TW202100572A - Catalyst component for olefin polymerization, its preparation method and catalyst containing the same wherein catalyst component contains magnesium, titanium, halogen, internal electron donor compound and precipitation-aiding agent - Google Patents

Abstract

The present invention relates to a catalyst component for olefin polymerization and a catalyst containing the same. The catalyst component contains magnesium, titanium, halogen, internal electron donor compound and precipitation-aiding agent. Wherein the precipitation-aiding agent includes the precipitation-aiding agent a given by the general formula (I). The precipitation-aiding agent a given by the general formula (I) contains isomers given by the general formula (I-a) and/or the general formula (I-b).

Description

Catalyst component for olefin polymerization, its preparation method and catalyst containing the same

The invention belongs to the technical field of catalysts, and specifically relates to a catalyst component for olefin polymerization, a preparation method thereof and a catalyst containing the catalyst component.

The solid catalyst component containing magnesium, titanium, halogen and electron donor as basic components, namely Ziegler-Natta catalyst known in the art, can be used for α-olefin polymerization, especially when it has 3 or more carbon atoms The α-olefin polymerization can provide a polymer with higher yield and higher stereoregularity. One of the preparation methods includes the following steps: firstly preparing magnesium chloride into a uniform solution, then performing solid precipitation, and loading active components containing titanium. In such a method, in the solid precipitation step, usually only in the presence of a precipitation aid, a solid with uniform fineness and good morphology can be obtained. The precipitation aids are generally organic acid anhydrides, organic acids, ketones, ethers, and esters. Etc., and it is sometimes regarded as an internal electron donor compound. See, for example, CN101864009, CN106317274, CN106317275, CN101906177, CN 102276765, CN 103012625, CN 103012626, CN 103012627, CN 106608933.

It can be expected that when a precipitation assistant is used in the preparation of the solid catalyst component, the prepared solid catalyst component will contain a certain amount of the precipitation assistant, and the precipitation assistant can affect the performance of the solid catalyst component. However, the prior art has hardly paid attention to the influence of the type of precipitation aid and its content in the solid catalyst component on the performance of the solid catalyst component.

In addition, the literature discloses various internal electron donor compounds that can impart the desired performance to the Ziegler-Natta catalyst. For example, CN1020448 discloses 1,3-diether internal electron donor compounds. The catalyst component containing the 1,3-diether internal electron donor compound has high activity and good hydrogen modulation sensitivity when used for olefin polymerization, and the prepared olefin polymer has a narrow molecular weight distribution. For another example, CN102311513 and CN102603931 disclose the use of diethyl 2-cyanosuccinate as an internal electron donor compound. The obtained polyolefin catalyst is not sensitive to hydrogen modulation, has good stereospecificity, and the polypropylene prepared by using the catalyst has a wide molecular weight distribution.

However, the prior art has not taught how to reduce the interference of the precipitation aid on the effect of the internal electron donor compound.

There is still a need in the art for improved Ziegler-Natta catalysts that exhibit various desired properties and methods for their preparation.

In order to overcome the problems encountered in the prior art, the inventors conducted extensive and in-depth research. As a result, it has now been surprisingly found that when a specific configuration of isomers (ie R, R-configuration and/or S, S-configuration isomers) content is greater than 80% in the preparation of solid catalyst components When the diol ester is used as a precipitation aid, solid particles with better particle shape can be precipitated, and the content of the residual precipitation aid in the obtained solid catalyst component is extremely low, thereby avoiding the effect of the precipitation aid on the internal electron donor. interference. The present invention has been completed on this basis.

（I）              （I-a）        （I-b） 其中，R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基和C₇ -C₁₀ 的芳烷基；R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₂₀ 的烷基、C₃ -C₂₀ 的環烷基、C₆ -C₂₀ 的芳基和C₇ -C₂₀ 的芳烷基，並且 其中基於催化劑組分的總重量計，該助析出劑a的含量低於1.0wt%。Therefore, an object of the present invention is to provide a catalyst component for olefin polymerization, which contains magnesium, titanium, halogen, internal electron donor compound and co-precipitation agent, wherein the co-precipitation agent contains at least one of the general formula (I ) The precipitation assistant a shown in, and the precipitation assistant a contains the isomers represented by the general formula (Ia) and/or the general formula (Ib):

(I) (Ia) (Ib) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl, and C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted alkyl group a C ₁ -C _20, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl group and C ₇ -C ₂₀ aralkyl group, and wherein based on the total weight of the catalyst components, the content of the co-precipitator a is less than 1.0 wt%.

Another object of the present invention is to provide a method for preparing the above-mentioned catalyst component.

Another object of the present invention is to provide a catalyst for olefin polymerization, which comprises the following components: 1) The catalyst component of the present invention; 2) Alkyl aluminum compounds; and Optionally 3) External electron donor compound.

Another object of the present invention is to provide a prepolymerization catalyst for olefin polymerization, which includes the catalyst component of the present invention or a prepolymer obtained by prepolymerizing the catalyst and olefin.

Another object of the present invention is to provide a method for olefin polymerization, the general formula of the olefin is CH2=CHR, where R is hydrogen, a C1-C6 alkyl group or an aryl group, and the method includes subjecting the olefin to the catalyst or Polymerizing in the presence of a prepolymerized catalyst to form a polyolefin polymer; and recovering the obtained polyolefin polymer. Detailed description of the preferred embodiment definition

The term "substituted" or "substituted" as used herein means that one or more of the hydrogen atoms on the group in question is replaced by a halogen atom, a heteroatom, a C1-C6 alkyl group or a C1-C6 alkoxy group, or The carbon atoms in the main chain are replaced by heteroatoms.

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

The term "heteroatom" used herein refers to at least one selected from O, S, N, P, Si, and Ge.

The term "polymerization" as used herein includes homopolymerization and copolymerization. The term "polymer" as used herein includes homopolymers, copolymers and terpolymers.

The term "(solid) catalyst component" as used herein refers to the main catalyst component or procatalyst, which together with conventional cocatalysts such as aluminum alkyl and optional external electron donors constitute a catalyst for olefin polymerization ( It is also called a catalyst system in the art).

（I）            （I-a）          （I-b） 其中，R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基和C₇ -C₁₀ 的芳烷基，較佳R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₈ 的烷基、C₃ -C₈ 的環烷基和C₆ -C₈ 的芳基，更佳R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₄ 的烷基，甚至更佳R₁ 和R₂ 各自獨立地選自甲基、乙基、正丙基和異丙基；R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₂₀ 的烷基、C₃ -C₂₀ 的環烷基、C₆ -C₂₀ 的芳基和C₇ -C₂₀ 的芳烷基，較佳R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基和C₆ -C₁₀ 的芳基，更佳R₃ 和R₄ 各自獨立地選自取代或未取代的C₅ -C₁₀ 的烷基、C₅ -C₁₀ 環烷基、C₆ -C₁₀ 芳基和C₇ -C₁₀ 芳烷基，甚至更佳R₃ 和R₄ 各自獨立地選自環戊基、環己基、苯基、對甲基苯基、對乙基苯基、對正丙基苯基，和對正丁基苯基。In the first aspect, the present invention provides a catalyst component for olefin polymerization, which comprises magnesium, titanium, halogen, co-precipitation agent and internal electron donor compound, wherein the co-precipitation agent includes as shown in general formula (I) The precipitant a shown below, and the precipitant a contains isomers represented by general formula (Ia) and/or general formula (Ib):

(I) (Ia) (Ib) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ The aryl group and the C ₇ -C ₁₀ aralkyl group, preferably R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl groups, C ₃ -C ₈ cycloalkyl groups and C ₆ -C ₈ aryl group, more preferably R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₄ alkyl groups, even more preferably R ₁ and R ₂ are each independently selected from methyl , Ethyl, n-propyl and isopropyl; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl, C ₃ -C ₂₀ cycloalkyl, C ₆ -C ₂₀ aryl groups and C ₇ -C ₂₀ aralkyl groups, preferably R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cycloalkyl groups And C ₆ -C ₁₀ aryl groups, more preferably R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₅ -C ₁₀ alkyl groups, C ₅ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ Aryl and C ₇ -C ₁₀ aralkyl, even more preferably R ₃ and R ₄ are each independently selected from cyclopentyl, cyclohexyl, phenyl, p-methylphenyl, p-ethylphenyl, p-n-propyl Phenyl, and p-n-butylphenyl.

（I-a）      （I-b）         （I-c）              （I-d）The precipitation aid a represented by the general formula (I) that can be used in the present invention is a glycol ester compound, which contains two chiral carbon atoms. When R ₁ and R _{2 are} not the same and/or R ₃ and R _{4 are} not the same, the two chiral carbon atoms are different chiral carbon atoms, and the compound represented by the general formula (I) includes the compounds represented by the general formula ( Ia), (Ib), (Ic) and (Id) show four isomers of R, R-configuration, S, S-configuration, R, S-configuration and S, R-configuration. When R ₁ and R _{2 are the} same and R ₃ and R ₄ are the same, the two chiral carbon atoms are the same chiral carbon atoms, and the R,S-configuration and S,R-configuration become exactly the same configuration , And therefore the compound represented by the general formula (I) has R, R- configuration, S, S- configuration and R, S- configuration represented by the general formulas (Ia), (Ib) and (Ic), respectively /S, R-configuration three isomers.

(Ia) (Ib) (Ic) (Id)

In some embodiments, examples of the precipitation aid a represented by the general formula (I) include, but are not limited to, 2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-toluene Formate, 2,4-pentanediol di-p-ethyl benzoate, 2,4-pentanediol di-p-n-propyl benzoate, 2,4-pentanediol di-p-n-butylbenzene Formate, 3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methyl benzoate, 3,5-heptanediol di-p-ethyl benzoate, 3 ,5-Heptanediol di-p-n-propyl benzoate, 3,5-heptanediol di-p-n-butyl benzoate and their mixtures.

According to the present invention, a precipitation assistant is used in the preparation of the catalyst component, which includes the precipitation assistant a represented by the general formula (I). The precipitant a raw material is usually more than 80wt% based on its total weight, preferably more than 90wt%, more preferably more than 95wt%, still more preferably more than 98wt% containing (R, R)- and/or (S, S )-isomer. Compared with the (R,S)- and (S,R)-configuration isomers, the (R,R)-and/or (S,S)-configuration isomers are There is a big difference in binding ability and it is easy to be eluted. Therefore, the precipitant a retained in the final catalyst component will contain a significantly reduced ratio of (R,R)- and (S,S)-isomers and significant Increased ratio of (R,S)- and (S,R)-isomers, compared with the precipitant a raw material. Depending on the composition of the precipitant a used in the preparation of the catalyst component, the (R,R)- and (S,S)-isomer content of the residual precipitant a in the final catalyst component and (R ,S)- and (S,R)-isomer content can vary within a wide range. However, preferably, the (R,R)- and (S,S)-isomer content of the residual co-precipitant a in the final catalyst component is the same as the (R,S)- and (S,R)-isomer content The volume ratio is not less than 1:10, preferably not less than 1:5, more preferably not less than 1:3, still more preferably not less than 1:2. This can be achieved by selecting a raw material for the precipitant a with high (R,R)- and (S,S)-isomer content.

In some specific embodiments, for the purpose of the present invention, the precipitant a raw material used in the preparation of the catalyst component is greater than 80wt% based on its total weight, preferably greater than 90wt%, more preferably greater than 95wt%, Still more preferably, an amount greater than 98% by weight contains at least one of the following isomer combinations: (R,R)-2,4-pentanediol dibenzoate and (S,S)-2,4-pentanediol dibenzoate, (R,R)-2,4-pentane dibenzoate Alcohol di-p-methyl benzoate and (S,S)-2,4-pentanediol di-p-methyl benzoate, (R,R)-2,4-pentanediol di-p-ethyl benzene Formate and (S,S)-2,4-pentanediol di-p-ethyl benzoate, (R,R)-2,4-pentanediol di-p-n-propyl benzoate and ( S,S)-2,4-pentanediol di-p-n-propyl benzoate, (R,R)-2,4-pentanediol di-p-n-butyl benzoate and (S,S) -2,4-pentanediol di-p-n-butyl benzoate, (R,R)-3,5-heptanediol dibenzoate and (S,S)-3,5-heptanediol Dibenzoate, (R,R)-3,5-heptanediol dimethyl benzoate and (S,S)-3,5-heptanediol dimethyl benzoate, (R,R)-3,5-heptanediol di-p-ethyl benzoate and (S,S)-3,5-heptanediol di-p-ethyl benzoate, (R,R)- 3,5-Heptanediol two-p-n-propyl benzoate and (S,S)-3,5-Heptanediol two-p-n-propyl benzoate, (R,R)-3,5- Heptanediol di-p-n-butyl benzoate and (S,S)-3,5-heptanediol di-p-n-butyl benzoate.

Preferably, the precipitant a raw material used in the preparation of the catalyst component is greater than 80wt% based on its total weight, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt%, including the following At least one of the combination of isomers: (R,R)-2,4-pentanediol dibenzoate and (S,S)-2,4-pentanediol dibenzoate, (R, R)-2,4-pentanediol bis-p-methyl benzoate and (S,S)-2,4-pentanediol bis-p-methyl benzoate, (R,R)-2,4 -Pentanediol di-p-ethyl benzoate and (S,S)-2,4-pentanediol di-p-ethyl benzoate, (R,R)-2,4-pentanediol two pairs N-propyl benzoate and (S,S)-2,4-pentanediol di-p-n-propyl benzoate, (R,R)-3,5-heptanediol dibenzoate and (S,S)-3,5-heptanediol dibenzoate, (R,R)-3,5-heptanediol bis-p-methylbenzoate and (S,S)-3,5 -Heptanediol di-p-methylbenzoate, (R,R)-3,5-heptanediol di-p-ethyl benzoate and (S,S)-3,5-heptanediol two pairs Ethyl benzoate, (R,R)-3,5-heptanediol di-p-n-propyl benzoate and (S,S)-3,5-heptanediol di-p-n-propyl benzoate Acid ester.

Most preferably, the precipitant a raw material used in the preparation of the catalyst component is contained in an amount greater than 80wt% based on its total weight, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt% At least one of the following isomer combinations: (R,R)-2,4-pentanediol dibenzoate and (S,S)-2,4-pentanediol dibenzoate, (R ,R)-2,4-pentanediol bis-p-methylbenzoate and (S,S)-2,4-pentanediol bis-p-methylbenzoate, (R,R)-2, 4-pentanediol di-p-ethyl benzoate and (S,S)-2,4-pentanediol di-p-ethyl benzoate, (R,R)-3,5-heptanediol two Benzoate and (S,S)-3,5-heptanediol dibenzoate, (R,R)-3,5-heptanediol dimethyl benzoate and (S,S) )-3,5-heptanediol di-p-methylbenzoate, (R,R)-3,5-heptanediol di-p-ethyl benzoate and (S,S)-3,5- Heptanediol di-p-ethyl benzoate.

In some embodiments of the present invention, based on the total weight of the catalyst component, the content of the precipitation promoter a in the catalyst component is less than 1.0 wt%, preferably less than 0.5 wt%, more preferably less than 0.2 wt% , Still better than 0.15wt%.

In some embodiments of the present invention, the precipitation assistant optionally further includes a precipitation assistant b represented by the general formula (II): Ti(OR ₇ ) _n X _4-n (II) wherein R _{7 is} selected From a C ₁ -C ₁₀ alkyl group or a C ₃ -C ₁₀ cycloalkyl group, X is halogen, and n is 1, 2, 3, or 4.

In some preferred embodiments of the present invention, the precipitation aid b is selected from tetramethyl titanate, tetraethyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, tetra-n-butyl titanate At least one of propyl ester and tetraisopropyl titanate is preferably tetraethyl titanate or tetra-n-butyl titanate.

In some embodiments, the precipitation assistant in the catalyst component of the present invention basically consists of the above precipitation assistant a and the precipitation assistant b.

In some other embodiments, the precipitation assistant in the catalyst component of the present invention consists essentially of the above precipitation assistant a.

In some embodiments, the catalyst component of the present invention does not contain other precipitation assistants except for the above-mentioned precipitation assistants a and b.

According to 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 can impart desired performance to the catalyst component can be included in the catalyst component.

（III） 其中，R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基和C₇ -C₁₀ 的烷芳基；較佳R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₈ 的烷基、C₃ -C₈ 的環烷基和C₆ -C₈ 的芳基；更佳R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₆ 的烷基；進一步較佳R₅ 和R₆ 各自獨立地選自甲基，乙基，正丙基，異丙基，正丁基，異丁基，特丁基，正戊基，異戊基，特戊基，環戊基，環己基，苯基。R₅ 和R₆ 任選地連接成環。相應的其它醚如二乙基醚、二丙基醚、甲乙醚等也已經被想到。In some embodiments, the catalyst component of the present invention contains at least one 2,2-dihydrocarbyl-1,3-propanediol dimethyl ether compound represented by the general formula (III) as an internal electron donor:

(III) Wherein, R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₀ alkylaryl; preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ Aryl; more preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl; more preferably R ₅ and R ₆ are each independently selected from methyl, ethyl, n-propyl Base, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, cyclopentyl, cyclohexyl, phenyl. R ₅ and R _{6 are} optionally connected to form a ring. Corresponding other ethers such as diethyl ether, dipropyl ether, methyl ethyl ether, etc. have also been conceived.

Examples of suitable 2,2-dihydrocarbyl-1,3-propanediol dimethyl ether compounds represented by the general formula (III) include, but are not limited to: 2,2-di-n-propyl-1,3-propanediol dimethyl ether Ether, 2,2-Diisopropyl-1,3-propanediol dimethyl ether, 2,2-Di-n-butyl-1,3-propanediol dimethyl ether, 2,2-Diisobutyl-1,3 -Propylene glycol dimethyl ether, 2,2-di-n-pentyl-1,3-propanediol dimethyl ether, 2,2-diisopentyl-1,3-propanediol dimethyl ether, 2,2-di-n-hexyl- 1,3-propanediol dimethyl ether, 2,2-diisohexyl-1,3-diether, 2-n-propyl-2-isopropyl-1,3-propanediol dimethyl ether, 2-n-propyl -2-n-butyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-isobutyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-n-pentyl-1 ,3-Propanediol dimethyl ether, 2-n-propyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-n-hexyl-1,3-propanediol dimethyl ether, 2 -N-propyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-n-butyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isobutyl Dimethyl ether, 2-isopropyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isopentyl-1,3-propanediol Methyl ether, 2-isopropyl-2-n-hexyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-n-butyl-2 -Isobutyl-1,3-propanediol dimethyl ether, 2-n-butyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-n-butyl-2-isopentyl-1,3 -Propylene glycol dimethyl ether, 2-n-butyl-2-n-hexyl-1,3-propanediol dimethyl ether, 2-n-butyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-isobutyl 2-n-pentyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-n-hexyl-1 ,3-Propanediol dimethyl ether, 2-isobutyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-n-pentyl-2-isopentyl-1,3-propanediol dimethyl ether, 2 -N-pentyl-2-n-hexyl-1,3-propanediol dimethyl ether, 2-n-pentyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-isopentyl-2-n-hexyl- 1,3-propanediol dimethyl ether, 2-isopentyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-n-hexyl-2-isohexyl-1,3-propanediol dimethyl ether.

In some preferred embodiments, the catalyst component of the present invention contains at least one compound selected from the following group as an internal electron donor: 2,2-diisopropyl-1,3-propanediol dimethyl ether, 2, 2-Di-n-butyl-1,3-propanediol dimethyl ether, 2,2-diisobutyl-1,3-propanediol dimethyl ether, 2,2-di-n-pentyl-1,3-propanediol dimethyl ether Ether, 2,2-Diisopentyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-isopropyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-iso Butyl-1,3-propanediol dimethyl ether, 2-n-propyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-n-butyl-1,3-propanediol Dimethyl ether, 2-isopropyl-2-isobutyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isopropyl 2-isopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-n-butyl-2-isobutyl-1 ,3-Propanediol dimethyl ether, 2-n-butyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-n-butyl-2-isohexyl-1,3-propanediol dimethyl ether, 2 -Isobutyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-n-hexyl Butyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-isohexyl-1,3-propanediol dimethyl ether and 2-n-pentyl-2-isopentyl-1,3-propanediol dimethyl ether ether.

In some preferred embodiments, the catalyst component of the present invention contains at least one compound selected from the following group as an internal electron donor: 2,2'-diisopropyl-1,3-propanediol dimethyl ether, 2 ,2'-Diisobutyl-1,3-propanediol dimethyl ether, 2,2'-Diisopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isobutyl-1 ,3-propanediol dimethyl ether, 2-isopropyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether, 2-isopropyl-2-isohexyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-n-pentyl-1,3-propanediol dimethyl ether, 2-isobutyl-2-iso Pentyl-1,3-propanediol dimethyl ether and 2-n-pentyl-2-isopentyl-1,3-propanediol dimethyl ether.

（III） 其中，R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基和C₇ -C₁₀ 的芳烷基；較佳R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₈ 的烷基、C₃ -C₈ 的環烷基和C₆ -C₈ 的芳基；更佳R₅ 和R₆ 各自獨立地選自取代或未取代的C₁ -C₆ 的烷基和苯基；進一步較佳R₅ 和R₆ 各自獨立地選自甲基，乙基，正丙基，異丙基，正丁基，異丁基，特丁基，正戊基，異戊基，特戊基，環戊基，環己基，和苯基。相應的其它酯如二甲酯、二丙酯、甲乙酯等也已經被想到。In some embodiments, the catalyst component of the present invention contains at least one diethyl 2-cyano-2,3-dihydrocarbylsuccinate compound represented by general formula (III') as an internal electron donor:

(III) Wherein, R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₀ aralkyl; preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ Aryl; more preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl and phenyl; more preferably R ₅ and R ₆ are each independently selected from methyl, ethyl , N-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, t-pentyl, cyclopentyl, cyclohexyl, and phenyl. Corresponding other esters such as dimethyl ester, dipropyl ester, methyl ethyl ester, etc. have also been conceived.

Examples of suitable 2-cyano-2,3-dihydrocarbyl diethyl succinate compounds represented by the general formula (III') include but are not limited to: 2-cyano-2,3-di-n-propyl Diethyl succinate, diethyl 2-cyano-2,3-diisopropyl succinate, diethyl 2-cyano-2,3-di-n-butyl succinate, 2-cyano 2-cyano-2,3-diisobutyl diethyl succinate, 2-cyano-2,3-di-n-pentyl diethyl succinate, 2-cyano-2,3-diisopentyl Diethyl succinate, 2-cyano-2,3-dicyclopentyl diethyl succinate, 2-cyano-2,3-di-n-hexyl diethyl succinate, 2-cyano -2,3-Diisohexyl diethyl succinate, 2-cyano-2-isopropyl-3-n-propyl diethyl succinate, 2-cyano-2-isopropyl-3 -Diethyl n-butyl succinate, diethyl 2-cyano-2-isopropyl-3-isobutyl succinate, 2-cyano-2-isopropyl-3-n-pentyl Diethyl succinate, 2-cyano-2-isopropyl-3-isopentyl diethyl succinate, 2-cyano-2-isopropyl-3-cyclopentyl succinate Ethyl ester, diethyl 2-cyano-2-n-butyl-3-n-propyl succinate, diethyl 2-cyano-2-n-butyl-3-isopropyl succinate, 2 -Cyano-2-n-butyl-3-isobutyl diethyl succinate, 2-cyano-2-n-butyl-3-n-pentyl diethyl succinate, 2-cyano- Diethyl 2-n-butyl-3-isopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-cyclopentylsuccinate, 2-cyano-2-isobutyl Diethyl-3-n-propyl succinate, diethyl 2-cyano-2-isobutyl-3-isopropyl succinate, 2-cyano-2-isobutyl-3- Diethyl n-butyl succinate, diethyl 2-cyano-2-isobutyl-3-n-pentyl succinate, 2-cyano-2-isobutyl-3-isopentyl butyl Diethyl diacid, diethyl 2-cyano-2-isobutyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-pentyl-3-n-propyl succinate Ester, 2-cyano-2-n-pentyl-3-isopropyl diethyl succinate, 2-cyano-2-n-pentyl-3-n-butyl diethyl succinate, 2- Cyano-2-n-pentyl-3-isobutyl diethyl succinate, 2-cyano-2-n-pentyl-3-isopentyl diethyl succinate, 2-cyano-2 -Diethyl n-pentyl-3-cyclopentyl succinate, diethyl 2-cyano-2-isopentyl-3-n-propyl succinate, 2-cyano-2-isopentyl Diethyl-3-isopropyl succinate, diethyl 2-cyano-2-isopentyl-3-n-butyl succinate, 2-cyano-2-isopentyl-3-iso Diethyl butyl succinate, diethyl 2-cyano-2-isopentyl-3-n-pentyl succinate, 2-cyano-2-isopentyl-3-cyclopentyl succinate Diethyl acrylate, 2-cyano-2-cyclopentyl-3-n-propyl diethyl succinate, 2-cyano-2-cyclopentyl-3-isopropyl succinate diethyl , 2-cyano-2-cyclopentyl-3-n-butyl diethyl succinate, 2-cyano-2-cyclopentyl-3-isobutyl Diethyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-pentyl succinate and 2-cyano-2-cyclopentyl-3-isopentyl succinate Diethyl ester.

In some preferred embodiments, the catalyst component of the present invention contains at least one compound selected from the following group as an internal electron donor: diethyl 2-cyano-2,3-diisopropyl succinate, 2-cyano-2,3-di-n-butyl diethyl succinate, 2-cyano-2,3-diisobutyl diethyl succinate, 2-cyano-2,3-di Diethyl n-pentyl succinate, diethyl 2-cyano-2,3-diisopentyl succinate, 2-cyano-2-isopropyl-3-n-propyl succinate Ethyl ester, 2-cyano-2-isopropyl-3-n-butyl diethyl succinate, 2-cyano-2-isopropyl-3-isobutyl diethyl succinate, 2 -Cyano-2-isopropyl-3-n-pentyl diethyl succinate, 2-cyano-2-isopropyl-3-isopentyl diethyl succinate, 2-cyano- Diethyl 2-isopropyl-3-cyclopentylsuccinate, diethyl 2-cyano-2-n-butyl-3-isopropylsuccinate, 2-cyano-2-n-butyl Diethyl-3-isobutylsuccinate, diethyl 2-cyano-2-n-butyl-3-n-pentylsuccinate, 2-cyano-2-isobutyl-3- Diethyl isopropyl succinate, diethyl 2-cyano-2-isobutyl-3-n-butyl succinate, 2-cyano-2-isobutyl-3-n-pentyl butyl Diethyl diacid, 2-cyano-2-n-pentyl-3-isopropyl diethyl succinate, 2-cyano-2-n-pentyl-3-n-butyl diethyl succinate Ester, 2-cyano-2-n-pentyl-3-isobutyl diethyl succinate, 2-cyano-2-isopentyl-3-isopropyl diethyl succinate, 2- Cyano-2-isopentyl-3-n-butyl diethyl succinate, 2-cyano-2-isopentyl-3-isobutyl diethyl succinate, 2-cyano-2 -Diethyl cyclopentyl-3-isopropyl succinate, diethyl 2-cyano-2-cyclopentyl-3-n-butyl succinate and 2-cyano-2-cyclopentyl Diethyl-3-isobutyl succinate.

In some preferred embodiments, the catalyst component of the present invention contains at least one compound selected from the following group as an internal electron donor: diethyl 2-cyano-2,3-diisopropyl succinate, 2-cyano-2,3-di-n-butyl diethyl succinate, 2-cyano-2,3-diisobutyl diethyl succinate, 2-cyano-2,3-di Diethyl n-pentyl succinate, diethyl 2-cyano-2,3-diisopentyl succinate, 2-cyano-2-isopropyl-3-n-butyl succinate Ethyl ester, 2-cyano-2-isopropyl-3-isobutyl diethyl succinate, 2-cyano-2-isopropyl-3-n-pentyl diethyl succinate, 2 -Cyano-2-isopropyl-3-isopentyl diethyl succinate, 2-cyano-2-isopropyl-3-cyclopentyl diethyl succinate, 2-cyano- Diethyl 2-n-butyl-3-isopropylsuccinate, diethyl 2-cyano-2-isobutyl-3-isopropylsuccinate, 2-cyano-2-n-pentyl Diethyl-3-isopropylsuccinate, diethyl 2-cyano-2-isopentyl-3-isopropylsuccinate and 2-cyano-2-cyclopentyl-3- Diethyl isopropyl succinate.

（III"） 其中，R₇ 和R₈ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基和C₇ -C₁₀ 的烷芳基；較佳R₇ 和R₈ 各自獨立地選自取代或未取代的C₁ -C₈ 的烷基、C₃ -C₈ 的環烷基和C₆ -C₈ 的芳基；更佳R₇ 和R₈ 各自獨立地選自取代或未取代的C₁ -C₆ 的烷基；進一步較佳，R₇ 和R₈ 各自獨立地選自甲基，乙基，正丙基，異丙基，正丁基，異丁基，正戊基和異戊基。In some embodiments, the catalyst component of the present invention contains at least one phthalate compound represented by general formula (III") as an internal electron donor;

(III") wherein R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ aryl groups, and C ₇ -C ₁₀ alkylaryl; preferably R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ More preferably, R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl groups; more preferably, R ₇ and R ₈ are each independently selected from methyl, ethyl, N-propyl, isopropyl, n-butyl, isobutyl, n-pentyl and isopentyl.

Examples of suitable phthalate compounds represented by general 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 diisopentyl phthalate.

Preferably, the phthalate compound represented by the general formula (III") is selected from the group consisting of diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, and Di-n-butyl phthalate, diisobutyl phthalate and di-n-pentyl phthalate. Most preferably, the phthalate compound represented by the general formula (III") is selected from Diethyl phthalate, diisopropyl phthalate, di-n-butyl phthalate and diisobutyl phthalate.

In the catalyst component of the present invention, based on the total weight of the catalyst component, the content of titanium is 1.0wt%-8.0wt%, preferably 1.6wt%-6.0wt%; the content of magnesium is 10.0wt% -70.0wt%, preferably 15.0wt%-40.0wt%; the content of the halogen is 20.0wt%-90.0wt%, preferably 30.0wt%-85.0wt%; the content of the internal electron donor compound is 2.0 wt%-30.0wt%, preferably 3.0wt%-20.0wt%.

In some embodiments, the catalyst component of the present invention includes the reaction product of a magnesium compound, a titanium compound, at least one internal electron donor compound, and at least one precipitation assistant compound represented by general formula (I) a . Titanium compounds, magnesium compounds, and internal electron donor compounds that can be used to prepare Ziegler-Natta catalyst components by the dissolution-precipitation method are well known to those skilled in the art, and they can all be used in conventional amounts in the art This forms the catalyst component of the present invention. Some examples of the titanium compound and the magnesium compound are described later.

In some embodiments of the present invention, per mole of magnesium compound, the amount of the precipitation aid a can be 0.005-0.3 moles, preferably 0.01-0.05; the moles of the precipitation aid a and the internal electron donor compound The ratio can be 0.05:1 to less than 0.8:1, preferably 0.1:1 to 0.7:1.

In some embodiments of the present invention, the precipitation assistant used to prepare the catalyst component further includes the precipitation assistant b as described above, and the amount of the precipitation assistant b is 0.01 to per mole of the precipitation assistant a. 5 moles, preferably 0.5-3 moles.

In the second aspect, the present invention provides a method for preparing the olefin polymerization catalyst component of the present invention. In principle, any method known in the art that can be used to prepare Ziegler-Natta catalysts by the dissolution-precipitation procedure can be used to prepare the catalyst component of the present invention, provided that the solid particles are introduced into the reaction system before precipitation Precipitating aids including the precipitating aid a described above.

（I） 其中，R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基或C₇ -C₁₀ 的芳烷基；R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₂₀ 的烷基、C₃ -C₂₀ 的環烷基、C₆ -C₂₀ 的芳基或C₇ -C₂₀ 的芳烷基； 其中通式（I）所示的助析出劑a以大於80wt%，較佳大於90wt%，更佳大於95wt%，仍更佳大於98wt%的量包含如通式（I-a）和/或通式（I-b）所示的異構體，基於通式（I）所示的助析出劑a的總重量計；

（I-a）                  （I-b）；和 3）在該顆粒狀含鎂固體物上負載鈦基活性組分，以形成固體催化劑組分。Therefore, the present invention provides a method for preparing a catalyst component for olefin polymerization. The method includes the following steps: 1) dissolving a magnesium compound in a solvent system to form a magnesium compound solution; 2) removing a magnesium compound in the presence of a precipitation aid The magnesium-containing compound solution precipitates particulate magnesium-containing solids, wherein the precipitation aid includes at least one precipitation aid a represented by the general formula (I);

(I) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₆ -C ₂₀ aryl groups Or a C ₇ -C ₂₀ aralkyl group; wherein the precipitation aid a represented by the general formula (I) is contained in an amount greater than 80wt%, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt% The isomers represented by general formula (Ia) and/or general formula (Ib) are based on the total weight of the precipitation aid a represented by general formula (I);

(Ia) (Ib); and 3) A titanium-based active component is supported on the particulate magnesium-containing solid to form a solid catalyst component.

（I） 其中，R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基或C₇ -C₁₀ 的芳烷基；R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₂₀ 的烷基、C₃ -C₂₀ 的環烷基、C₆ -C₂₀ 的芳基或C₇ -C₂₀ 的芳烷基； 其中通式（I）所示的助析出劑a以大於80wt%，較佳大於90wt%，更佳大於95wt%，仍更佳大於98wt%的量包含如通式（I-a）和/或通式（I-b）所示的異構體，基於通式（I）所示的助析出劑a的總重量計；

（I-a）                 （I-b）； （3）使步驟（2）所得的混合物與第一內給電子體化合物接觸，得到一種懸浮液； （4）將步驟（3）得到的懸浮液進行固液分離以獲得第一固體中間產物，並且使得到的第一固體中間產物與第二鈦化合物和任選地第二內給電子體化合物接觸，以提供一種混合物； （5）將步驟（4）得到的混合物進行固液分離，得到第二固體中間產物，並且將該第二固體中間產物用第三鈦化合物處理，以形成固體催化劑組分；和 （6） 回收該固體催化劑組分。The first exemplary method that can be used to prepare the catalyst component for olefin polymerization of the present invention includes the following steps: (1) The magnesium compound and the alcohol compound are optionally reacted in the presence of an inert hydrocarbon solvent to obtain a homogeneous magnesium compound alcohol (2) In the presence of a precipitation assistant, the magnesium compound alcoholate solution obtained in step (1) is reacted with the first titanium compound to obtain a mixture containing a solid precipitate, wherein the precipitation assistant contains at least one such as The precipitation aid a represented by the general formula (I);

(I) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₆ -C ₂₀ aryl groups Or a C ₇ -C ₂₀ aralkyl group; wherein the precipitation aid a represented by the general formula (I) is contained in an amount greater than 80wt%, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt% The isomers represented by general formula (Ia) and/or general formula (Ib) are based on the total weight of the precipitation aid a represented by general formula (I);

(Ia) (Ib); (3) Contact the mixture obtained in step (2) with the first internal electron donor compound to obtain a suspension; (4) subject the suspension obtained in step (3) to solid-liquid separation to Obtain a first solid intermediate product, and contact the obtained first solid intermediate product with a second titanium compound and optionally a second internal electron donor compound to provide a mixture; (5) Combine the mixture obtained in step (4) Solid-liquid separation is performed to obtain a second solid intermediate product, and the second solid intermediate product is treated with a third titanium compound to form a solid catalyst component; and (6) the solid catalyst component is recovered.

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) the magnesium compound and the alcohol compound are subjected to a first contact reaction in an inert hydrocarbon solvent to obtain a uniform magnesium compound alcoholate solution; (2) ) In the presence of a precipitation aid, the homogeneous solution obtained in step (1) is subjected to a second contact reaction with the first titanium compound to obtain a mixture containing solid precipitation; (3) the mixture obtained in step (2) is combined with the first titanium compound; The internal electron donor compound undergoes a third contact reaction to obtain a suspension; (4) the suspension obtained in step (3) is subjected to solid-liquid separation, and the obtained solid intermediate product is combined with the second titanium compound and the second internal electron donor compound Perform the fourth contact reaction, and then perform solid-liquid separation to obtain a solid intermediate product; (5) Perform a fifth contact reaction between the solid intermediate product obtained in step (4) and the third titanium compound, and then perform solid-liquid separation to obtain a solid The product is washed with an inert solvent and dried to obtain the final solid catalyst component.

The alcohol compound used in the first method may be selected from C ₁ -C ₁₀ linear or branched fatty alcohols, C ₃ -C ₁₂ alicyclic alcohols, C ₆ -C ₂₀ aryl alcohols, and C _7- one or more arylalkyl alcohols in the C _20. Examples of alcohol compounds include, but are not limited to, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, n-pentanol, isoamyl alcohol, n-hexanol, isohexanol, 2-ethyl Hexanol, benzyl alcohol, phenethyl alcohol, cyclopentanol, methylcyclopentanol, cyclohexanol and mixtures thereof, preferably 2-ethylhexanol.

In the first method, the amount of alcohol compound used is 2-4 moles per mole of magnesium, preferably 2.5-3.5 moles, and the titanium compound used in steps (2), (4) and (5) The total amount is 1-40 moles, preferably 1.5-35 moles.

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

More details of the above method can be found in CN 106317275, and the entire disclosure of this application is incorporated herein by reference.

（I） 其中，R₁ 和R₂ 各自獨立地選自取代或未取代的C₁ -C₁₀ 的烷基、C₃ -C₁₀ 的環烷基、C₆ -C₁₀ 的芳基或C₇ -C₁₀ 的芳烷基；R₃ 和R₄ 各自獨立地選自取代或未取代的C₁ -C₂₀ 的烷基、C₃ -C₂₀ 的環烷基、C₆ -C₂₀ 的芳基或C₇ -C₂₀ 的芳烷基； 其中通式（I）所示的助析出劑a以大於80wt%，較佳大於90wt%，更佳大於95wt%，仍更佳大於98wt%的量包含如通式（I-a）和/或通式（I-b）所示的異構體，基於通式（I）所示的助析出劑a的總重量計；

（I-a）                 （I-b）； （3）將步驟（2）得到的懸浮液進行固液分離，得到第一固體中間產物，並且使該第一固體中間產物與第二鈦化合物和任選地第二內給電子體化合物接觸，以提供一種混合物； （4）將步驟（3）得到的混合物進行固液分離，以得到第二固體中間產物； （5）將該第二固體中間產物用第三鈦化合物處理1-4次，以形成進行固體催化劑組分；和 （6）回收該固體催化劑組分。The second exemplary method that can be used to prepare the catalyst component for olefin polymerization of the present invention includes the following steps: (1) Contacting a magnesium compound, an organic epoxy compound, and an organic phosphorus compound optionally in the presence of an inert hydrocarbon solvent, A uniform magnesium compound solution is formed; (2) In the presence of a precipitation aid, the magnesium compound solution obtained in step (1) is reacted with the first titanium compound and the first internal electron donor compound to obtain a suspension containing solid precipitates , Wherein the precipitation assistant comprises at least one precipitation assistant a represented by the general formula (I);

(I) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₆ -C ₂₀ aryl groups Or a C ₇ -C ₂₀ aralkyl group; wherein the precipitation aid a represented by the general formula (I) is contained in an amount greater than 80wt%, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt% The isomers represented by general formula (Ia) and/or general formula (Ib) are based on the total weight of the precipitation aid a represented by general formula (I);

(Ia) (Ib); (3) The suspension obtained in step (2) is subjected to solid-liquid separation to obtain a first solid intermediate product, and the first solid intermediate product is combined with the second titanium compound and optionally the second Contact the internal electron donor compound to provide a mixture; (4) subject the mixture obtained in step (3) to solid-liquid separation to obtain a second solid intermediate product; (5) use a third titanium for the second solid intermediate product The compound is treated 1-4 times to form a solid catalyst component; and (6) the solid catalyst component is recovered.

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) the magnesium compound, the organic epoxy compound, and the organic phosphorus compound are subjected to a first contact reaction in an inert hydrocarbon solvent to obtain a uniform magnesium compound solution; (2) In the presence of the precipitation aid, the homogeneous solution obtained in step (1) is subjected to a second contact reaction with the first titanium compound and the first internal electron donor compound to obtain a suspension containing solid precipitates; (3) ) The suspension containing the solid precipitate obtained in step (2) is subjected to solid-liquid separation, and the obtained solid intermediate product A is subjected to a third contact reaction with the second titanium compound and the second internal electron donor compound, and after solid-liquid separation , Obtain a solid intermediate product B; (4) perform a fourth contact reaction between the solid intermediate product B obtained in step (3) and the third titanium compound, and after solid-liquid separation, the obtained solid intermediate product C; the obtained solid intermediate product C is then treated with the third titanium compound for 1-3 times for solid-liquid separation, and the obtained solid product is washed with an inert solvent and dried to obtain the final solid catalyst component.

The organic epoxy compound used in the second method may be selected from ethylene oxide, propylene oxide, butylene oxide, butadiene oxide, butadiene double oxide, epichlorohydrin, methyl At least one of glycidyl ether and diglycidyl ether, preferably epichlorohydrin.

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

In the second method, per mole of magnesium, the amount of organic epoxy compound used is 0.2-10 moles, preferably 0.5-4.0 moles; the amount of organic phosphorus compound used is 0.1-3.0 moles, preferably 0.3-1.5 moles. The total amount of titanium compound is 3-40 moles, preferably 5-35 moles.

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

More details of the above method can be found in CN 101864009, the entire disclosure of this application is incorporated herein by reference.

Any internal electron donor compound known in the art that can impart desired properties to the polyolefin catalyst component can be used in the method of the present invention as the internal electron donor or the first and/or second internal electron donor. In some embodiments, the method of the present invention utilizes at least one compound represented by the aforementioned formula (III), formula (III') or formula (III") 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 preparation 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, More preferably, it is (0.2-1):1.

Examples of the magnesium compound that can be used in the above-mentioned first and second preparation methods include compounds represented by general formula (IV), hydrates represented by general formula (V), and alcohol compounds represented by general formula (VI) One or more of: MgR ₈ R ₉ (IV) MgR ₈ R ₉ ·qH ₂ O (V) MgR ₈ R ₉ ·pR ₀ OH (VI) wherein R ₈ and R ₉ are each independently selected from halogen, C _1- C ₅ hydrocarbyl group, C ₁ -C ₅ hydrocarbyloxy group, C ₁ -C ₅ halogenated hydrocarbyl group or C ₁ -C ₅ halogenated hydrocarbyloxy group; preferably R ₈ and R ₉ are each independently Fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, wherein in general formula (V), q is 0.1-6.0, preferably 2.0-3.5; wherein in general formula (VI), R _{0 is} selected from C of ₁ -C ₁₈ hydrocarbon group, preferably a C ₁ -C ₅ alkyl group; p is 0.1 to 6.0, preferably 2.0 to 3.5.

In some preferred embodiments of the present invention, the magnesium compound is at least selected from magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride One kind.

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

The inert hydrocarbon solvent may be any hydrocarbon solvent commonly used in the field that does not chemically interact with the magnesium compound, such as at least one of alkane, cycloalkane or aromatic hydrocarbon, preferably decane, benzene, toluene or xylene At least one of them is more preferably toluene.

The titanium compound that can be used in the method of the present invention includes at least one compound represented by the general formula (VII): TiX _m (OR ₁₀ ) _4-m (VII) wherein R ₁₀ is a C ₁ -C ₂₀ hydrocarbon group, preferably Is a C ₁ -C ₅ alkyl group; X is chlorine, bromine or iodine; m is 1, 2, 3 or 4.

In some preferred embodiments of the present invention, the titanium compound is selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraalkoxy, alkoxy titanium trihalide, dialkoxy At least one of titanium dihalide and trialkoxy titanium halide.

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

In the third aspect, the present invention provides a catalyst for olefin polymerization, which comprises the following components: 1) The catalyst component according to the first aspect of the present invention; 2) Alkyl aluminum compounds; And optionally 3) external electron donor compound.

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

The component 2) aluminum alkyl compound can be one or more of various aluminum alkyl compounds commonly used in the field of olefin polymerization that can be used as a co-catalyst of Ziegler-Natta catalysts.

In some preferred embodiments of the present invention, the component 2) an alkyl aluminum compound comprises at least one compound of formula (VIII) as _{shown; AlR 'n' X '3} -n' (VIII) wherein, R 'Selected from H, C ₁ -C ₂₀ alkyl group or C ₆ -C ₂₀ aryl group, X'is halogen, and 1≤n'≤3.

In some more preferred embodiments of the present invention, the alkyl aluminum compound is selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, monohydrogen di At least one of ethyl aluminum, diisobutyl aluminum monohydrogen, diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, and ethyl aluminum dichloro.

According to the present invention, the type and amount of the external electron donor compound are not particularly limited. The external electron donor compound may be one or more of various external electron donor compounds commonly used in the field of olefin polymerization that can be used as Ziegler-Natta catalysts. If used, the external electron donor compound is used in an amount generally used in the art.

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

In some preferred embodiments of the present invention, the external electron donor compound includes at least one compound represented by the general formula (IX): R ¹ "_m" R ² "_n" Si(OR ^3" ) _{4-m "-n"} (IX) wherein 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; R ³ "is selected from C ₁ -C ₂₀ alkyl or haloalkyl, C ₃ -C ₂₀ cycloalkyl and C ₆ -C ₂₀ aryl; m" and n" are independently An integer of 0-3, and m" + n"<4.

In some more preferred embodiments of the present invention, the external electron donor compound is selected from trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxytriethylmethoxysilane , Triethyl ethoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, ethyl isopropyl dimethoxy silane, propyl isopropyl dimethoxy silane, two Isopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, Tert-Butyl Ethyl Dimethoxy Silane, Tert-Butyl Propyl Dimethoxy Silane, Tert-Butyl Isopropyl Dimethoxy Silane, Tert-Butyl Butyl Dimethoxy Silane, Tert-Butyl Isobutyl Dimethoxysilane, tert-butyl(sec-butyl)dimethoxysilane, tert-butylpentyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butylhexyldimethoxysilane , Tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butyldecyldimethoxysilane, methyl tert-butyldimethoxysilane, cyclohexylmethyldimethoxysilane Cyclohexyl Ethyl Dimethoxy Silane, Cyclohexyl Propyl Dimethoxy Silane, Cyclohexyl Isobutyl Dimethoxy Silane, Dicyclohexyl Dimethoxy Silane, Cyclohexyl Tert-Butyl Dimethyl Oxysilane, cyclopentyl methyl dimethoxy silane, cyclopentyl ethyl dimethoxy silane, cyclopentyl propyl dimethoxy silane, cyclopentyl tert-butyl dimethoxy silane, two Cyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane, diphenyldimethoxysilane, diphenyldiethyl Oxysilane, phenyl triethoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, propyl trimethoxy silane, iso Propyl trimethoxy silane, butyl trimethoxy silane, butyl triethoxy silane, isobutyl trimethoxy silane, tert-butyl trimethoxy silane, sec-butyl trimethoxy silane, pentyl trimethoxy silane Silane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane , Phenyltriethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, 2-ethylpiridinyl- 2-tert-Butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpyridinyldimethoxysilane and (1,1,1-trifluoro- At least one of 2-propyl)-methyldimethoxysilane.

In some further preferred embodiments of the present invention, the external electron donor compound is selected from the group consisting of dicyclopentyldimethoxysilane, diisopropyldimethoxysilane, and diisobutyldimethoxysilane. At least one of silane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane, and tetramethoxysilane.

In a fourth aspect, the present invention provides a prepolymerization catalyst for olefin polymerization, which comprises the catalyst component according to the first aspect of the present invention or a prepolymer obtained by prepolymerizing the catalyst and olefin according to the third aspect of the present invention. Polymer; wherein the prepolymerization multiple of the prepolymer is 5-1000 g olefin polymer/g catalyst component, preferably 10-500 g olefin polymer/g catalyst component. Preferably, the olefin used in the prepolymerization is ethylene or propylene.

In some embodiments of the present invention, the pre-polymerization temperature is -20 to 80°C, preferably 10-50°C.

In the fifth aspect, the present invention provides an olefin polymerization method, wherein the olefin is prepolymerized in the catalyst component of the first aspect of the present invention, the catalyst of the third aspect of the present invention, or the fourth aspect of the present invention. The polymerization is carried out under the action of the catalyst. The general formula of the olefin is CH ₂ =CHR, where R is hydrogen, a C ₁ -C ₆ alkyl group or a phenyl group.

The olefin polymerization method provided by the present invention can be used for homopolymerization of olefins, and can also be used for copolymerization of multiple olefins. The olefin is selected from at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 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 preparation of polyolefins, the various components of the catalyst of the present invention, namely the catalyst component provided by the present invention, the aluminum alkyl compound as a co-catalyst, and the optional external electron donor compound can be used before contacting the olefin monomer. Contact, which is called "pre-contact" or "pre-complexation" in the industry; the three components can also be added to the polymerization reactor separately for polymerization reaction, that is, "pre-contact" is not implemented. In the olefin polymerization method provided by the present invention, it is preferable to perform "pre-contact" of each component of the olefin polymerization catalyst. The time of "pre-contact" is 0.1-30 min, preferably 1-10 minutes; the temperature of "pre-contact" is -20°C to 80°C, preferably 10-50°C.

In some embodiments, the catalyst of the present invention is pre-polymerized to a certain extent in the presence of a small amount of olefin monomer to obtain a pre-polymerized catalyst, and then the pre-polymerized catalyst is further contacted with olefin monomer to react to obtain an olefin polymer. This technology is called "pre-polymerization" process in the industry, and it helps to increase the polymerization activity of the catalyst and the increase of the polymer bulk density. In the olefin polymerization method provided by the present invention, a "pre-polymerization" process may be used or not. Preferably, a "pre-polymerization" process is used.

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

Without being bound by any specific theory, it is believed that the precipitant a used in the present invention, that is, the isomers of specific optical configuration (R, R-configuration and/or S, S-configuration isomer) content is greater than 80 % Of the glycol ester can be more easily removed from the solid catalyst component, compared with the conventional corresponding glycol ester industrial products (R, R-configuration and/or S, S-configuration isomer content is usually 40 % Or so) compared to. Therefore, the solid catalyst component prepared according to the method of the present invention contains a relatively low residual precipitation aid, so as not to interfere with the function of the internal electron donor component.

Moreover, the inventors have discovered that the precipitation aid a is a glycol ester with a specific optical configuration of isomers (R, R-configuration and/or S, S-configuration isomers) content of more than 80% It can play a good role, so that the obtained catalyst component has a better particle shape.

In order to make the present invention easier to understand, the present invention will be described in detail below in conjunction with embodiments. These embodiments are only illustrative and do not limit the scope of the present invention.

The test methods used in the present invention are as follows: (1) The purity of the precipitant a glycol ester compound and the ratio of diastereomers are measured by an Acquity UPLC ultra-high performance liquid chromatograph from Waters, USA. (2) The configuration of the precipitant compound was determined by Brukerdmx nuclear magnetic resonance instrument (300MHz, solvent CDCl ₃ , internal standard TMS, measuring temperature 300K). (3) The content of the glycol ester compound in the catalyst component: It is determined by the Acquity UPLC ultra-high performance liquid chromatograph of American Waters Company. (4) Polymer melt index (MI): measured according to GB/T3682-2000. (5) Propylene polymer isotacticity index (II): Measured by heptane extraction method: 2 g of dried polymer sample is placed in an extractor and extracted with boiling heptane for 6 hours, and the remainder is dried The ratio of the polymer weight (g) to 2 (g) obtained to a constant weight is the isotacticity. (6) Calculation of activity (Ac): catalyst activity = (quality of prepared polyolefin)/(quality of catalyst solid component) kg/g; (7) Measurement of bulk density (BD): Put the prepared polymer powder in Free fall from a height of 10 cm in the funnel into a 100 mL container, weigh the polymer powder in the container as M g, and the polymer bulk density is M/100 g/cm ³ . (8) Polymer molecular weight distribution MWD (MWD=Mw/Mn): PL-GPC220 is used, with trichlorobenzene as the solvent, and measured at 150°C (standard sample: polystyrene, flow rate: 1.0 mL/min, column: 3 x Plgel 10 um MlxED-B 300 x 7.5 nm).

In the present invention, an ultra-high performance liquid chromatograph is used to adjust the separation conditions of liquid chromatography to make R, R-configuration and S, S-configuration diol esters and R, S-configuration diols The esters have different retention times to distinguish R,R-configuration and S,S-configuration glycol esters from R,S-configuration glycol esters. The specific separation conditions are: (1) Chromatographic column: ACQUITY UPLC BEH Shield RP18 (100 mm×2.1 mm, 1.7μm); (2) Column temperature: 35℃; (3) Mobile phase: 75% methanol, 25% ultrapure water; (4) Flow rate 0.3 mL/min; (5) PDA detection wavelength is 229 nm.

Under this condition, the retention time of the diol esters of the R, R-configuration and the S,S-configuration is the same and relatively short, and the retention time of the diol esters of the R,S-configuration is relatively long. At the same time, the configuration of diastereomers can also be judged according to the proton nuclear magnetic resonance spectrum signal peaks. Preparation examples

The synthesis method of the precipitant a glycol ester compound represented by the general formula (I) used in the examples is as follows. Compound 1: 2,4-pentanediol dibenzoate (R, R-configuration + S, S-configuration): R, S-configuration = 99.1:0.16 (1) R, R-2, Preparation of the mixture of 4-pentanediol and S,S-2,4-pentanediol Add 500g of 2,4-pentanediol to 1200mL of anhydrous ethyl ether, stir well, cool to -50°C, keep for 1-1.5 hours , The precipitated solid was collected by rapid filtration, and the obtained solid was continuously recrystallized with ether at -20°C, repeated three times to obtain 184.4 g of the final product with a purity of 99.4% (GC). ¹ H NMR (CDCl ₃ /TMS, 300MHz) δ (ppm): 1.202-1.258 (m, 6H, -CH(OH)C H ₃ ), 1.536-1.632 (m, 2H, -C H ₂ CH(OH) CH ₃ ), 4.048-4.211 (m, 2H, rac-C H (OH)CH ₃ ). (2) Synthesis of 2,4-pentanediol dibenzoate

259.3g of benzyl chloride was added to 500mL of toluene to obtain a benzyl chloride solution; 80g of the mixture of R,R-2,4-pentanediol and S,S-2,4-pentanediol prepared above, 152.3 g of anhydrous pyridine and 4.0 g of 4-dimethylaminopyridine were added to 100 mL of toluene, and after all the solids were dissolved, they were dropped into the benzyl chloride solution, keeping the temperature below 50°C. After the addition, the temperature was raised to 80°C for 4 hours, and the temperature was continued to reflux for 8 hours. After the reaction, the reaction mixture was cooled to room temperature, filtered, and part of the toluene was removed from the filtrate. The remaining filtrate was washed with an equal amount of 10% sodium carbonate solution with vigorous stirring until pH=12, and the organic phase was separated using saturated ammonium chloride. The solution was washed to pH=6-7, the organic phase was dried with anhydrous magnesium sulfate after liquid separation, the solvent was spin-dried after filtration, and the crude product was obtained by distillation under reduced pressure. The crude product was recrystallized with n-hexane at -20°C to obtain 142.7g of the final product , The purity is 99.26% (LC). Among them, the content of R,R-configuration and S,S-configuration isomer is 99.1%, and the ratio of diastereomers (R,R-configuration+S,S-configuration): R,S -Configuration = 99.1:0.16. ¹ H NMR (CDCl ₃ /TMS, 300MHz) δ (ppm): 1.397-1.418 (d, 6H, -CH(OCO)C H ₃ ), 2.074-2.116 (m, 2H, -C H ₂ CH(OCO) CH ₃ ), 5.287-5.350 (m, 2H, -CH ₂ C H (OCO)CH ₃ ), 7.253-7.987 (m, 5H, -C ₆ H ₅ ).

Compound 2: 3,5-Heptanediol Dibenzoate (R,R-configuration + S,S-configuration): R,S-configuration=96.3:1.0 (1) Preparation of mixture of R,R-3,5-heptanediol and S,S-3,5-heptanediol

Using a method similar to step (1) in the synthesis of compound 1, replace 2,4-pentanediol with 3,5-heptanediol to prepare R,R-3,5-heptanediol and S,S-3 The mixture of ,5-heptanediol is 181.3g, and the purity is 99.6% (GC).

¹ H NMR (CDCl ₃ /TMS, 300MHz) δ (ppm): 0.923-0.972 (m, 6H, -CH(OH)CH ₂ C H ₃ ), 1.476-1.589 (m, 4H, -CH ₂ CH(OH )C H ₂ CH ₃ ), 1.607-1.627 (m, 2H, -C H ₂ CH(OH)CH ₂ CH ₃ ), 3.815-3.909 (m, 2H, rac-C H (OH)CH ₃ ). (2) Synthesis of 3,5-heptanediol dibenzoate

Using a method similar to step (2) in the synthesis of compound 1, replace the mixture of R,R-2,4-pentanediol and S,S-2,4-pentanediol with the R,R-3, A mixture of 5-heptanediol and S,S-3,5-heptanediol, synthesized 3,5-heptanediol dibenzoate 142.7g, purity 97.3% (LC). Among them, the content of R, R-configuration and S, S-configuration isomers is 96.3%, and the ratio of diastereomers (R, R-configuration + S, S-configuration): R, S -Configuration = 96.3:1.0.

¹ H NMR (CDCl ₃ /TMS, 300MHz) δ (ppm): 0.933-0.983 (d, 6H, -CH(OCO)CH ₂ C H ₃ ), 1.737-1.785 (m, 4H, -CH ₂ CH(OCO )C H ₂ CH ₃ ), 2.062-2.103 (m, 2H, -C H ₂ CH(OCO)CH ₂ CH ₃ ), 5.194-5.275 (m, 2H, -CH ₂ C H (OCO)CH ₂ CH ₃ ), 7.243-7.981 (m, 5H, -C ₆ H ₅ ). Compound 3: 2,4-pentanediol dibenzoate (R, R-configuration + S, S-configuration): R, S-configuration=37:60

The compound is commercially available and used in the received form. The content of R,R-configuration and S,S-configuration isomers in this compound is 37%, and the ratio of diastereomers (R,R-configuration+S,S-configuration): R, S-configuration = 37:60. Compound 4: 3,5-Heptanediol dibenzoate (R, R-configuration + S, S-configuration): R, S-configuration=35:61

The compound is commercially available and used in the received form. The content of R,R-configuration and S,S-configuration isomers in this compound is 35%, and the ratio of diastereomers (R,R-configuration+S,S-configuration): R, S-configuration=35:61. Example 1 1. Preparation of catalyst components

(1) Preparation of magnesium chloride alkoxide solution: In a reactor that has been repeatedly replaced with high-purity nitrogen, add 1400 mL of isooctyl alcohol, 1400 mL of toluene, and 350 g of anhydrous magnesium chloride. The contents were reacted for 3.5 hours under the conditions of a stirring speed of 1300 rpm and a temperature of 115° C. to dissolve all the solids and form a uniform magnesium chloride alcoholate solution. Add 52.5 mL of tetrabutyl titanate, and react for 1.5 hours at a stirring speed of 1300 rpm and a temperature of 110° C., then add 1960 mL of toluene and keep the temperature constant for half an hour. Then, 140 mL of toluene and 45 g of compound 1 were added, and reacted for 0.5 hours at a stirring speed of 1300 rpm and a temperature of 50° C. and then cooled to room temperature to form a magnesium chloride alcoholate solution containing a precipitation aid.

(2) Preparation of catalyst components: The above-mentioned magnesium chloride alcoholate solution containing the precipitation aid was added dropwise to a reactor fully replaced by nitrogen and filled with 4200 mL of titanium tetrachloride and 2800 mL of toluene, and the addition time was 3 hours. After the addition is complete, stir the contents to fully react at -25°C for 0.5 hours, then increase the temperature to 110°C over 6 hours, and add 35g of 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether and 100mL of toluene, kept at 110°C, constant temperature for 2 hours, and then filtered to remove the liquid. Add 6300mL of toluene and 700mL of titanium tetrachloride to the obtained solid intermediate product. After stirring for 1 hour at 80°C, it was cooled to room temperature and filtered by pressure. The solid intermediate product was then added to 6300mL Toluene and 700mL titanium tetrachloride, heat to 80℃, add 112g 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether and 100mL toluene, keep the temperature for 1 hour, filter out the liquid, and obtain the solid The intermediate product was added with 5600 mL of toluene and 1400 mL of titanium tetrachloride, heated to 110° C., stirred for 1 hour, and the solid product obtained after filtering off the liquid was washed 4 times with 6000 mL of hexane and dried to obtain olefin polymerization catalyst component 1. 2. Propylene polymerization

The catalyst component 1 prepared above was subjected to propylene polymerization. The specific method is: in a 5L autoclave, after fully replacing gas phase propylene, add 5mL triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5mmol/mL), 1mL cyclohexyl at room temperature A hexane solution of methyldimethoxysilane (CHMMS) (the concentration of CHMMS is 0.10 mmol/mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst component 1. The polymerization reaction was carried out under two conditions, and the polymerization results are shown in Table 1: (1) 4.5 standard liters of hydrogen and 2L of liquid propylene; polymerize at 70°C for 1 hour, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. (2) 1.0 standard liter of hydrogen and 2L of liquid propylene; polymerize at 70°C for 2 hours, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. Example 2

The preparation of the catalyst component is the same as that in Example 1, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 2.

The propylene polymerization method is the same as that in Example 1, except that the catalyst component 1 is replaced with the catalyst component 2, and the polymerization results are shown in Table 1. Example 3 1. Preparation of catalyst components

(1) Preparation of magnesium chloride solution: Add 350g of anhydrous magnesium chloride, 4667mL of toluene, 576mL of epichlorohydrin, and 649mL of tributyl phosphate in a reactor that has been repeatedly replaced by high-purity nitrogen at room temperature. The stirring speed is 1300rpm and the temperature is increased. To 55°C, react for 3.0 hours to dissolve all the solids and form a uniform magnesium chloride solution.

(2) Preparation of catalyst components: the magnesium chloride solution was cooled to -28°C, 4100mL titanium tetrachloride, 290mL toluene, 58g compound 1, 36g 2-isopropyl-2-isopentyl-1,3-propanediol Dimethyl ether was added dropwise to the above magnesium chloride solution. After the dripping is completed, the reaction mixture is stirred to fully react at -28°C for 1.0 hour, and then the temperature is increased to 80°C over 4.5 hours, and the liquid is removed by pressure filtration after a constant temperature of 1.5 hours, and 8750 mL of toluene is added to wash and wash twice. Add 51g of 2-isopropyl-2-isopentyl-1,3-propanediol dimethyl ether and 6560mL of toluene, keep at 80°C for 1 hour, add 4375mL of titanium tetrachloride, heat to 110°C and stir for 1 hour, press Filter to remove the liquid. 4200mL toluene and 2800mL titanium tetrachloride were added, stirred for 1 hour, and filtered to remove the liquid. 4200 mL of toluene and 2800 mL of titanium tetrachloride were added, stirred for 1 hour, and the solid obtained after removing the liquid by pressure filtration was washed 5 times with 6000 mL of hexane and dried to obtain an olefin polymerization catalyst component 3. 2. Propylene polymerization

The catalyst component 3 prepared above was subjected to propylene polymerization. The specific method is: in a 5L autoclave, after fully replacing gas phase propylene, add 5mL triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5mmol/mL), 1mL cyclohexyl at room temperature A hexane solution of methyldimethoxysilane (CHMMS) (the concentration of CHMMS is 0.10 mmol/mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst component 3. The polymerization reaction was carried out under two conditions, and the polymerization results are shown in Table 1: (1) 4.5 standard liters of hydrogen and 2L of liquid propylene; polymerize at 70°C for 1 hour, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. (2) 1.0 standard liter of hydrogen and 2L of liquid propylene; polymerize at 70°C for 2 hours, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. Example 4

The preparation of the catalyst component is the same as that in Example 3, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 4.

The propylene polymerization method is the same as that in Example 3, except that the catalyst component 3 is replaced with the catalyst component 4. The polymerization results are shown in Table 1. Comparative example 1

The preparation of the catalyst component is the same as that of Example 1, except that in step (1), compound 1 is replaced with compound 3 to prepare catalyst component C1.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component C1, and the polymerization results are shown in Table 1. Comparative example 2

The preparation of the catalyst component is the same as that in Example 1, except that in step (1), compound 1 is replaced with compound 4 to prepare catalyst component C2.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component C2. The polymerization results are shown in Table 1. Comparative example 3

The preparation of the catalyst component is the same as that of Example 3, except that in step (1), compound 1 is replaced with compound 3 to prepare a catalyst component C3.

The propylene polymerization method is the same as in Example 3, except that the catalyst component 3 is replaced with the catalyst component C3. The polymerization results are shown in Table 1. Comparative example 4

The preparation of the catalyst component is the same as that of Example 3, except that in step (1), compound 1 is replaced with compound 4 to prepare catalyst component C4.

The propylene polymerization method is the same as in Example 3, except that the catalyst component 3 is replaced with the catalyst component C4. The polymerization results are shown in Table 1. Table 1 catalyst Glycol ester content wt% A: B ^* Polymerization conditions Ac kgPP/gcat BD g/cm ³ MI g/10min II% MWD Example 1 0.16 0.08:0.09 4.5L/1h 72.7 0.42 41.3 97.9 4.5 1.0L/2h 84.7 0.42 2.84 99.8 Example 2 0.11 0.04:0.06 4.5L/1h 74.6 0.44 44.6 98.0 4.6 1.0L/2h 88.3 0.47 3.29 99.3 Example 3 0.17 4.5L/1h 72.0 0.43 32.9 97.8 4.7 1.0L/2h 85.1 0.43 3.16 99.3 Example 4 0.14 4.5L/1h 74.7 0.43 38.1 97.9 4.6 1.0L/2h 86.1 0.44 2.76 99.2 Comparative example 1 4.10 0.10:4.00 4.5L/1h 70.5 0.42 46.6 97.8 6.9 1.0L/2h 78.3 0.42 3.14 99.2 Comparative example 2 3.81 0.08:3.73 4.5L/1h 71.6 0.43 42.7 97.8 6.7 1.0L/2h 82.7 0.44 2.99 99.0 Comparative example 3 4.61 4.5L/1h 70.6 0.44 31.4 97.2 6.8 1.0L/2h 79.1 0.44 2.96 98.9 Comparative example 4 4.19 4.5L/1h 71.1 0.43 35.9 97.4 6.6 1.0L/2h 80.3 0.43 2.61 99.0 ^* A:B=(R,R-configuration+S,S-configuration): (R,S-configuration)

It can be seen from the information in Table 1 that when the R, R- and S, S-configuration glycol ester compounds are used as the precipitation aid in the preparation of the catalyst component, the catalyst component obtained has two precipitation aids. The content of alcohol ester is extremely low, but it still maintains high activity and stereospecificity, and the prepared polypropylene has a narrow molecular weight distribution. It has been observed that the particle morphology of the polypropylene powder is good, indicating that the particle morphology of the catalyst component is good. Example 5 1. Preparation of catalyst components

(1) Preparation of magnesium chloride alkoxide solution: In a reactor that has been repeatedly replaced by high-purity nitrogen, add 1400 mL of isooctyl alcohol, 1400 mL of toluene, and 350 g of anhydrous magnesium chloride in sequence, so that the contents are stirred at a speed of 1300 rpm and a temperature of 115°C. Under the conditions, react for 3.5 hours to dissolve all the solids to form a uniform magnesium chloride alcoholate solution. Add 52.5 mL of tetrabutyl titanate, and react for 1.5 hours at a stirring speed of 1300 rpm and a temperature of 110° C., then add 1960 mL of toluene and keep the temperature constant for half an hour. Then, 140 mL of toluene and 45 g of compound 1 were added, and reacted for 0.5 hours at a stirring speed of 1300 rpm and a temperature of 50° C. and then cooled to room temperature to form a magnesium chloride alcoholate solution containing a precipitation aid.

(2) Preparation of catalyst components: The above-mentioned magnesium chloride alcoholate solution containing the precipitation aid was added dropwise to a reactor fully replaced by nitrogen and filled with 4200 mL of titanium tetrachloride and 2800 mL of toluene, and the addition time was 3 hours. After the addition is complete, the reaction mixture is stirred to fully react at -25°C for 0.5 hours, and then the temperature is raised to 110°C over 6 hours, and 35g of diethyl 2-cyano-2,3-diisopropylsuccinate and 100mL of toluene are added. , Keep at 110℃, keep constant temperature for 2 hours, then filter out the liquid, add 6300mL toluene and 700mL titanium tetrachloride to the obtained solid intermediate product, stir at 80℃ for 1 hour, then cool to room temperature and press filter, add 6300mL solid intermediate product Toluene and 700 mL of titanium tetrachloride, heat to 80°C, add 112 g of 2-cyano 2,3-diisopropyl succinate diethyl and 100 mL of toluene, keep the temperature for 1 hour, filter out the liquid, and obtain the solid middle The product was added with 5600 mL of toluene and 1400 mL of titanium tetrachloride, heated to 110° C., stirred for 1 hour, filtered to remove the liquid, and the obtained solid product was washed 4 times with 6000 mL of hexane and dried to obtain olefin polymerization catalyst component 5. 2. Propylene polymerization

The catalyst component 5 prepared above was subjected to propylene polymerization. The specific method is: in a 5L autoclave, after fully replacing gas phase propylene, add 5mL triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 1mL cyclohexyl at room temperature A hexane solution of methyldimethoxysilane (CHMMS) (the concentration of CHMMS is 0.10 mmol/mL), 10 mL of anhydrous hexane, and 10 mg of solid catalyst component 5. The polymerization reaction was carried out under two conditions, and the polymerization results are shown in Table 2: (1) 4.5 standard liters of hydrogen and 2L of liquid propylene; polymerize at 70°C for 1 hour, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. (2) 1.0 standard liter of hydrogen and 2L of liquid propylene; polymerize at 70°C for 2 hours, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. Example 6

The preparation of the catalyst components is the same as in Example 5, the difference is that in step (2), 35 g of diethyl 2-cyano 2,3-diisopropyl succinate is replaced with 35 g of di-n-phthalate. Butyl ester (DNBP), catalyst component 6 was prepared.

The propylene polymerization method is the same as in Example 5, except that the catalyst component 5 is replaced with the catalyst component 6. The polymerization results are shown in Table 2. Example 7

The preparation of the catalyst component is the same as that in Example 5, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 7.

The propylene polymerization method is the same as in Example 5, except that the catalyst component 5 is replaced with the catalyst component 7. The polymerization results are shown in Table 2. Example 8

The preparation of the catalyst component is the same as in Example 5, except that in step (1), compound 1 is replaced with compound 2, and in step (2), 35 g of 2-cyano 2,3-diisopropylbutyl Diethyl diacid was replaced with 35 g of di-n-butyl phthalate (DNBP), and catalyst component 8 was prepared.

The propylene polymerization method is the same as that in Example 5, except that the catalyst component 5 is replaced with the catalyst component 8. The polymerization results are shown in Table 2. Example 9 1. Preparation of catalyst components

(1) Preparation of magnesium chloride solution: Add 350g of anhydrous magnesium chloride, 4667mL of toluene, 576mL of epichlorohydrin, and 649mL of tributyl phosphate into a reactor that has been repeatedly replaced by high-purity nitrogen at room temperature. The stirring speed is 1300rpm and the temperature is increased. To 55°C, react for 3.0 hours to dissolve all the solids and form a uniform magnesium chloride solution.

(2) Preparation of catalyst components: the magnesium chloride solution was cooled to -28°C, and then 4100mL of titanium tetrachloride, 290mL of toluene, 58g of compound 1, 36g of 2-cyano-2,3-diisopropyl succinate The ethyl ester was added dropwise to the above magnesium chloride solution. After the dropwise addition is completed, the reaction mixture is stirred to fully react at -28°C for 1.0 hour, then the temperature is increased to 80°C over 4.5 hours, and the liquid is removed by pressure filtration after constant temperature for 1.5 hours. Add 8750 mL of toluene to the solid and wash it twice. Add 51g of diethyl 2-cyano-2,3-diisopropylsuccinate and 6560mL of toluene, keep the temperature at 80℃ for 1 hour, then add 4375mL of titanium tetrachloride, heat to 110℃, stir for 1 hour, and filter to remove the liquid . 4200mL toluene and 2800mL titanium tetrachloride were added, stirred for 1 hour, and filtered to remove the liquid. 4200 mL of toluene and 2800 mL of titanium tetrachloride were added, stirred for 1 hour, and the solid obtained after removing the liquid by pressure filtration was washed 5 times with 6000 mL of hexane and dried to obtain olefin polymerization catalyst component 9. 2. Propylene polymerization

The catalyst component 9 prepared above was subjected to propylene polymerization. The specific method is: in a 5L autoclave, after fully replacing gas phase propylene, add 5mL triethylaluminum hexane solution (the concentration of triethylaluminum is 0.5 mmol/mL), 1mL cyclohexyl at room temperature A hexane solution of methyldimethoxysilane (CHMMS) (the concentration of CHMMS is 0.10 mmol/mL), 10 mL of anhydrous hexane and 10 mg of solid catalyst component 9. The polymerization reaction was carried out under two conditions, and the polymerization results are shown in Table 2: (1) 4.5 standard liters of hydrogen and 2L of liquid propylene; polymerize at 70°C for 1 hour, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. (2) 1.0 standard liter of hydrogen and 2L of liquid propylene; polymerize at 70°C for 2 hours, stop stirring, remove unpolymerized propylene monomer, and collect the polymer. Example 10

The preparation of the catalyst components is the same as in Example 9, except that in step (2), 36 g of diethyl 2-cyano 2,3-diisopropyl succinate is replaced with 36 g of di-n-phthalate. Butyl ester (DNBP), catalyst component 10 was prepared.

The propylene polymerization method is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component 10. The polymerization results are shown in Table 2. Example 11

The preparation of the catalyst component is the same as in Example 9, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 11.

The method of propylene polymerization is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component 11. The polymerization results are shown in Table 2. Example 12

The preparation of the catalyst components is the same as that of Example 9, except that in step (1), compound 1 is replaced with compound 2, and in step (2), 36 g of 2-cyano 2,3-diisopropylbutyl Diethyl diacid was replaced with 36 g of di-n-butyl phthalate (DNBP), and catalyst component 12 was prepared.

The propylene polymerization method is the same as in Example 9, except that the catalyst component 9 is replaced with the catalyst component 12. The polymerization results are shown in Table 2. Comparative example 5

The preparation of the catalyst component is the same as that of Example 5, except that in step (1), compound 1 is replaced with compound 3 to prepare catalyst component C5.

The propylene polymerization method is the same as in Example 5, except that the catalyst component 5 is replaced with the catalyst component C5. The polymerization results are shown in Table 2. Comparative example 6

The preparation of the catalyst component is the same as that of Example 6, except that in step (1), compound 1 is replaced with compound 3 to prepare catalyst component C6.

The propylene polymerization method is the same as that in Example 6, except that the catalyst component 6 is replaced with the catalyst component C6. The polymerization results are shown in Table 2. Comparative example 7

The preparation of the catalyst component is the same as that in Example 7, except that in step (1), compound 1 is replaced with compound 4 to prepare catalyst component C7.

The propylene polymerization method is the same as in Example 7, except that the catalyst component 7 is replaced with the catalyst component C7. The polymerization results are shown in Table 2. Comparative example 8

The preparation of the catalyst component is the same as that of Example 8, except that in step (1), compound 1 is replaced with compound 4 to prepare catalyst component C8.

The propylene polymerization method is the same as in Example 8, except that the catalyst component 8 is replaced with the catalyst component C8. The polymerization results are shown in Table 2. Comparative example 9

The preparation of the catalyst component is the same as that of Example 9, except that in step (1), compound 1 is replaced with compound 3 to prepare a catalyst component C9.

The propylene polymerization method is the same as that in Example 9, except that the catalyst component 9 is replaced with the catalyst component C9. The polymerization results are shown in Table 2. Comparative example 10

The preparation of the catalyst component is the same as that of Example 10, except that in step (1), compound 1 is replaced with compound 3 to prepare a catalyst component C10.

The propylene polymerization method is the same as that of Example 10, except that the catalyst component 10 is replaced with the catalyst component C10. The polymerization results are shown in Table 2. Comparative example 11

The preparation of the catalyst component is the same as that of Example 11, except that in step (1), the compound 1 is replaced with the compound 4 to prepare the catalyst component C11.

The propylene polymerization method is the same as that in Example 11, except that the catalyst component 11 is replaced with the catalyst component C11. The polymerization results are shown in Table 2. Comparative example 12

The preparation of the catalyst component is the same as that of Example 12, except that in step (1), compound 1 is replaced with compound 4 to prepare a catalyst component C12.

The propylene polymerization method is the same as in Example 12, except that the catalyst component 12 is replaced with the catalyst component C12. The polymerization results are shown in Table 2. Table 2 catalyst Glycol ester content wt% A: B ^* Polymerization conditions Ac kgPP/gcat BD g/cm ³ MI g/10min II% MWD Example 5 0.17 0.08:0.09 4.5L/1h 63.9 0.42 7.40 96.6 12.8 1.0L/2h 72.8 0.42 0.94 97.6 Example 6 0.18 4.5L/1h 71.4 0.42 9.06 96.7 11.9 1.0L/2h 80.8 0.42 1.98 97.4 Example 7 0.17 0.08:0.09 4.5L/1h 67.2 0.42 7.20 96.8 12.5 1.0L/2h 76.4 0.42 0.92 97.7 Example 8 0.10 4.5L/1h 74.3 0.42 8.89 97.0 11.8 1.0L/2h 82.8 0.42 1.36 97.8 Example 9 0.18 0.06:0.12 4.5L/1h 62.8 0.43 8.20 97.4 12.7 1.0L/2h 76.2 0.43 0.98 98.1 Example 10 0.15 4.5L/1h 66.4 0.43 9.52 97.4 11.6 1.0L/2h 79.2 0.43 1.24 98.3 Example 11 0.11 0.04:0.07 4.5L/1h 65.2 0.42 7.35 97.6 12.4 1.0L/2h 78.2 0.43 0.98 98.4 Example 12 0.13 4.5L/1h 65.5 0.43 7.17 97.6 11.5 1.0L/2h 78.3 0.43 0.91 98.6 Comparative example 5 4.09 0.10:3.99 4.5L/1h 60.4 0.41 8.30 96.0 10.6 1.0L/2h 68.5 0.42 0.82 97.1 Comparative example 6 3.62 4.5L/1h 70.5 0.42 9.64 96.2 10.3 1.0L/2h 79.2 0.42 2.19 97.5 Comparative example 7 3.45 0.10:3.35 4.5L/1h 68.4 0.41 8.25 95.7 10.7 1.0L/2h 74.7 0.42 1.21 97.0 Comparative example 8 3.92 4.5L/1h 71.7 0.42 9.11 96.7 10.2 1.0L/2h 78.2 0.43 1.08 97.4 Comparative example 9 3.89 4.5L/1h 60.1 0.44 7.31 97.4 10.8 1.0L/2h 75.3 0.43 0.81 98.2 Comparative example 10 4.12 0.08:4.04 4.5L/1h 64.5 0.43 8.13 97.2 10.0 1.0L/2h 77.1 0.43 1.06 98.3 Comparative example 11 4.13 4.5L/1h 63.4 0.43 8.21 96.8 10.5 1.0L/2h 77.0 0.43 1.29 97.9 Comparative example 12 3.53 0.07:3.46 4.5L/1h 63.7 0.42 8.94 97.3 10.0 1.0L/2h 77.4 0.43 1.47 98.0 ^* A:B=(R,R-configuration+S,S-configuration): (R,S-configuration)

It can be seen from the data in Table 2 that when R, R- and S, S-configuration glycol ester compounds are used as the precipitation aid in the preparation of the catalyst component, the obtained catalyst component contains the glycol ester as the precipitation aid. The content is extremely low, but the catalyst components still have high activity and stereospecific ability, and the prepared polypropylene has a wide molecular weight distribution. It has been observed that the particle morphology of the polypropylene powder is good, indicating that the particle morphology of the catalyst component is good. Example 13 1. Preparation of catalyst components

(1) Preparation of magnesium chloride alkoxide solution: Add 1400mL isooctyl alcohol, 1400mL toluene, and 350g anhydrous magnesium chloride in a reactor that has been repeatedly replaced by high-purity nitrogen, and the contents are stirred at 1300rpm at a temperature of 115℃. Under the conditions of 3.5 hours, the solids were dissolved to form a uniform magnesium chloride alcoholate solution. Add 52.5 mL of tetrabutyl titanate, and react for 1.5 hours at a stirring speed of 1300 rpm and a temperature of 110° C., then add 1960 mL of toluene and keep the temperature constant for half an hour. Then, 140 mL of toluene and 45 g of compound 1 were added, and reacted for 0.5 hours at a stirring speed of 1300 rpm and a temperature of 50° C. and then cooled to room temperature to form a magnesium chloride alcoholate solution containing a precipitation aid.

(2) Preparation of the catalyst components: the above-mentioned magnesium chloride alcoholate solution containing the precipitation aid was added dropwise to a reactor fully replaced by nitrogen and filled with 4200mL of titanium tetrachloride and 2800mL of toluene. The addition time was 3 hours. After the addition is complete, stir the reaction mixture to fully react at -25°C for 0.5 hours, and then heat up to 110°C over 6 hours, add 35g di-n-butyl phthalate and 100mL toluene, keep at 110°C, and filter at constant temperature for 2 hours. Remove the liquid, add 6300mL toluene and 700mL titanium tetrachloride to the obtained solid intermediate product, stir at 80°C for 1 hour, then cool to room temperature and press filter, add 6300mL toluene and 700mL titanium tetrachloride to the solid intermediate product, and heat up to 80°C , Add 112g of di-n-butyl phthalate and 100mL of toluene, filter to remove the liquid after constant temperature for 1 hour, add 5600mL of toluene and 1400mL of titanium tetrachloride to the obtained solid intermediate product, heat up to 110℃, stir for 1 hour, filter to remove the liquid The resulting solid product was washed 4 times with 6000 mL of hexane and dried to obtain an olefin polymerization catalyst component 13. 2. Propylene polymerization

The catalyst component 13 prepared above was subjected to propylene polymerization as in Example 1. The polymerization results are shown in Table 3. 3. Preparation of impact copolymer polypropylene

The polymerization reaction is carried out on a horizontal gas phase polypropylene pilot plant. The polymerization reactor is two horizontal stirring reactors connected in series. The polymerization method and steps are as follows: The catalyst component 13, triethylaluminum, and isobutyl dimethoxysilane are continuously added to the horizontal stirred reactor from the front end of the first stirred reactor under the carrying of propylene, and polymerized under the gas phase conditions to produce homopolymerization. For polypropylene, the reaction heat is taken away by the sprayed propylene vaporization. The produced polymer is discharged from the end of the stirred tank. The catalyst and the polymer move in the reactor in a manner close to plug flow. The polymerization temperature is 66°C or the specified temperature, and the reaction pressure is 2.3 MPa.

The homopolypropylene is discharged from the first reactor, and the polymer is transferred to the second horizontal stirred reactor by means of a transfer device between the two reactors. The polymer enters from the front end of the second stirred tank and polymerizes under the condition of introducing ethylene to produce impact-resistant copolymerized polypropylene, and the reaction heat is taken away by the sprayed propylene vaporization. During the polymerization procedure, the molar ratio of ethylene to propylene was maintained at 0.38-0.40. The produced polymer is discharged from the end of the stirred tank. The catalyst and polymer move in the reactor in a manner close to the plug flow. The polymerization temperature is 66°C or the specified temperature, and the reaction pressure is 2.2 MPa. After the polymer obtained by the reaction was degassed and deactivated by wet nitrogen, a polyimpact copolymer polypropylene was obtained. The polymerization results are shown in Table 4. Example 14

The preparation of the catalyst component is the same as that of Example 13, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 14.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component 14. The polymerization results are shown in Table 3.

The preparation method of impact copolymerized polypropylene is the same as that of Example 13, except that the catalyst component 13 is replaced with the catalyst component 14. The polymerization results are shown in Table 4. Example 15

The preparation of the catalyst component is the same as in Example 13, except that in step (1), compound 1 is replaced with compound 2, and in step (2), di-n-butyl phthalate (DNBP) is replaced with ortho Diisobutyl phthalate (DIBP) was prepared to obtain catalyst component 15.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component 15. The polymerization results are shown in Table 3.

The preparation method of impact copolymerized polypropylene is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component 15. The polymerization results are shown in Table 4. Example 16 1. Preparation of catalyst components

(1) Preparation of magnesium chloride solution: Add 350g of anhydrous magnesium chloride, 4667mL of toluene, 576mL of epichlorohydrin, and 649mL of tributyl phosphate into a reactor that has been repeatedly replaced by high-purity nitrogen at room temperature. The stirring speed is 1300rpm and the temperature is increased. To 55°C, react for 3.0 hours to dissolve all the solids and form a uniform magnesium chloride solution.

(2) Preparation of catalyst components: the magnesium chloride solution was cooled to -28°C, and then 4100 mL of titanium tetrachloride, 290 mL of toluene, 58 g of compound 1, and 36 g of di-n-butyl phthalate were added dropwise to the above magnesium chloride solution. After the dripping is completed, the reaction mixture is stirred to fully react at -28°C for 1.0 hour, and then the temperature is increased to 80°C over 4.5 hours, and the liquid is removed by pressure filtration after a constant temperature of 1.5 hours, and 8750 mL of toluene is added to wash and wash twice. Add 51 g of di-n-butyl phthalate and 6560 mL of toluene, maintain a constant temperature of 80°C for 1 hour, add 4375 mL of titanium tetrachloride, raise the temperature to 110°C, stir for 1 hour, and remove the liquid by pressure filtration. 4200mL toluene and 2800mL titanium tetrachloride were added, stirred for 1 hour, and filtered to remove the liquid. 4200 mL of toluene and 2800 mL of titanium tetrachloride were added, stirred for 1 hour, and the solid obtained after removing the liquid by pressure filtration was washed 5 times with 6000 mL of hexane and dried to obtain olefin polymerization catalyst component 16. 2. Propylene polymerization

The catalyst component 16 prepared above was combined with propylene as in Example 1. The polymerization results are shown in Table 3. 3. Preparation of impact copolymer polypropylene

The above-prepared catalyst component 16 was used to prepare impact copolymer polypropylene as in Example 13. The polymerization results are shown in Table 4. Example 17

The preparation of the catalyst component is the same as that of Example 16, except that in step (1), compound 1 is replaced with compound 2 to prepare catalyst component 17.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component 17. The polymerization results are shown in Table 3.

The preparation method of impact copolymer polypropylene is the same as that of Example 13, except that the catalyst component 13 is replaced with the catalyst component 17. The polymerization results are shown in Table 4. Example 18

The preparation of the catalyst component is the same as 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 ortho Diisobutyl phthalate (DIBP), catalyst component 18 was prepared.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component 18. The polymerization results are shown in Table 31.

The preparation method of impact copolymerized polypropylene is the same as that of Example 13, except that the catalyst component 13 is replaced with the catalyst component 18. The polymerization results are shown in Table 4. Comparative example 13

The preparation of the catalyst component is the same as that in Example 13, except that in step (1), compound 1 is replaced with compound 3 to prepare a catalyst component C13.

The propylene polymerization method is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component C13. The polymerization results are shown in Table 3.

The preparation method of impact copolymer polypropylene is the same as that of Example 13, except that the catalyst component 13 is replaced with the catalyst component C13. The polymerization results are shown in Table 4. Comparative example 14

The preparation of the catalyst component is the same as that of Example 14, except that in step (1), compound 2 is replaced with compound 4 to prepare catalyst component C14.

The propylene polymerization method is the same as in Example 13, except that the catalyst component 13 is replaced with the catalyst component C14. The polymerization results are shown in Table 3.

The preparation method of impact-resistant copolymerized polypropylene is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component C14. The polymerization results are shown in Table 4. Comparative example 15

The preparation of the catalyst component is the same as that of Example 16, except that in step (1), compound 1 is replaced with compound 3 to prepare a catalyst component C15.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component C15. The polymerization results are shown in Table 3.

The preparation method of impact-resistant copolymerized polypropylene is the same as that of Example 13, except that the catalyst component 13 is replaced with the catalyst component C15. The polymerization results are shown in Table 4. Comparative example 16

The preparation of the catalyst component is the same as that in Example 17, except that in step (1), compound 2 is replaced with compound 4 to prepare a catalyst component C16.

The propylene polymerization method is the same as in Example 1, except that the catalyst component 1 is replaced with the catalyst component C16. The polymerization results are shown in Table 3.

The preparation method of impact-resistant copolymerized polypropylene is the same as that in Example 13, except that the catalyst component 13 is replaced with the catalyst component C16. The polymerization results are shown in Table 4. table 3 catalyst Glycol ester content wt% A:B ^* Polymerization conditions Ac kgPP/gcat BD g/cm ³ MI g/10min II% Example 13 0.12 0.05:0.07 4.5L/1h 71.4 0.43 24.7 97.6 1.0L/2h 82.2 0.43 6.01 98.5 Example 14 0.13 0.06:0.07 4.5L/1h 71.0 0.44 21.2 97.5 1.0L/2h 89.4 0.44 5.50 98.8 Example 15 0.10 4.5L/1h 69.1 0.42 31.8 97.5 1.0L/2h 78.2 0.43 5.73 98.6 Example 16 0.19 0.09:0.10 4.5L/1h 68.0 0.42 22.6 97.5 1.0L/2h 80.1 0.42 5.38 98.3 Example 17 0.18 4.5L/1h 69.8 0.42 23.0 97.7 1.0L/2h 81.2 0.42 6.46 98.6 Example 18 0.16 0.07:0.09 4.5L/1h 66.3 0.41 26.8 97.3 1.0L/2h 79.6 0.42 5.96 98.2 Comparative example 13 4.28 0.10:4.18 4.5L/1h 68.0 0.42 23.6 97.4 1.0L/2h 76.9 0.43 5.41 98.2 Comparative example 14 3.92 0.08:3.84 4.5L/1h 71.2 0.41 20.2 97.2 1.0L/2h 82.5 0.42 3.68 98.3 Comparative example 15 3.88 4.5L/1h 65.4 0.42 22.4 97.5 1.0L/2h 77.8 0.42 6.01 98.0 Comparative example 16 4.17 4.5L/1h 66.4 0.41 21.9 97.1 1.0L/2h 78.6 0.42 4.73 98.2 ^* A:B=(R,R-configuration+S,S-configuration): (R,S-configuration) Table 4 ^a catalyst Ac kgPP/gcat BD g/cm3 MI g/10min 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= is the total ethylene content in the copolymer polypropylene, RCC2 is the ethylene content in the rubber phase, and RC is the rubber phase content in the copolymer polypropylene.

It can be seen from the data in Table 3 that when R, R- and S, S-configuration glycol ester compounds are used as the precipitation aid in the preparation of the catalyst component, the obtained catalyst component contains the glycol ester as the precipitation aid. The content is extremely low, while the catalyst component shows high polymerization activity and high stereospecificity. It has been observed that the particle morphology of the polypropylene powder is good, indicating that the particle morphology of the catalyst component is good.

It can be seen from the data in Table 4 that when the catalyst component of the present invention is used to prepare impact copolymerized polypropylene, under the same ethylene/propylene molar ratio, the ethylene content in the prepared copolymerized polypropylene and the ethylene content in the rubber phase are higher. High, indicating that the catalyst of the present invention has better copolymerization ability.

Although the illustrative embodiments of the present invention have been specifically described, it should be understood that various other modifications are obvious to those skilled in the art and can be easily made by those skilled in the art without departing from the invention. Spirit and scope. Therefore, it is not intended to limit the scope of the appended patent application to the examples and descriptions set forth herein, but the scope of the patent application should be understood to include all the features of patent novelty existing in the present invention, including All features regarded as equivalents by those skilled in the art to which this invention belongs. The present invention has been described above in conjunction with many embodiments and specific examples. Considering the above detailed description, many variations are obvious to those skilled in the art. All such various modifications are within the scope of the entire intent of the scope of the attached patent application.

In this disclosure, when a composition, element or element group is preceded by the transitional phrase "comprises", it should be understood that we also think of the same composition, element or element group, where the composition, element or element group is preceded by The transitional phrase "basically composed of", "consisting of", "selected from the group consisting of" or "is" leads, and vice versa.

Claims (12)

A catalyst component for olefin polymerization, comprising magnesium, titanium, halogen, an internal electron donor compound and a precipitation aid, wherein the precipitation aid includes at least one precipitation aid a represented by general formula (I);

(I) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl or C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₆ -C ₂₀ aryl groups Or a C ₇ -C ₂₀ aralkyl group, and wherein based on the total weight of the catalyst components, the content of the precipitation assistant a is less than 1.0wt%; the precipitation assistant a represented by the general formula (I) contains the general formula (Ia) and/or isomers represented by general formula (Ib):

(Ia) (Ib). The catalyst component according to item 1 of the scope of patent application, wherein in the general formula (I), R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl groups, C _3- C ₈ cycloalkyl and C ₆ -C ₈ aryl; preferably R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₄ alkyl; R ₃ and R ₄ are each independently Selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl and C ₆ -C ₁₀ aryl; preferably R ₃ and R ₄ are each independently selected from substituted or unsubstituted Substituted C ₅ -C ₁₀ alkyl groups, C ₅ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ aryl groups, and C ₇ -C ₁₀ aralkyl groups. The catalyst component according to any one of item 1 of the scope of patent application and item 2 of the scope of patent application, wherein, based on the total weight of the catalyst component, the content of the precipitation promoter a is less than 0.5 wt%, more preferably Less than 0.2wt%. The catalyst component according to any one of items 1 to 3 in the scope of the patent application, wherein the precipitation assistant further includes the precipitation assistant b represented by the general formula (II); Ti(OR ₇ ) _n X _4-n (II) wherein each R _{7 is} independently selected from C ₁ -C ₁₀ alkyl and C ₃ -C ₁₀ cycloalkyl, each X is halogen and n is 1, 2, 3 or 4. The catalyst component according to any one of items 1 to 4 in the scope of the patent application, wherein the internal electron donor compound contains at least one selected from the group consisting of: 2, as represented by general formula (III), 2-Dihydrocarbyl-1,3-propanediol dimethyl ether compounds:

(III) Wherein, R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl, C ₃ -C ₁₀ cycloalkyl, C ₆ -C ₁₀ aryl and C ₇ -C ₁₀ alkylaryl; preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ Aryl; more preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl and phenyl; R ₅ and R _{6 are} optionally connected to form a ring; as in the general formula (III' ) The 2-cyano-2,3-dihydrocarbyl diethyl succinate compounds shown:

(III') wherein R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ aryl groups, and C ₇ -C ₁₀ aralkyl; preferably R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ More preferably, R ₅ and R ₆ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl groups and phenyl groups; and phthalate esters represented by general formula (III") Compound:

(III") wherein R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ aryl groups, and C ₇ -C ₁₀ alkylaryl; preferably R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₈ alkyl, C ₃ -C ₈ cycloalkyl and C ₆ -C ₈ The aryl group; more preferably R ₇ and R ₈ are each independently selected from substituted or unsubstituted C ₁ -C ₆ alkyl groups. The catalyst component according to any one of the first to the fifth in the scope of patent application, wherein, based on the total weight of the catalyst component, the content of the titanium is 1.0wt%-8.0wt%, preferably 1.6wt% -6.0wt%; the magnesium content is 10.0wt%-70.0wt%, preferably 15.0wt%-40.0wt%; the halogen content is 20.0wt%-90.0wt%, preferably 30.0wt%-85.0 wt%; the content of the internal electron donor compound is 2.0wt%-30.0wt%, preferably 3.0wt%-20.0wt%. The catalyst component according to item 1 of the scope of the patent application, wherein the catalyst component includes a magnesium compound, a titanium compound, at least one internal electron donor compound, and at least one precipitation promoter represented by the general formula (I) a The reaction product of the precipitation aid agent; Wherein, per mole of magnesium compound, the amount of the precipitation assistant a is 0.005-0.3 moles, preferably 0.01-0.05 moles, and the precipitation assistant a is greater than 80wt% based on the total weight of the precipitation assistant a. Preferably more than 90wt%, more preferably more than 95wt%, still more preferably more than 98wt% contains the isomers as shown in general formula (Ia) and/or general formula (Ib). A method for preparing a catalyst component for olefin polymerization, the method comprising the following steps: (1) Dissolving a magnesium compound in a solvent system to form a magnesium-containing compound solution; (2) From the magnesium-containing compound solution in the presence of a precipitation aid Precipitate particulate magnesium-containing solids, wherein the precipitation aid includes at least one precipitation aid a represented by the general formula (I);

(I) wherein R ₁ and R ₂ are each independently selected from substituted or unsubstituted C ₁ -C ₁₀ alkyl groups, C ₃ -C ₁₀ cycloalkyl groups, C ₆ -C ₁₀ aryl groups, and C ₇ -C ₁₀ aralkyl group; R ₃ and R ₄ are each independently selected from substituted or unsubstituted C ₁ -C ₂₀ alkyl groups, C ₃ -C ₂₀ cycloalkyl groups, C ₆ -C ₂₀ aryl groups And C ₇ -C ₂₀ aralkyl groups; wherein the precipitation aid a represented by the general formula (I) is contained in an amount greater than 80wt%, preferably greater than 90wt%, more preferably greater than 95wt%, still more preferably greater than 98wt% The isomers represented by general formula (Ia) and/or general formula (Ib) are based on the total weight of the precipitation aid a represented by general formula (I);

(Ia) (Ib); and (3) supporting a titanium-based active component on the particulate magnesium-containing solid to form a solid catalyst component. As the method described in item 8 of the scope of patent application, the method includes the following steps: (1) The magnesium compound and the alcohol compound are optionally reacted in the presence of an inert hydrocarbon solvent to obtain a uniform magnesium compound alcoholate solution; (2) reacting the magnesium compound alcoholate solution obtained in step (1) with the first titanium compound in the presence of the precipitation assistant to obtain a mixture containing solid precipitates; (3) Contact the mixture obtained in step (2) with the first internal electron donor compound to obtain a suspension; (4) The suspension obtained in step (3) is subjected to solid-liquid separation to obtain a first solid intermediate product, and the obtained first solid intermediate product is brought into contact with the second titanium compound and optionally the second internal electron donor compound To provide a mixture; (5) subjecting the mixture obtained in step (4) to solid-liquid separation to obtain a second solid intermediate product, and treating the second solid intermediate product with a third titanium compound to form a solid catalyst component; and (6) Recover the solid catalyst component, Alternatively, the method includes the following steps: (1) The magnesium compound, the organic epoxy compound, and the organic phosphorus compound are optionally contacted in the presence of an inert hydrocarbon solvent to form a uniform magnesium compound solution; (2) In the presence of the precipitation aid, contacting the magnesium compound solution obtained in step (1) with the first titanium compound and the first internal electron donor compound to obtain a suspension containing solid precipitates; (3) subjecting the suspension obtained in step (2) to solid-liquid separation to obtain a first solid intermediate product, and contacting the first solid intermediate product with the second titanium compound and optionally the second internal electron donor compound, To provide a mixture; (4) The mixture obtained in step (3) is subjected to solid-liquid separation to obtain a second solid intermediate product; (5) Treat the second solid intermediate product with a third titanium compound for 1-4 times to form a solid catalyst component; and (6) Recover the solid catalyst component. A catalyst for olefin polymerization, which contains the following components: 1) The catalyst component described in any one of items 1 to 7 in the scope of the patent application; 2) Alkyl aluminum compounds; and Optionally 3) external electron donor compound; Wherein, the molar ratio of component 1) to component 2) is (5-5000):1 in terms of titanium:aluminum, preferably (20-1000):1, and more preferably (50-500):1. A pre-polymerization catalyst for olefin polymerization, which comprises the catalyst component as described in any one of items 1 to 7 in the scope of patent application or the catalyst as described in item 10 in the scope of patent application for pre-polymerization of olefins The obtained prepolymer; wherein the prepolymerization multiple of the prepolymer is 5-1000g olefin polymer/g catalyst component, preferably 10-500g olefin polymer/g catalyst component; the preferred olefin used for prepolymerization is Ethylene or propylene. An olefin polymerization method, the general formula of the olefin is CH ₂ =CHR, where R is hydrogen, a C ₁ -C ₆ alkyl group or an aryl group, and the method includes making the olefin in the range of the first to seventh The catalyst component described in any one of items, the catalyst described in item 10 of the scope of patent application or the prepolymerized catalyst described in item 11 of the scope of patent application is polymerized to form a polyolefin polymer; and The resulting polyolefin polymer.