysts commonly used in the field of olefin polymerization.

In some preferred embodiments, the alkylaluminum compound of component 2) comprises at least one compound represented by formula (VIII):

AlR'_n'X'_3-n' (VIII),

where Deputy R' is selected from H, C ₁ -C ₂₀ -alkyl and C ₆ -C ₂₀ -aryl, X' represents halogen, and 1≤n'≤3.

In some more preferred embodiments, the alkyl aluminum compound is at least one selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, monohydrodiethylaluminum, monohydrodiisobutyl aluminum, diethylaluminum chloride, diisobutyl chloride. aluminium, sesquiethylaluminum chloride and ethylaluminum dichloride.

According to the present invention, there is no particular limitation on the type and amount of the external electron donor compound. The external electron donor may be one or more of the various compounds commonly used in the field of olefin polymerization, which may be used as the external electron donor in a Ziegler-Natta catalyst. When used, the external electron donor compound is used in an amount conventional in the art.

In some preferred embodiments of the invention, the molar ratio of component 3) to component 2) in terms of (silicon:aluminum) is 1:(0.1-500), preferably 1:(1-300) and more preferably 1:(3-100 ).

In some preferred embodiments, the external electron donor compound comprises at least a compound represented by formula (IX):

R ¹ ''_m'' R ² ''_n'' Si(OR ^3'' ) _4-m''-n'' (IX),

where the substituents R ¹ '' and R ² '' are each independently selected from H, halogen, C ₁ -C ₂₀ -alkyl or haloalkyl, C ₃ -C ₂₀ -cycloalkyl and C ₆ -C ₂₀ -aryl; Deputy R ³ '' is selected from C ₁ -C ₂₀ -alkyl or halo-alkyl, C ₃ -C ₂₀ -cycloalkyl and C ₆ -C ₂₀ -aryl; m'' and n'' are independently integers from 0 to 3, and m''+n''<4.

In some more preferred embodiments, the external electron donor compound is at least a compound selected from trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane, triethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane -tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butylisobutyldimethoxysilane, tert-butyl-second-butyl-dimethoxysilane, tert-butylpentyldimethoxysilane, tert-butyldimethoxysilane, tert-butylpentyldimethoxysilane, tert-butyldimethoxysilane, tert-butyldimethoxysilane, -butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butyldecyldimethoxysilane, methyl tert-butyldimethoxysilane, cyclohexylmethyldimethoxysilane ана, циклогексилэтилдиметоксисилана, циклогексилпропилдиметоксисилана, циклогексилизобутилдиметокси-силана, дициклогексилдиметоксисилана, циклогексил-трет-бутил-диметоксисилана, циклопентилметилдиметоксисилана, циклопентил-этилдиметоксисилана, циклопентилпропилдиметоксисилана, циклопентил-трет-бутилдиметоксисилана, дициклопентилдиметокси-силана, циклопентилциклогексилдиметоксисилана, ди(2-метил-циклопентил)диметоксисилана, дифенилдиметоксисилана, дифенил-диэтоксисилана, фенилтриэтоксисилана, метилтриметоксисилана, метилтриэтоксисилана, этилтриметоксисилана, этилтриэтоксисилана, пропилтриметоксисилана, изопропилтриметоксисилана, бутил-триметоксисилана, бутилтриэтоксисилана, изобутилтриметокси-силана, трет-бутилтриметоксисилана, втор-бутилтриметоксисилана, пентилтриметоксисилана, изопентилтриметоксисилана, циклопентил-триметоксисилана, циклогексилтриметоксисилана, дифенилдиметокси- silane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, vinyl trimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiperidyl-2-tert-butyldimethoxysilane, 1,1,1-trifluoro-2-propyl-2-ethylpiperidyldimethoxysilane and 1,1,1-trifluoro-2-propylmethyldimethoxysilane.

In some other preferred embodiments of the present invention, the external electron donor compound is at least a compound selected from dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, methyl t-butyldimethoxysilane, and tetramethoxysilane.

In a fourth aspect, the present invention provides a prepolymerized olefin polymerization catalyst comprising a prepolymer obtained by carrying out prepolymerization using a catalyst component as described in the first aspect of the present invention or a catalyst as described in the third aspect of the present invention and an olefin, wherein the prepolymer has a prepolymerization factor of 5 to 1000 g polyolefin/g catalytic component, preferably 10 to 500 g polyolefin/g catalytic component. Preferably, the olefin used in the prepolymerization is ethylene or propylene.

In some embodiments of the invention, the prepolymerization temperature is from -20 to 80°C, and preferably from 10 to 50°C.

In a fifth aspect, the present invention provides an olefin polymerization process, wherein the olefin is polymerized by the action of a catalyst component as described in the first aspect of the present invention, a catalyst as described in the third aspect of the present invention, or a prepolymerized catalyst as described in the fourth aspect of the present invention. The olefin has the formula CH ₂ =CHR where R is hydrogen, C ₁ -C ₆ alkyl or phenyl.

The olefin polymerization process of the present invention can be used to homopolymerize olefins as well as to copolymerize multiple olefins. The olefin is at least an olefin selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexane, 1-octene and 4-methyl-1-pentene. Preferably, the olefin may be at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene. Preferably the olefin is propylene.

In the production of polyolefins, the catalyst components of the present invention, i.e., the catalyst component of the present invention, the alkyl aluminum compound as a co-catalyst, and an optional external electron donor compound may be contacted with each other prior to contacting the olefin monomer (in this is referred to in the industry as "pre-contacting" or "pre-complexing"), and it is also possible to separately add the three components to the polymerization reactor to carry out the polymerization reaction, i.e., no "pre-contacting" is carried out. In the olefin polymerization process of the present invention, it is preferable to carry out "pre-contacting" the components of the olefin polymerization catalyst. The "pre-contact" time is 0.1-30 minutes and preferably 1-10 minutes, and the "pre-contact" temperature is -20 to 80°C and preferably 10 to 50°C.

In some embodiments, the catalyst of the present invention is first prepolymerized to some extent in the presence of a small amount of olefin monomer to form a prepolymerized catalyst, and then the prepolymerized catalyst is further contacted with an olefin monomer to form an olefin polymer. In the industry, this technology is referred to as the "prepolymerization" process, and it helps to improve the polymerization activity of the catalyst and increase the bulk density of the polymer. In the olefin polymerization process of the present invention, a "prepolymerization" process may or may not be used. Preferably, a "prepolymerization" process is used.

In the olefin polymerization process of the present invention, the polymerization conditions may be conventional conditions in the art.

Without wishing to be bound by any particular theory, it is believed that the co-precipitant a used in the present invention, that is, the diol ester having a content of isomers with a specific optical configuration (R, R-configuration isomers and/or S, S-configuration ) greater than 80% can be easily removed from the solid catalyst component compared to the conventional corresponding commercial diol ester (typically having an R, R-configuration and/or S, S-configuration isomer content of about 40%). Therefore, the content of residual precipitant additive in the solid catalyst component obtained according to the method of the present invention is relatively low and does not interfere with the function of the internal electron donor component.

Moreover, it has been found that a precipitant a, i.e., a diol ester having a content of isomers with a certain optical configuration (R, R-configuration and/or S, S-configuration isomers) of more than 80% can function well, so that the particle shape of the obtained catalyst component becomes better.

Examples

To make the present invention easier to understand, it is described in detail with reference to examples, which are provided for illustrative purposes only and do not limit the scope of the present invention.

The following test methods are used in the present invention.

(1) Purity and diastereomeric ratio of precipitating aid a, diol ester: determined using an Acquity UPLC high performance liquid chromatograph from Waters Company, USA.

(2) Auxiliary precipitant compound configuration: determined using a Brukerdmx nuclear magnetic resonance instrument (300 MHz, CDCl ₃ solvent, TCM internal standard (TMS) and measurement temperature 300°K).

(3) Diol ester content of the catalyst component: determined using an Acquity UPLC high performance liquid chromatograph from Waters Company, USA.

(4) Polymer melt flow index (MFR (MI)): determined according to GB/T3682-2000.

(5) Stereoregularity index (TS(II)) of propylene polymer: determined by the heptane extraction method in which 2 g of a sample of dry polymer is extracted with boiling heptane in an extractor for 6 hours, then the remaining substance is dried to constant weight and the weight ratio (g) of the remaining polymer to 2 g is taken as an indicator of stereoregularity.

(6) Calculation of activity (Ac): catalyst activity = (mass of polyolefin produced/(mass of solid catalyst component) (kg/g).

(7) Measurement of Bulk Density (BD)): The obtained polymer powder is dropped freely from a funnel from a height of 10 cm into a 100 ml container, and the polymer powder in the container is weighed (M in g), then the bulk density M/100 g/ is calculated. cm ³ .

(8) Polymer Molecular Weight Distribution, MWD (MWD) (MWD=Mw/Mn): measured at 150° C. using a PL-GPC220 instrument with trichlorobenzene as solvent (polystyrene standard, flow rate 1.0 ml/min, column 3×Plgel 10 μm MlxED-B 300×7.5 nm).

In the present invention, an ultra high performance liquid chromatograph is used, and the separation conditions for the liquid chromatograph are adjusted so that R, R-configuration and S, S-configuration diol esters and R, S-configuration diol esters have different retention times. As a result, diol esters with R, R and S, S configurations are distinguished from diol esters with R, S configuration. The specific separation conditions are as follows:

(1) Column: ACQUITY UPLC BEH Shield RP18 (100 mm×2.1 mm, 1.7 µm);

(2) Column temperature: 35°C;

(3) Mobile phase: 75% methanol, 25% ultrapure water;

(4) Flow rate: 0.3ml/min;

(5) PDA detector detection wavelength: 229nm.

Under such conditions, the retention time of R, R and S, S diol esters is the same and relatively short, and the retention time of R, S diol esters is relatively long. However, diastereomer configurations can be determined based on ¹ H NMR signals.

Receiving Example

Methods for synthesizing the precipitating aid a represented by formula (I) of the diol ester type compounds used in the examples are as follows.

Compound 1: 2,4-pentylenedibenzoate (R, R-config + S, S-config): R, S-config=99.1:0.16

(1) Preparation of a mixture of R, R-2,4-pentylene glycol and S, S-2,4-pentylene glycol

Add 500 g of 2,4-pentylene glycol to 1200 ml of anhydrous diethyl ether, mix well, cool to -50°C and incubate from 1 to 1.5 hours. The reaction mixture is rapidly filtered, the precipitated solids are collected, and the solids thus obtained are then recrystallized with diethyl ether at -20° C. three times to give the title product (184.4 g, 99.4% pure (GC)).

¹ H NMR spectrum (CDCl ₃ /TMS, 300 MHz) δ (ppm): 1.202-1.258 (m, 6H, -CH(OH)CH ₃ ), 1.536-1.632 (m, 2H, -CH ₂ CH (OH)CH ₃ ), 4.048-4.211 (m, 2H, rac-CH(OH)CH ₃ ).

(2) Synthesis of 2,4-pentylenedibenzoate

259.3 g of benzoyl chloride in 500 ml of toluene are added to give a solution of benzoyl chloride. 80 g of the mixture of R, R-2,4-pentylene glycol and S, S-2,4-pentylene glycol prepared above, 152.3 g of anhydrous pyridine and 4.0 g of 4-dimethylaminopyridine are added to 100 ml of toluene, after complete dissolution of the solid substances, the resulting solution is added dropwise to the benzoyl chloride solution and the temperature is maintained below 50°C. Upon completion of the dropwise addition, the temperature was raised to 80° C. over 4 hours, then the temperature was raised again to reflux for 8 hours. After completion of the reaction, the reaction mixture is cooled to room temperature, filtered, part of the toluene is removed from the filtrate by rotary evaporation, and the remaining filtrate is vigorously stirred and washed to pH=12 with the same amount of 10% sodium carbonate solution. Liquid separation is carried out and the organic phase is washed with saturated ammonium chloride solution until pH=6-7. After separation, the organic phase was dried over anhydrous magnesium sulfate, filtered, rotary dried and distilled under reduced pressure to give a crude product. The crude product is recrystallized using n-hexane at -20° C. to give the desired product (142.7 g, 99.26% purity (LC)), in which the content of the R, R-configuration and S, S-configuration isomers is 99.1%, and the diastereomeric ratio (R, R-configuration +S, S-configuration): R, S-configuration is 99.1:0.16.

¹ H NMR spectrum (CDCl ₃ /TMS, 300 MHz) δ (ppm): 1.397-1.418 (d, 6H, -CH(OCO)CH ₃ ), 2.074-2.116 (m, 2H, -CH ₂ CH (OCO)CH ₃ ), 5.287-5.350 (m, 2H, -CH ₂ CH(OCO)CH ₃ ), 7.253-7.987 (m, 5H, -C ₆ H ₅ ).

Compound 2: 3,5-heptylenedibenzoate (R, R-configuration+S, S-configuration): R, S-configuration=96.3:1.0

(1) Preparation of a mixture of R, R-3,5-heptylene glycol and S, S-3,5-heptylene glycol

A mixture of R,R-3,5-heptylene glycol and S,S-3,5-heptylene glycol (181.3 g, having a purity of 99.6% (GC)) is prepared using a method similar to step (1) in the synthesis of the compound 1, but 2,4-pentylene glycol is replaced by 3,5-heptylene glycol.

¹ H NMR spectrum (CDCl ₃ /TMS, 300 MHz) δ (ppm): 0.923-0.972 (m, 6H, -CH(OH)CH ₂ CH ₃ ), 1.476-1.589 (m, 4H, -CH ₂ CH(OH)CH ₂ CH ₃ ), 1.607-1.627 (m, 2H, -CH ₂ CH(OH)CH ₂ CH ₃ ), 3.815-3.909 (m, 2H, rac-CH(OH)CH ₃ ).

(2) Synthesis of 3,5-heptylenedibenzoate

3,5-heptylenedibenzoate (142.7 g, 97.3% purity (LC)) was synthesized using a method similar to step (2) in the synthesis of compound 1, but a mixture of R, R-2,4-pentylene glycol and S, S -2,4-pentylene glycol is replaced with the mixture of R, R-3,5-heptylene glycol and S, S-3,5-heptylene glycol described above. 3,5-heptylenedibenzoate has an isomer content of R, R-configuration and S, S-configuration of 96.3%, and the diastereomeric ratio (R, R-configuration +S, S-configuration):R, S-configuration is 96.3 :1.0.

¹ H NMR spectrum (CDCl ₃ /TMS, 300 MHz) δ (ppm): 0.933-0.983 (d, 6H, -CH(OCO)CH ₂ CH ₃ ), 1.737-1.785 (m, 4H, -CH ₂ CH(OCO)CH ₂ CH ₃ ), 2.062-2.103 (m, 2H, -CH ₂ CH(OCO)CH ₂ CH ₃ ), 5.194-5.275 (m, 2H, -CH ₂ CH(OCO)CH ₂ CH ₃ ), 7.243-7.981 (m, 5H, -C ₆ H ₅ ).

Compound 3: 2,4-pentylenedibenzoate (R, R-config + S, S-config): R, S-config=37:60

This compound is obtained commercially and is used as received. This compound has an isomer content of R, R-configuration and S, S-configuration of 37%, and the diastereomeric ratio (R, R-configuration +S, S-configuration): R, S-configuration is 37:60.

Compound 4: 3,5-heptylenedibenzoate (R, R-config +S, S-config): R, S-config =35:61

This compound is obtained commercially and is used as received. This compound has an isomer content of R, R-configuration and S, S-configuration of 35%, and the diastereomeric ratio (R, R-configuration +S, S-configuration): R, S-configuration is 35:61.

Example 1

I. Preparation of the catalyst component

(1) Preparation of (magnesium dichloride)-alcohol adduct solution:

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 1400 ml of isooctanol, 1400 ml of toluene and 350 g of anhydrous magnesium dichloride are charged successively. The contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 115°C for 3.5 hours until the solids are completely dissolved to form a homogeneous solution of the adduct (magnesium dichloride)-alcohol. 52.5 ml of tetrabutyl titanate are added and the contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 110° C. for 1.5 hours. Then 1960 ml of toluene are added and the temperature is kept constant for half an hour. Then 140 ml of toluene and 45 g of compound 1 are added and the mixture is allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 50°C for 0.5 hour, then cooled to room temperature, an adduct solution (magnesium dichloride) is obtained - alcohol containing an auxiliary precipitating additive.

(2) Preparation of the catalyst component

The (magnesium dichloride)-alcohol adduct solution obtained above containing the precipitating aid was added dropwise over 3 hours to a reactor in which the air had been sufficiently replaced with nitrogen containing 4200 ml of titanium tetrachloride and 2800 ml of toluene. Upon completion of the dropwise addition, the contents were stirred at -25°C for complete reaction within 0.5 hour and then heated to 110°C for 6 hours. 35 g of 2-isopropyl-2-isopentyl-1,3-propylene glycol dimethyl ether and 100 ml of toluene are added and the temperature is maintained at 110° C. for 2 hours. The liquid is then filtered off to give a solid intermediate. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate, and the mixture is stirred at 80° C. for 1 hour, cooled to room temperature and filtered under reduced pressure. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 80° C. and 112 g of 2-isopropyl-2-isopentyl-1,3-propylene glycol dimethyl ether and 100 ml of toluene are added. After keeping at this temperature for 1 hour, the liquid is filtered off. 5600 ml of toluene and 1400 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 110° C., stirred for 1 hour and then the liquid is filtered off. The solid product thus obtained was washed 4 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 1.

II. Polymerization of propylene

The catalyst component 1 prepared above was used in the polymerization of propylene as follows.

To a 5 L autoclave after complete replacement of propylene gas phase, add at room temperature 5 ml of a solution of triethylaluminum in hexane (having a triethylaluminum concentration of 0.5 mmol/ml), 1 ml of a solution of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (having a CHMMS concentration of 0.10 mmol /ml), 10 ml of anhydrous hexane and 10 mg of solid catalyst component 1. The polymerization is carried out under two sets of conditions: (1) 4.5 standard liters of hydrogen gas and 2 liters of liquid propylene, 70°C, polymerization time 1 hour, and after stopping the stirring, the unpolymerized propylene monomer is removed and the resulting polymer is collected; (2) 1.0 standard liter of hydrogen gas and 2 L of liquid propylene, 70° C., polymerization time 2 hours, and after stopping stirring, unpolymerized propylene monomer is removed and the obtained polymer is collected. Polymerization data are shown in Table 1 below.

Example 2

Catalyst component 2 was prepared following the preparation procedure described in Example 1, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 1, except that Catalyst Component 1 was replaced with Catalyst Component 2. The polymerization results are shown in Table 1.

Example 3

I. Preparation of the catalyst component

(1) Preparation of magnesium dichloride solution

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 350 g of anhydrous magnesium dichloride, 4667 ml of toluene, 576 ml of epichlorohydrin and 649 ml of tributyl phosphate are charged successively at room temperature. The contents are heated to 55°C at a stirring speed of 1300 rpm and allowed to react for 3.0 hours until complete dissolution of the solids, get a homogeneous solution of magnesium chloride.

(2) Preparation of the catalyst component

The magnesium dichloride solution is cooled to -28°C and 4100 ml of titanium tetrachloride, 290 ml of toluene, 58 g of compound 1 and 36 g of 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether are added dropwise. Upon completion of the dropwise addition, the reaction mixture was stirred at -28°C for complete reaction within 1.0 hour and then heated to 80°C for 4.5 hours. After keeping at this temperature for 1.5 hours, the liquid is removed by pressure filtration and the residue is washed twice with 8750 ml of toluene for each time. 51 g of 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether and 6560 ml of toluene are added and the temperature is maintained at 80° C. for 1 hour. Then add 4375 ml of titanium tetrachloride and the mixture is heated to 110°C and stirred for 1 hour. The liquid is removed by pressure filtration and 4200 ml of toluene and 2800 ml of titanium tetrachloride are added. The mixture is stirred for 1 hour and the liquid is removed by pressure filtration. Then 4200 ml of toluene and 2800 ml of titanium tetrachloride are added and the mixture is stirred for 1 hour. After the liquid was removed by pressure filtration, the resulting solids were washed 5 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 3.

II. Polymerization of propylene

The catalyst component 3 prepared above was used in the polymerization of propylene as follows.

To a 5 L autoclave after complete replacement of propylene gas phase, add at room temperature 5 ml of a solution of triethylaluminum in hexane (having a triethylaluminum concentration of 0.5 mmol/ml), 1 ml of a solution of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (having a CHMMS concentration of 0.10 mmol /ml), 10 ml of anhydrous hexane and 10 mg of solid catalyst component 3. The polymerization is carried out under two sets of conditions: (1) 4.5 standard liters of hydrogen gas and 2 liters of liquid propylene, 70°C, polymerization time 1 hour, and after stopping the stirring, the unpolymerized propylene monomer is removed and the resulting polymer is collected; (2) 1.0 standard liter of hydrogen gas and 2 L of liquid propylene, 70° C., polymerization time 2 hours, and after stopping stirring, unpolymerized propylene monomer is removed and the obtained polymer is collected. Polymerization data are shown in Table 1 below.

Example 4

Catalyst component 4 was prepared following the preparation procedure described in Example 3, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 3, except that catalyst component 3 was replaced with catalyst component 4. The polymerization results are shown in Table 1.

Comparative Example 1

Catalyst component C1 was prepared following the preparation procedure described in Example 1, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 1, except that catalyst component 1 was replaced with catalyst component C1. The results of polymerization are presented in table 1.

Comparative Example 2

Catalyst component C2 was prepared following the preparation procedure described in Example 1, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in Example 1, except that catalyst component 1 was replaced with catalyst component C2. The results of polymerization are presented in table 1.

Comparative Example 3

Catalyst component C3 was prepared following the preparation procedure described in Example 3, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 3, except that catalyst component 3 was replaced with catalyst component C3. The results of polymerization are presented in table 1.

Comparative Example 4

Catalyst component C4 was prepared following the preparation procedure described in Example 3, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in Example 3, except that catalyst component 3 was replaced with catalyst component C4. The results of polymerization are presented in table 1.

Table 1 Catalyst Diol ether content
wt% A:B ^* Polymerization conditions Activity
kg PP/g cat OP
g/cm ³ PTR
g/10min PS
% MMR Example 1 0.16 0.08:0.09 4.5 l/1 hour 72.7 0.42 41.3 97.9 4.5 1.0 l/2 hour 84.7 0.42 2.84 99.8 Example 2 0.11 0.04:0.06 4.5 l/1 hour 74.6 0.44 44.6 98.0 4.6 1.0 l/2 hour 88.3 0.47 3.29 99.3 Example 3 0.17 4.5 l/1 hour 72.0 0.43 32.9 97.8 4.7 1.0 l/2 hour 85.1 0.43 3.16 99.3 Example 4 0.14 4.5 l/1 hour 74.7 0.43 38.1 97.9 4.6 1.0 l/2 hour 86.1 0.44 2.76 99.2 Ref. example 1 4.10 0.10:4.00 4.5 l/1 hour 70.5 0.42 46.6 97.8 6.9 1.0 l/2 hour 78.3 0.42 3.14 99.2 Ref. example 2 3.81 0.08:3.73 4.5 l/1 hour 71.6 0.43 42.7 97.8 6.7 1.0 l/2 hour 82.7 0.44 2.99 99.0 Ref. example 3 4.61 4.5 l/1 hour 70.6 0.44 31.4 97.2 6.8 1.0 l/2 hour 79.1 0.44 2.96 98.9 Ref. example 4 4.19 4.5 l/1 hour 71.1 0.43 35.9 97.4 6.6 1.0 l/2 hour 80.3 0.43 2.61 99.0

^* A:B=(R, R-configuration +S, S-configuration):(R, S-configuration)

From the data in Table 1, it can be seen that when R, R- and S, S-configuration diol ester compounds are used as a precipitating aid in the preparation of a catalyst component, the diol ester content as a precipitating aid in the resulting catalyst component is extremely low, but the catalyst component still retains high activity and stereoregularity, and the resulting polypropylene has a narrow molecular weight distribution. A good particle morphology of the polypropylene powder is observed, indicating that the particle morphology of the catalyst component is good.

Example 5

I. Preparation of the catalyst component

(1) Preparation of adduct solution (magnesium dichloride)-alcohol

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 1400 ml of isooctanol, 1400 ml of toluene and 350 g of anhydrous magnesium dichloride are charged successively. The contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 115°C for 3.5 hours until complete dissolution of the solids, get a homogeneous solution of the adduct (magnesium dichloride)-alcohol. 52.5 ml of tetrabutyl titanate are added and the contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 110° C. for 1.5 hours. Then 1960 ml of toluene are added and the temperature is kept constant for half an hour. Then 140 ml of toluene and 45 g of compound 1 are added and the mixture is allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 5°C for 0.5 hour, then cooled to room temperature, an adduct solution (magnesium dichloride) is obtained - alcohol containing an auxiliary precipitating additive.

(2) Preparation of the catalyst component

The (magnesium dichloride)-alcohol adduct solution prepared above containing the precipitating aid was added dropwise over 3 hours to a reactor in which the air had been sufficiently replaced with nitrogen containing 4200 ml of titanium tetrachloride and 2800 ml of toluene. Upon completion of the dropwise addition, the reaction mixture was stirred at -25°C for complete reaction within 0.5 hour and then heated to 110°C for 6 hours. 35 g of diethyl 2-cyano-2,3-diisopropyl-succinate and 100 ml of toluene are added and the temperature is maintained at 110° C. for 2 hours. The liquid is then filtered off to give a solid intermediate. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate, and the mixture is stirred at 80° C. for 1 hour, cooled to room temperature and filtered under reduced pressure. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 80° C. and 112 g of diethyl 2-cyano-2,3-diisopropylsuccinate and 100 ml of toluene are added thereto. After keeping at this temperature for 1 hour, the liquid is filtered off. 5600 ml of toluene and 1400 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 110° C. and stirred for 1 hour, then the liquid is filtered off. The resulting solid was washed 4 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 5.

II. Polymerization of propylene

The catalyst component 5 prepared above was used in the polymerization of propylene as follows.

To a 5 L autoclave after complete replacement of propylene gas phase, add at room temperature 5 ml of a solution of triethylaluminum in hexane (having a triethylaluminum concentration of 0.5 mmol/ml), 1 ml of a solution of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (having a CHMMS concentration of 0.10 mmol /ml), 10 ml of anhydrous hexane and 10 mg of solid catalyst component 5. The polymerization is carried out under two sets of conditions: (1) 4.5 standard liters of hydrogen gas and 2 liters of liquid propylene, 70°C, polymerization time 1 hour, and after stopping the stirring, the unpolymerized propylene monomer is removed and the resulting polymer is collected; (2) 1.0 standard liter of hydrogen gas and 2 L of liquid propylene, 70° C., polymerization time 2 hours, and after stopping stirring, unpolymerized propylene monomer is removed and the obtained polymer is collected. Polymerization data are presented in Table 2 below.

Example 6

Catalyst component 6 is prepared following the preparation procedure described in Example 5, except that in step (2) 35 g of diethyl 2-cyano-2,3-di-isopropyl succinate is replaced by 35 g of di-n-butyl phthalate (DNBP) .

Polymerization of propylene was carried out following the procedure described in Example 5, except that catalyst component 5 was replaced with catalyst component 6. The polymerization results are shown in Table 2.

Example 7

Catalyst component 7 was prepared following the preparation procedure described in Example 5, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 5, except that catalyst component 5 was replaced with catalyst component 7. The polymerization results are shown in Table 2.

Example 8

Catalyst component 8 was prepared following the preparation procedure described in Example 5, except that in step (1) compound 1 was replaced with compound 2 and in step (2) 35 g of diethyl 2-cyano-2,3-diisopropyl succinate was replaced with 35 g di-n-butyl phthalate (DNBP).

Polymerization of propylene was carried out following the procedure described in Example 5, except that catalyst component 5 was replaced with catalyst component 8. The polymerization results are shown in Table 2.

Example 9

I. Preparation of the catalyst component

(1) Preparation of magnesium dichloride solution

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 350 g of anhydrous magnesium dichloride, 4667 ml of toluene, 576 ml of epichlorohydrin and 649 ml of tributyl phosphate are charged successively at room temperature. The contents are heated to 55°C at a stirring speed of 1300 rpm and allowed to react for 3.0 hours until complete dissolution of the solids, get a homogeneous solution of magnesium chloride.

(2) Preparation of the catalyst component

The magnesium dichloride solution is cooled to -28°C and 4100 ml of titanium tetrachloride, 290 ml of toluene, 58 g of compound 1 and 36 g of diethyl 2-cyano-2,3-diisopropyl succinate are added dropwise to it. Upon completion of the dropwise addition, the reaction mixture was stirred at -28°C for complete reaction within 1.0 hour and then heated to 80°C for 4.5 hours. After holding at this temperature for 1.5 hours, the liquid is removed by pressure filtration and the remaining solids are washed twice with 8750 ml of toluene each time. 51 g of diethyl 2-cyano-2,3-diisopropyl succinate and 6560 ml of toluene are added and the temperature is maintained at 80° C. for 1 hour. Then add 4375 ml of titanium tetrachloride and the mixture is heated to 110°C and stirred for 1 hour. The liquid is removed by pressure filtration and 4200 ml of toluene and 2800 ml of titanium tetrachloride are added. The mixture is stirred for 1 hour, the liquid is removed by pressure filtration. Then 4200 ml of toluene and 2800 ml of titanium tetrachloride are added and the mixture is stirred for 1 hour. After the liquid was removed by pressure filtration, the resulting solids were washed 5 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 9.

II. Polymerization of propylene

The catalyst component 9 prepared above is used in the polymerization of propylene as follows.

To a 5 L autoclave after complete replacement of propylene gas phase, add at room temperature 5 ml of a solution of triethylaluminum in hexane (having a triethylaluminum concentration of 0.5 mmol/ml), 1 ml of a solution of cyclohexylmethyldimethoxysilane (CHMMS) in hexane (having a CHMMS concentration of 0.10 mmol /ml), 10 ml of anhydrous hexane and 10 mg of solid catalyst component 9. The polymerization is carried out under two sets of conditions: (1) 4.5 standard liters of hydrogen gas and 2 liters of liquid propylene, 70°C, polymerization time 1 hour, and after stopping the stirring, the unpolymerized propylene monomer is removed and the resulting polymer is collected; (2) 1.0 standard liter of hydrogen gas and 2 L of liquid propylene, 70° C., polymerization time 2 hours, and after stopping stirring, unpolymerized propylene monomer is removed and the obtained polymer is collected. Polymerization data are presented in Table 2 below.

Example 10

Catalyst component 10 is prepared following the preparation procedure described in Example 9, except that in step (2) 36 g of diethyl 2-cyano-2,3-diisopropyl succinate is replaced by 36 g of di-n-butyl phthalate (DNBP).

Polymerization of propylene was carried out following the procedure described in Example 9, except that catalyst component 9 was replaced with catalyst component 10. The polymerization results are shown in Table 2.

Example 11

Catalyst component 11 was prepared following the preparation procedure described in Example 9, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 9, except that catalyst component 9 was replaced with catalyst component 11. The polymerization results are shown in Table 2.

Example 12

Catalyst component 12 was prepared following the preparation procedure described in Example 9, except that in step (1) compound 1 was replaced with compound 2 and in step (2) 36 g of diethyl 2-cyano-2,3-diisopropyl succinate was replaced with 36 g di-n-butyl phthalate (DNBP).

Polymerization of propylene was carried out following the procedure described in Example 9, except that catalyst component 9 was replaced with catalyst component 12. The polymerization results are shown in Table 2.

Comparative Example 5

Catalyst component C5 was prepared following the preparation procedure described in Example 5, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 5, except that catalyst component 5 was replaced with catalyst component C5. The results of polymerization are presented in table 2.

Comparative Example 6

Catalyst component C6 was prepared following the preparation described in Example 6, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 6, except that catalyst component 6 was replaced with catalyst component C6. The results of polymerization are presented in table 2.

Comparative Example 7

Catalyst component C7 was prepared following the preparation procedure described in Example 7, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in Example 7, except that catalyst component 7 was replaced with catalyst component C7. The results of polymerization are presented in table 2.

Comparative Example 8

Catalyst component C8 was prepared following the preparation described in Example 8, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in Example 8, except that catalyst component 8 was replaced with catalyst component C8. The polymerization results are shown in Table 2 below.

Comparative Example 9

Catalyst component C9 was prepared following the preparation procedure described in Example 9, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 9, except that catalyst component 9 was replaced with catalyst component C9. The polymerization results are shown in Table 2 below.

Comparative Example 10

Catalyst component C10 was prepared following the preparation described in Example 10, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in Example 10, except that catalyst component 10 was replaced with catalyst component C10. The polymerization results are shown in Table 2 below.

Comparative Example 11

Catalyst component C11 was prepared following the preparation procedure described in Example 11, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in Example 11, except that catalyst component 11 was replaced with catalyst component C11. The polymerization results are shown in Table 2 below.

Comparative example12

Catalyst component C12 was prepared following the preparation described in Example 12, except that in step (1), compound 1 was replaced with compound 4.

Polymerization of propylene was carried out following the procedure described in example 12, except that the catalyst component 12 was replaced with a C12 catalyst component. The polymerization results are shown in Table 2 below.

table 2 Catalyst Diol ether content,
wt% A:B ^* Polymerization conditions Activity
kg PP/g cat OP
g/cm ³ PTR
g/10min PS
% MMR Example 5 0.17 0.08:0.09 4.5 l/1 hour 63.9 0.42 7.40 96.6 12.8 1.0 l /2 hour 72.8 0.42 0.94 97.6 Example 6 0.18 4.5 l /1 hour 71.4 0.42 9.06 96.7 11.9 1.0 l /2 hour 80.8 0.42 1.98 97.4 Example 7 0.17 0.08:0.09 4.5 l /1 hour 67.2 0.42 7.20 96.8 12.5 1.0 l /2 hour 76.4 0.42 0.92 97.7 Example 8 0.10 4.5 l /1 hour 74.3 0.42 8.89 97.0 11.8 1.0 l /2 hour 82.8 0.42 1.36 97.8 Example 9 0.18 0.06:0.12 4.5 l /1 hour 62.8 0.43 8.20 97.4 12.7 1.0 l /2 hour 76.2 0.43 0.98 98.1 Example 10 0.15 4.5 l /1 hour 66.4 0.43 9.52 97.4 11.6 1.0 l /2 hour 79.2 0.43 1.24 98.3 Example 11 0.11 0.04:0.07 4.5 l/1 hour 65.2 0.42 7.35 97.6 12.4 1.0 l/2 hour 78.2 0.43 0.98 98.4 Example 12 0.13 4.5 l/1 hour 65.5 0.43 7.17 97.6 11.5 1.0 l/2 hour 78.3 0.43 0.91 98.6 Ref. example 5 4.09 0.10:3.99 4.5 l/1 hour 60.4 0.41 8.30 96.0 10.6 1.0 l/2 hour 68.5 0.42 0.82 97.1 Ref. example 6 3.62 4.5 l/1 hour 70.5 0.42 9.64 96.2 10.3 1.0 l/2 hour 79.2 0.42 2.19 97.5 Ref. example 7 3.45 0.10:3.35 4.5 l/1 hour 68.4 0.41 8.25 95.7 10.7 1.0 l/2 hour 74.7 0.42 1.21 97.0 Ref. example 8 3.92 4.5 l/1 hour 71.7 0.42 9.11 96.7 10.2 1.0 l/2 hour 78.2 0.43 1.08 97.4 Ref. example 9 3.89 4.5 l/1 hour 60.1 0.44 7.31 97.4 10.8 1.0 l/2 hour 75.3 0.43 0.81 98.2 Ref. example 10 4.12 0.08:4.04 4.5 l/1 hour 64.5 0.43 8.13 97.2 10.0 1.0 l/2 hour 77.1 0.43 1.06 98.3 Ref. example 11 4.13 4.5 l/1 hour 63.4 0.43 8.21 96.8 10.5 1.0 l/2 hour 77.0 0.43 1.29 97.9 Ref. example 12 3.53 0.07:3.46 4.5 l/1 hour 63.7 0.42 8.94 97.3 10.0 1.0 l/2 hour 77.4 0.43 1.47 98.0

^* A:B=(R, R-configuration+S, S-configuration):(R, S-configuration)

From the data in Table 2, it can be seen that when R, R- and S, S-configuration diol ester compounds are used as a precipitant in the preparation of the catalyst component, the content of the precipitant, diol ester, in the finished catalyst component is extremely low, but the catalyst component still has high activity and stereospecificity, and the resulting polypropylene has a broad molecular weight distribution. A good particle morphology of the polypropylene powder is observed, indicating that the particle morphology of the catalyst component is good.

Example 13

I. Preparation of the catalyst component

(1) Preparation of adduct solution (magnesium dichloride)-alcohol

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 1400 ml of isooctanol, 1400 ml of toluene and 350 g of anhydrous magnesium dichloride are charged successively. The contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 115°C for 3.5 hours until complete dissolution of the solids, get a homogeneous solution of the adduct (magnesium dichloride)-alcohol. 52.5 ml of tetrabutyl titanate are added and the contents are allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 110° C. for 1.5 hours. Then 1960 ml of toluene are added and the temperature is kept constant for half an hour. Then 140 ml of toluene and 45 g of compound 1 are added and the mixture is allowed to react under conditions with a stirring speed of 1300 rpm and at a temperature of 50°C for 0.5 hour, then cooled to room temperature, an adduct solution (magnesium dichloride) is obtained - alcohol containing an auxiliary precipitating additive.

(2) Preparation of the catalyst component

The (magnesium dichloride)-alcohol adduct solution prepared above containing the precipitating aid was added dropwise over 3 hours to a reactor in which the air had been sufficiently replaced with nitrogen containing 4200 ml of titanium tetrachloride and 2800 ml of toluene. Upon completion of the dropwise addition, the reaction mixture was stirred at -25°C for complete reaction within 0.5 hour and then heated to 110°C for 6 hours. 35 g of di-n-butyl phthalate and 100 ml of toluene are added and the temperature is maintained at 110° C. for 2 hours. The liquid is then filtered off to give a solid intermediate. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate, and the mixture is stirred at 80° C. for 1 hour, cooled to room temperature and filtered under reduced pressure. 6300 ml of toluene and 700 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 80° C., and 112 g of di-n-butyl phthalate and 100 ml of toluene are added thereto. After keeping at this temperature for 1 hour, the liquid is filtered off. 5600 ml of toluene and 1400 ml of titanium tetrachloride are added to the solid intermediate thus obtained, the mixture is heated to 110° C. and stirred for 1 hour, and then the liquid is filtered off. The solid product thus obtained was washed 4 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 13.

II. Polymerization of propylene

Polymerization of propylene was carried out using the catalyst component 13 prepared above, following the procedure described in Example 1. The polymerization results are shown in Table 3 below.

III. Preparation of impact-resistant copolymer polypropylene

The polymerization is carried out on a horizontal pilot plant for gas-phase polypropylene. The polymerization reactors are two successive horizontal stirred reactors, and the polymerization method is as follows.

Catalyst component 13, triethylaluminum and isobutyldimethoxysilane under the propylene carrier action are continuously added from the front of the first stirred tank to the horizontal stirred reactor and the polymerization is carried out under gas phase conditions to form a polypropylene homopolymer, the heat of reaction being removed by evaporation of the propylene spray. The resulting polymer is discharged from the end of the vessel with stirring. The catalyst and polymer move in the reactor in a manner close to plug flow. The polymerization temperature is 66° C. or the target temperature, and the reaction pressure is 2.3 MPa.

The homopolypropylene is discharged from the first reactor and transferred to the second horizontal stirred reactor via a transfer device installed between the two reactors. The polymer enters from the front end of the second stirred tank and the polymerization is carried out with the introduction of ethylene to produce high impact copolymer polypropylene, the heat of reaction being removed by evaporation of the sprayed propylene. During the polymerization, the molar ratio of ethylene to propylene is maintained at the level of 0.38-0.40. The resulting polymer is discharged from the end of the vessel with stirring. The catalyst and polymer move in the reactor in a manner close to plug flow. The polymerization temperature is 66° set temperature, and the reaction pressure is 2.2 MPa. The polymer obtained from this reaction is discharged and deactivated with wet nitrogen to obtain an impact-resistant copolymer polypropylene. Polymerization data are presented in Table 4.

Example 14

Catalyst component 14 was prepared following the preparation described in Example 13, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 1, except that Catalyst Component 1 was replaced with Catalyst Component 14. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component 14. The polymerization results are shown in Table 4 below.

Example 15

Catalyst component 15 was prepared following the preparation procedure described in Example 13, except that in step (1) compound 1 was replaced with compound 2 and in step (2) di-n-butyl phthalate (DNBP) was replaced with di-isobutyl phthalate (DIBP) .

Polymerization of propylene was carried out following the procedure described in Example 1, except that Catalyst Component 1 was replaced with Catalyst Component 15. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component 15. The polymerization results are shown in Table 4.

Example 16

I. Preparation of the catalyst component

(1) Preparation of magnesium dichloride solution

Into a reactor in which the air has been repeatedly replaced with high purity nitrogen, 350 g of anhydrous magnesium dichloride, 4667 ml of toluene, 576 ml of epichlorohydrin and 649 ml of tributyl phosphate are charged successively at room temperature. The contents are heated to 55°C at a stirring speed of 1300 rpm and allowed to react for 3.0 hours until complete dissolution of the solids, get a homogeneous solution of magnesium chloride.

(2) Preparation of the catalyst component

The magnesium dichloride solution is cooled to -28°C and 4100 ml of titanium tetrachloride, 290 ml of toluene, 58 g of compound 1 and 36 g of di-n-butyl phthalate are added dropwise. Upon completion of the dropwise addition, the reaction mixture was stirred at -28°C for complete reaction within 1.0 hour and then heated to 80°C for 4.5 hours. After holding at this temperature for 1.5 hours, the liquid is removed by pressure filtration and the remaining solids are washed twice with 8750 ml of toluene each time. 51 g of di-n-butyl phthalate and 6560 ml of toluene are added and the temperature is maintained at 80° C. for 1 hour. Then add 4375 ml of titanium tetrachloride and the mixture is heated to 110°C and stirred for 1 hour. The liquid is removed by pressure filtration and 4200 ml of toluene and 2800 ml of titanium tetrachloride are added. The mixture is stirred for 1 hour and the liquid is removed by pressure filtration. Then 4200 ml of toluene and 2800 ml of titanium tetrachloride are added and the mixture is stirred for 1 hour. After the liquid was removed by pressure filtration, the resulting solids were washed 5 times with 6000 ml of hexane and dried to give olefin polymerization catalyst component 16.

II. Polymerization of propylene

Polymerization of propylene was carried out using the catalyst component 16 prepared above, following the procedure described in Example 1. The polymerization results are shown in Table 3 below.

III. Preparation of impact-resistant copolymer polypropylene

High impact copolymer polypropylene was prepared using the catalyst component 16 prepared above, following the procedure described in Example 13. The polymerization results are shown in Table 4.

Example 17

Catalyst component 17 was prepared following the preparation procedure described in Example 16, except that in step (1), compound 1 was replaced with compound 2.

Polymerization of propylene was carried out following the procedure described in Example 1, except that Catalyst Component 1 was replaced with Catalyst Component 17. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component 17. The polymerization results are shown in Table 4 below.

Example 18

Catalyst component 18 is prepared following the preparation procedure described in Example 16, except that in step (1) compound 1 is replaced with compound 2 and in step (2) di-n-butyl phthalate (DNBP) is replaced with di-isobutyl phthalate (DIBP) .

Polymerization of propylene was carried out following the procedure described in Example 1, except that Catalyst Component 1 was replaced with Catalyst Component 18. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component 18. The polymerization results are shown in Table 4 below.

Comparative Example 13

Catalyst component C13 was prepared following the preparation procedure described in Example 13, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in example 13, except that the catalyst component 13 was replaced by the catalyst component C13. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component C13. The polymerization results are shown in Table 4 below.

Comparative Example 14

Catalyst component C14 was prepared following the preparation described in Example 14, except that in step (1), compound 2 was replaced with compound 4.

The polymerization of propylene was carried out following the procedure described in example 13, except that the catalyst component 13 was replaced by the catalyst component C14. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component C14. The polymerization results are shown in Table 4 below.

Comparative Example 15

Catalyst component C15 was prepared following the preparation described in Example 16, except that in step (1), compound 1 was replaced with compound 3.

Polymerization of propylene was carried out following the procedure described in example 1, except that the catalyst component 1 was replaced with a C15 catalyst component. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component C15. The polymerization results are shown in Table 4 below.

Comparative Example 16

Catalyst component C16 was prepared following the preparation described in Example 17, except that in step (1), compound 2 was replaced with compound 4.

The polymerization of propylene was carried out following the procedure described in example 1, except that the catalyst component 1 was replaced with a C16 catalyst component. The polymerization results are shown in Table 3 below.

High impact copolymer polypropylene was prepared following the procedure described in Example 13, except that catalyst component 13 was replaced with catalyst component C16. The polymerization results are shown in Table 4 below.

Table 3 Catalyst Diol ether content
wt% A:B ^* Polymerization conditions Activity
kg PP/g cat OP
g/cm ³ PTR
g/10 min PS
% Example 13 0.12 0.05:0.07 4.5 l/1 hour 71.4 0.43 24.7 97.6 1.0 l/2 hour 82.2 0.43 6.01 98.5 Example 14 0.13 0.06:0.07 4.5 l/1 hour 71.0 0.44 21.2 97.5 1.0 l/2 hour 89.4 0.44 5.50 98.8 Example 15 0.10 4.5 l/1 hour 69.1 0.42 31.8 97.5 1.0 l/2 hour 78.2 0.43 5.73 98.6 Example 16 0.19 0.09:0.10 4.5 l/1 hour 68.0 0.42 22.6 97.5 1.0 l/2 hour 80.1 0.42 5.38 98.3 Example 17 0.18 4.5 l/1 hour 69.8 0.42 23.0 97.7 1.0 l/2 hour 81.2 0.42 6.46 98.6 Example 18 0.16 0.07:0.09 4.5 l/1 hour 66.3 0.41 26.8 97.3 1.0 l/2 hour 79.6 0.42 5.96 98.2 Ref. example 13 4.28 0.10:4.18 4.5 l/1 hour 68.0 0.42 23.6 97.4 1.0 l/2 hour 76.9 0.43 5.41 98.2 Ref. example 14 3.92 0.08:3.84 4.5 l/1 hour 71.2 0.41 20.2 97.2 1.0 l/2 hour 82.5 0.42 3.68 98.3 Ref. example 15 3.88 4.5 l/1 hour 65.4 0.42 22.4 97.5 1.0 l/2 hour 77.8 0.42 6.01 98.0 Ref. example 16 4.17 4.5 l/1 hour 66.4 0.41 21.9 97.1 1.0 l/2 hour 78.6 0.42 4.73 98.2

^* A:B=(R, R-configuration +S, S-configuration):(R, S-configuration)

Table ^4a Catalyst Activity
kg PP/g cat OP
g/cm ³ PTR
g/10 min C2=
% RCC2
% RC
% Example 13 42.7 0.43 2.96 9.33 43.7 21.40 Example 14 44.4 0.43 2.54 10.1 44.2 22.85 Example 15 40.7 0.42 2.73 10.0 44.2 22.62 Example 16 43.6 0.42 2.53 10.2 44.6 22.87 Example 17 44.7 0.42 2.76 10.0 43.9 22.78 Example 18 42.9 0.41 2.79 10.3 44.7 23.04 Comparative Example 13 41.4 0.42 2.46 9.09 42.7 21.28 Comparative Example 14 42.8 0.42 2.71 9.13 42.1 21.69 Comparative Example 15 41.6 0.42 2.93 9.36 42.3 22.12 Comparative Example 16 42.5 0.41 2.48 9.47 42.2 22.44

a. C2=means the total content in the polypropylene copolymer, RCC2 means the content of ethylene in the rubber phase, and RC means the content of the rubber phase in the polypropylene copolymer.

From the data in Table 3, it can be seen that when R, R- and S, S-configuration diol ester compounds are used as a precipitant in the preparation of the catalyst component, the content of the precipitant, diol ester, in the finished catalyst component is extremely low and at the same time the catalytic component exhibits high polymerization activity and high stereospecificity. A good particle morphology of the polypropylene powder is observed, indicating that the particle morphology of the catalyst component is good.

From the data in Table 4, it can be seen that when the catalyst component of the present invention is used to produce high impact polypropylene copolymer under the conditions of the same ethylene/propylene mole ratio, the ethylene content of the resulting polypropylene copolymer and the ethylene content of the rubber phase are higher, indicating that the catalyst according to the present invention has a higher ability to copolymerize.

While exemplary embodiments of the invention have been described in detail, it should be understood that various other modifications will be apparent and can be easily made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, the scope of the claims appended herein is not intended to be limited to the examples and descriptions set forth herein, but rather the claims are to be construed as covering all features of patentable novelty that are present in the present invention, including all features that would considered as their equivalents by those skilled in the art to which this invention pertains. The present invention has been described above with reference to a variety of embodiments and specific examples. In view of the foregoing detailed description, a person skilled in the art will recognize a large number of variations. All of these variations will be in accordance with the general purpose of the appended claims.

In this disclosure, whenever a composition, element or group of elements is preceded by the transition phrase "comprising", it should be understood that the same composition, element or group of elements is also meant with the transition phrases "consisting essentially of", "consisting of", " selected from the group consisting of" or "are" preceding the listing of the composition, element or elements, and vice versa.

Claims (58)

1. Ziegler-Natta catalyst component for olefin polymerization containing magnesium, titanium, halogen, an internal electron donor compound and an auxiliary precipitant, wherein the auxiliary precipitant contains at least one auxiliary precipitant a represented by formula (I)

where the substituents R ₁ and R ₂ each independently represent C ₁ -C ₁₀ -alkyl, either substituted or unsubstituted; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₃ -C ₂₀ cycloalkyl and C ₆ -C ₂₀ aryl, either substituted or unsubstituted; and where the content of the auxiliary precipitating additives and is less than 1.0 wt.% based on the total weight of the catalytic component; moreover, the auxiliary precipitating additive a shown by formula (I) contains isomers represented by formula (I-a) and/or formula (I-b)

2. Catalyst component according to claim 1, wherein in formula (I) the substituents R ₁ and R ₂ are each independently C ₁ -C ₈ alkyl, either substituted or unsubstituted, preferably from the group consisting of substituted or unsubstituted C ₁ -C ₄ -alkyl groups; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₃ -C ₁₀ cycloalkyl and C ₆ -C ₁₀ aryl, either substituted or unsubstituted, preferably from the group consisting of C ₅ -C ₁₀ cycloalkyl and C ₆ -C ₁₀ -aryl, either substituted or unsubstituted. 3. The catalytic component according to any one of paragraphs. 1 and 2, characterized in that the content of the auxiliary precipitating additive a is less than 0.5 wt.% and more preferably less than 0.2 wt.% based on the total weight of the catalytic component. 4. The catalytic component according to any one of paragraphs. 1-3, characterized in that the auxiliary precipitating additive further comprises an auxiliary precipitating additive b represented by formula (II) Ti(OR ₇ ) _n X _4-n (II), where each R ₇ substituent is independently selected from the group consisting of C ₁ -C ₁₀ -alkyl and C ₃ -C ₁₀ -cycloalkyl, each X is halogen and n is 1, 2, 3 or 4. 5. Catalytic component according to any one of paragraphs. 1-4, wherein the internal electron donor compound comprises at least a compound selected from the group consisting of: 2,2-dihydrocarbyl-1,3-propylene glycol dimethyl ether type compounds represented by formula (III)

where the substituents R ₅ and R ₆ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -alkaryl, or substituted , or unsubstituted; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, either substituted or unsubstituted; and more preferably from the group consisting of C ₁ -C ₆ -alkyl and phenyl, either substituted or unsubstituted; substituents R ₅ and R ₆ are optionally connected to form a ring; diethyl 2-cyano-2,3-dihydrocarbyl succinate type compounds represented by formula (III')

where the substituents R ₅ and R ₆ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -aralkyl, or substituted , or unsubstituted; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, either substituted or unsubstituted; more preferably from the group consisting of C ₁ -C ₆ -alkyl and phenyl, either substituted or unsubstituted; and phthalate compounds represented by formula (III'')

where the substituents R ₇ and R ₈ are each independently selected from the group consisting of C ₁ -C ₁₀ -alkyl, C ₃ -C ₁₀ -cycloalkyl, C ₆ -C ₁₀ -aryl and C ₇ -C ₁₀ -alkaryl, or substituted , or unsubstituted; preferably from the group consisting of C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl and C ₆ -C ₈ -aryl, either substituted or unsubstituted; and more preferably from the group consisting of substituted or unsubstituted C ₁ -C ₆ alkyl groups. 6. The catalytic component according to any one of paragraphs. 1-5, characterized in that the titanium content is in the range from 1.0 to 8.0 wt.% and preferably from 1.6 to 6.0 wt.%; the magnesium content is in the range from 10.0 to 70.0 wt.% and preferably from 15.0 to 40.0 wt.%; the halogen content is in the range from 20.0 to 90.0 wt.% and preferably from 30.0 to 85.0 wt.%; and the content of the internal electron donor compound is in the range of 2.0 to 30.0 wt.% and preferably 3.0 to 20.0 wt.% based on the total weight of the catalyst component. 7. The catalytic component according to claim 1, characterized in that the catalyst component contains a reaction product of a magnesium compound, a titanium compound, at least one internal electron donor compound and an auxiliary precipitant containing at least one auxiliary precipitant additive a represented by formula (I ), where, with respect to one mol of magnesium compound, the amount of precipitating aid a used is in the range of 0.005 to 0.3 mol and preferably 0.01 to 0.05 mol and precipitating aid a contains isomers represented by formula (I-a) and/ or formula (I-b), in an amount of more than 80 wt.%, preferably more than 90 wt.%, more preferably more than 95 wt.% and even more preferably more than 98 wt.% based on the total weight of the auxiliary precipitating additive a . 8. A method for producing a catalyst component of a Ziegler-Natta catalyst for the polymerization of olefins, comprising the steps: 1) dissolving the magnesium compound in a solvent system to form a solution containing the magnesium compound; 2) precipitation of particles of magnesium-containing solids from a solution containing a magnesium compound in the presence of an auxiliary precipitating additive, where the auxiliary precipitating additive contains at least one auxiliary precipitating additive a represented by formula (I)

where the substituents R ₁ and R ₂ each independently represent C ₁ -C ₁₀ -alkyl, either substituted or unsubstituted; the R ₃ and R ₄ substituents are each independently selected from the group consisting of C ₃ -C ₂₀ cycloalkyl and C ₆ -C ₂₀ aryl, either substituted or unsubstituted; where the auxiliary precipitating additive a shown by formula (I) contains isomers represented by formula (I-a) and/or formula (I-b)

in an amount of more than 80 wt.% based on the total weight of the auxiliary precipitating additive a represented by formula (I); and 3) depositing the titanium-based active component on magnesium-containing solid particles to form a solid catalyst component. 9. The method according to claim 8, wherein the precipitating aid a shown by formula (I) contains the isomers represented by formula (I-a) and/or formula (I-b) in an amount of more than 90% by weight, more preferably more than 95 wt.% and even more preferably more than 98 wt.%, based on the total weight of the auxiliary precipitating additive a represented by formula (I). 10. The method according to p. 8 or 9, including the following stages: (1) reacting the magnesium compound with an alcohol compound, optionally in the presence of an inert hydrocarbon solvent, to obtain a homogeneous solution of the magnesium compound-alcohol adduct; (2) reacting the magnesium compound-alcohol adduct solution from step (1) with the first titanium compound in the presence of a precipitating aid to obtain a precipitated solid mixture; (3) contacting the mixture from step (2) with a first internal electron donor compound to form a slurry; (4) subjecting the slurry from step (3) to a solid/liquid separation to obtain a first solid intermediate, and contacting the resulting first solid intermediate with a second titanium compound and optionally a second internal electron donor compound to form a mixture; (5) subjecting the mixture from step (4) to a solid/liquid separation to form a second solid intermediate, and treating the second solid intermediate with a third titanium compound to form a solid catalyst component; and (6) isolation of the solid catalyst component, or including the following steps: (1) contacting the magnesium compound with an organic epoxy compound and an organophosphorus compound, optionally in the presence of an inert hydrocarbon solvent, to form a homogeneous solution of the magnesium compound; (2) contacting the magnesium compound solution from step (1) with the first titanium compound and the first internal electron donor compound in the presence of a precipitating aid to form a slurry containing a precipitate of a solid; (3) subjecting the slurry from step (2) to a solid/liquid separation to obtain a first solid intermediate and contacting the first solid intermediate with a second titanium compound and optionally a second internal electron donor compound to form a mixture; (4) subjecting the mixture from step (3) to a solid/liquid separation to obtain a second solid intermediate; (5) treating the second solid intermediate with a third titanium compound 1-4 times to form a solid catalyst component; and (6) isolation of the solid catalyst component. 11. Catalyst for the polymerization of olefins, containing: 1) a catalytic component according to any one of paragraphs. 1-7; and 2) alkyl aluminum compound; where the molar ratio of component 1) to component 2) in terms of (titanium:aluminum) is (5-5000):1. 12. The olefin polymerization catalyst of claim 11, further comprising 3) external electron-donor connection. 13. An olefin polymerization catalyst according to claim 11 or 12, wherein the molar ratio of component 1) to component 2) in terms of (titanium:aluminum) is (20-1000):1, more preferably (50-500):1. 14. Prepolymerized catalyst for the polymerization of olefins, containing a prepolymer obtained by carrying out prepolymerization using a catalyst component according to any one of paragraphs. 1-7 or a catalyst according to any one of paragraphs. 11-13 and an olefin, where the prepolymer has a prepolymerization ratio of 5 to 1000 g polyolefin/g catalytic component. 15. The prepolymerized olefin polymerization catalyst of claim 14, wherein the prepolymer has a prepolymerization ratio of 10 to 500 g polyolefin/g catalytic component. 16. The prepolymerized olefin polymerization catalyst of claim 14 or 15, wherein the olefin used in the prepolymerization is ethylene or propylene. 17. The method of polymerization of an olefin of the formula CH ₂ =CHR, where the substituent R represents hydrogen, C ₁ -C ₆ -alkyl or aryl, and the method includes the polymerization of an olefin in the presence of a catalyst component according to any one of paragraphs. 1-7, or a catalyst according to any one of paragraphs. 11-13, or prepolymerized catalyst according to any one of paragraphs. 14-16 to obtain a polyolefin polymer, and isolating the obtained polyolefin polymer.