CN109553711B

CN109553711B - Catalyst component for olefin polymerization and catalyst thereof

Info

Publication number: CN109553711B
Application number: CN201710886394.9A
Authority: CN
Inventors: 王军; 高明智; 刘海涛; 马晶; 陈建华; 蔡晓霞; 马吉星; 胡建军; 李昌秀; 何世雄
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-09-27
Filing date: 2017-09-27
Publication date: 2021-04-13
Anticipated expiration: 2037-09-27
Also published as: CN109553711A

Abstract

The invention discloses a catalyst component for olefin polymerization, which is prepared by a method comprising the following steps: 1) mixing a magnesium compound with an organic alcohol compound and an inert solvent, and adding a compound shown in a structural general formula I for treatment to obtain an alcohol compound; 2) contacting the alcohol compound with a titanium compound at a low temperature, adding an internal electron donor compound for reaction, and separating out first solid particles; 3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating second solid particles; 4) washing the second solid particles obtained in step 3) with an inert solvent to obtain the catalyst component;

Description

Catalyst component for olefin polymerization and catalyst thereof

Technical Field

The invention relates to a catalyst component for olefin polymerization and a preparation method thereof, a catalyst system for olefin polymerization, application of the catalyst component and the catalyst system in olefin polymerization reaction and an olefin polymerization method, and belongs to the field of olefin polymerization.

Background

As is well known, a polyolefin catalyst containing magnesium, titanium, halogen and an electron donor as essential components is obtained by supporting a transition metal compound on an inorganic substance such as magnesium chloride or silica as a carrier. The early magnesium chloride carrier prepared by grinding method has the disadvantages of poor particle shape of catalyst, poor particle shape of polymer obtained by catalysis, more fine powder and low apparent density. Currently, more chemical methods are used, i.e. the magnesium compound is dissolved in a solvent to prepare a homogeneous solution, and then precipitated by crystallization. In the process of dissolution, solid substances with uniform particle size can be obtained only in the presence of the precipitation aid. The auxiliary precipitation agent is usually a compound such as an organic acid anhydride, an organic ketone, an ether, or the like. The precipitation aids reported in the prior art can be of various types of compounds. Such as those reported using alkanes (CN200810223088.8 and CN03123950.1) or organosilicon compounds without active hydrogen as a precipitation aid (CN 201110269970.8). In CN101643519A, a diol ester compound with a special structure is taken as a precipitation aid, and a diol ester compound or a dicarboxylic acid ester compound with a special structure is simultaneously matched and applied as an electron donor to load at least one surface modifier, the catalyst shows high stereospecificity when used for olefin polymerization, and the obtained polymer has wide molecular weight distribution and less fine powder. CN1955195A discloses a catalyst system for olefin polymerization or copolymerization, which is prepared by compounding aromatic monocarboxylic ester and polycarboxylic ester, wherein the aromatic monocarboxylic ester is both a precipitation aid and an electron donor, the catalyst has good particle morphology and impurity resistance, and the obtained polymer has wider molecular weight distribution and less fine powder.

The preparation method of the traditional solid particle type Ziegler-Natta titanium catalyst loaded with magnesium halide generally comprises the steps of preparing homogeneous solution by halogenation, crystallizing and precipitating, and then loading the titanium-containing active component on the magnesium halide. In the process of dissolution, solid substances with uniform particle size can be obtained only in the presence of the precipitation aid. The separating aid in each patent mainly comprises one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic anhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether and amyl ether, or a mixture of the acetic anhydride, the phthalic anhydride, the succinic anhydride, the maleic anhydride, the pyromellitic anhydride, the acetic acid, the propionic acid, the butyric acid, the acrylic acid, the methacrylic acid, the acetone, the methyl ethyl. Such as CN85100997, CN98101108.x, CN98126383.6, CN98126385.2, CN98111780.5, cn98101108.x, CN99102813.9, CN98111780.5, CN201110335576.x, CN201010204493.2, CN201010294618.5, CN201010283061.5, CN200910209546.7, CN200910177286.x, CN200910091115.5, CN200910086590.3, CN200910084912.1, CN200910083987.7, CN200810117895.6, CN200810117895.1, CN200510114544.1, CN200410062290.9, etc. The precipitation aid with good effect for preparing the olefin polymerization catalyst reported in the patent literature usually adopts phthalic anhydride as the precipitation aid compound.

In the preparation method of the titanium-containing catalyst component disclosed in chinese patent CN1931885A, after magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound, a class of organic alcohol electron donors is added to form a uniform solution, and an alcohol or alkane is used as a coprecipitator to replace a conventional benzoic anhydride precipitation aid, so as to obtain a catalyst solid. In the chinese patent CN101864009B, after magnesium halide is dissolved in organic epoxy compound and organic phosphorus compound, polyol ester compound is used to replace the traditional benzoic anhydride precipitation aid, and the catalyst solid is obtained.

Disclosure of Invention

The invention aims to provide a catalyst component for olefin polymerization and a preparation method thereof aiming at the defects of the prior art, a compound with a special structure is introduced as a precipitation aid in the preparation process of the catalyst component, the use of a phthalic anhydride compound is omitted or reduced, and further the catalyst for olefin polymerization is provided.

According to one aspect of the present invention, there is provided a catalyst component for olefin polymerization, which is prepared by a process comprising the steps of:

1) mixing a magnesium compound with an organic alcohol compound and an inert solvent, and adding a compound shown in a structural general formula I for treatment to obtain an alcohol compound;

2) contacting the alcohol compound with a titanium compound at low temperature, adding an internal electron donor compound for reaction, and separating a first solid particle;

3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating second solid particles;

4) washing the second solid particles obtained in step 3) with an inert solvent to obtain the catalyst component;

wherein A is selected from- (CR)₁R₂)_n-and- (XR)₁R₂)_n(YR₃)_m-, wherein X is a carbon atom or a silicon atom, Y is a nitrogen atom or a phosphorus atom, n is 1 to 5, and m is 1 to 5; r₁～R₃Independently selected from hydrogen, substituted or unsubstituted C₁～C₃₀A substituted or unsubstituted C₂～C₃₀Heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C₁～C₃₀Preferably selected from hydrogen, substituted or unsubstituted C₁～C₃₀Linear alkyl, substituted or unsubstituted C of₃～C₃₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₃₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₃₀Substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₇～C₃₀Alkylaryl or arylalkyl of, substituted or unsubstituted C₂～C₃₀A substituted or unsubstituted C₄～C₃₀Aromatic heterocyclic group of (A), halogen, hydroxy and substituted or unsubstituted C₁～C₃₀Alkoxy group of (a); r₁And R₂Can be linked to form a ring;

R₄and R₅May be the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₃₀And substituted or unsubstituted C₂～C₃₀Preferably selected from substituted or unsubstituted C₁～C₃₀Linear alkyl, substituted or unsubstituted C of₃～C₃₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₃₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₃₀Substituted or unsubstituted C₆～C₃₀Aryl, substituted or unsubstituted C₇～C₃₀Alkylaryl or arylalkyl of, substituted or unsubstituted C₂～C₃₀And substituted or unsubstituted C₄～C₃₀The aromatic heterocyclic group of (1).

According to some embodiments of the invention, the R is₁～R₃Selected from hydrogen, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₂₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₂₀Substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₇～C₂₀Alkylaryl or arylalkyl of, substituted or unsubstituted C₂～C₂₀A substituted or unsubstituted C₄～C₂₀Aromatic heterocyclic group ofHalogen, hydroxy and substituted or unsubstituted C₁～C₂₀Preferably selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, propoxy, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group, chloro, bromo, iodo, hydroxy and hydroxyalkyl; r₁And R₂Optionally linked to form a ring, preferably R on each X₁And R₂Optionally linked to substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₃～C₁₀Or is substituted or unsubstituted C₂～C₁₀And heterocyclic groups such as cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl and cyclopentadienyl.

According to a preferred embodiment of the invention, said R₄And R₅May be the same or different and are each independently selected from hydrogen, substituted or unsubstituted C₁～C₂₀And substituted or unsubstituted C₂～C₂₀Preferably selected from substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₂₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₂₀Substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₇～C₂₀Alkylaryl or arylalkyl of, substituted or unsubstituted C₂～C₂₀And substituted or unsubstituted C₄～C₂₀Is preferably selected from substituted or unsubstituted C₁～C₁₀And substituted or unsubstituted C₂～C₁₀Preferably selected from substituted or unsubstituted C₁～C₁₀The linear alkyl group of,Substituted or unsubstituted C₃～C₁₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₁₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₁₀Substituted or unsubstituted C₆～C₁₀Aryl, substituted or unsubstituted C₇～C₁₀Alkylaryl or arylalkyl of, substituted or unsubstituted C₂～C₁₀And substituted or unsubstituted C₄～C₁₀More preferably from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, a pyrrole-containing group, a pyridine-containing group, a pyrimidine-containing group, a quinoline-containing group and hydroxyalkyl.

According to the invention, said substitution means R₁～R₃、R₄And R₅The hydrogen atom bonded to the carbon atom in the alkyl, cycloalkyl, aryl, alkaryl or aralkyl group in (1) may be optionally substituted with a heteroatom, an alkyl group or an alkoxy group, and the carbon atom in the main chain may be optionally substituted with a heteroatom. The hetero atom includes a halogen atom and the like.

According to some embodiments of the invention, the compound of formula I is selected from the group consisting of (acetoxycarbonyl) (phenyl) methyl benzoate, (propionyloxycarbonyl) (phenyl) methyl benzoate, (butyryloxycarbonyl) (phenyl) methyl benzoate, (valeryloxycarbonyl) (phenyl) methyl benzoate, (benzoyloxycarbonyl) (phenyl) methyl benzoate, (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-acetoxycarbonyl) (phenyl) methyl 4-methylbenzoate, Propionyloxycarbonyl (phenyl) methyl 4-methylbenzoate, (butyryloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (valeryloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (acetyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (propionyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (butyryloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (valeryloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (benzoyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (2-methylbenzoyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (acetyloxycarbonyl) (phenyl) methyl 4-ethylbenzoate, (propionyloxycarbonyl) (phenyl) methyl 4-ethylbenzoate, 4-ethylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate [ (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (acetyloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (propionyloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (butyryloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (valeryloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate, 2-n-propylbenzoic acid (acetoxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (acetoxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-Chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-Bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-methylbenzoic acid (cyclohexylcarbonyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclohexylcarbonyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl formate, (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl acetate, (benzoyloxycarbonyl) (phenyl) methyl propionate, (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl butyrate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl valerate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl hexanoate, (2-benzoyloxycarbonyl) ethyl benzoate, (2-benzoyloxycarbonyl) ethyl 4-methylbenzoate, (2-benzoyloxycarbonyl) ethyl 4-ethylbenzoate, (2-benzoyloxycarbonyl) ethyl 4-propylbenzoate, (2-benzoyloxycarbonyl) ethyl 4-butylbenzoate, (1-benzoyloxycarbonyl) ethyl benzoate, (1-benzoyloxycarbonyl) ethyl 4-propylbenzoate, (2-benzoyloxycarbonyl) propyl benzoate, (1-benzoyloxycarbonyl) propyl 4-propylbenzoate, (2-benzoyloxycarbonyl) propyl 4-methylbenzoate, (2-benzoyloxycarbonyl) propyl 4-ethylbenzoate, 2-benzoyloxycarbonyl-propyl-4-phenylbenzoate, 2-benzoyloxycarbonyl-propyl-4-butylbenzoate, 2-benzoyloxycarbonyl-butyl-benzoate, 1-benzoyloxycarbonyl-butyl-4-propylbenzoate, 2-benzoyloxycarbonyl-butyl-4-methylbenzoate, 2-benzoyloxycarbonyl-butyl-4-ethylbenzoate, 2-benzoyloxycarbonyl-butyl-4-propylbenzoate, 2-benzoyloxycarbonyl-butyl-4-butylbenzoate, 2-benzoyloxycarbonyl-pentyl-benzoate, 2-benzoyloxycarbonyl-2-methyl-propyl-benzoate, 2-benzoyloxycarbonyl-3-methyl-butyl-benzoate, (2-benzoyloxycarbonyl-2-ethyl) butyl benzoate, (2-benzoyloxycarbonyl-2-ethyl) butyl 4-propionate, (2-benzoyloxycarbonyl-2-ethyl) butyl 4-butyrate, (2-benzoyloxycarbonyl-3-methyl) pentyl benzoate, (2-benzoyloxycarbonyl-2-ethyl) pentyl benzoate, (2-benzoyloxycarbonyl-2-phenyl) ethyl benzoate, [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-isopropylbenzoyloxycarbonyl) 2-phenyl ] ethyl benzoate, [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, (2-acetyloxycarbonyl-2-phenyl) ethyl benzoate, (2-propionyloxycarbonyl-2-phenyl) ethyl benzoate, (2-benzoyloxycarbonyl) ethyl benzoate, (2-acetyloxycarbonyl) ethyl benzoate, (2-propionyloxycarbonyl) ethyl benzoate, (2-butyryloxycarbonyl) ethyl benzoate, (2-benzoyloxycarbonyl-2-phenyl) ethyl 4-propylbenzoate, [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-propylbenzoate, 4-Propylbenzoic acid [2- (4-isopropylbenzoyloxycarbonyl) 2-phenyl ] ethyl ester, 4-propylbenzoic acid [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-propylbenzoic acid [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-propylbenzoic acid [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-propylbenzoic acid (2-acetoxycarbonyl-2-phenyl) ethyl ester, 4-propylbenzoic acid (2-propionyloxycarbonyl-2-phenyl) ethyl ester, 4-propylbenzoic acid (2-benzoyloxycarbonyl) ethyl ester, 4-propylbenzoic acid (2-acetoxycarbonyl) ethyl ester, methyl ester, ethyl ester, methyl ester, ethyl ester, 4-Propyloxycarbonyl ethyl 4-propylbenzoate (2-butyryloxycarbonyl) ethyl 4-butylbenzoate (2-benzoyloxycarbonyl-2-phenyl) ethyl 4-butylbenzoate [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-butylbenzoate [2- (4-isopropylbenzoyloxycarbonyl) 2-phenyl ] ethyl 4-butylbenzoate [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-butylbenzoate [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-butylbenzoate [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-butylbenzoate, (2-acetoxycarbonyl-2-phenyl) ethyl 4-butylbenzoate, propyl (3-benzoyloxycarbonyl-3-phenyl) benzoate, [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-isobutylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (3-acetoxycarbonyl-3-phenyl) propyl benzoate, (3-propionyloxycarbonyl-3-phenyl) propyl benzoate, (3-benzoyloxycarbonyl) propyl benzoate, (3-acetyloxycarbonyl) propyl benzoate, (3-propionyloxycarbonyl) propyl benzoate, (3-butyryloxycarbonyl) propyl benzoate, (3-benzoyloxycarbonyl) propyl 4-propylbenzoate, (3-benzoyloxycarbonyl-3-phenyl) propyl 4-propylbenzoate, [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-propylbenzoate, [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-propylbenzoate, [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-propylbenzoate, and [3- (4-isobutylbenzoyloxycarbonyl) -3-propylbenzoate- Phenyl ] propyl ester, 4-propylbenzoic acid [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid (3-acetyloxycarbonyl-3-phenyl) propyl ester, 4-propylbenzoic acid (3-propionyloxycarbonyl-3-phenyl) propyl ester, 4-propylbenzoic acid (3-benzoyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-acetyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-propionyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-butyryloxycarbonyl) propyl ester, 4-butylbenzoic acid (3-benzoyloxycarbonyl-3-phenyl) propyl ester, 4-butylbenzoic acid [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-butylbenzoic acid [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-butylbenzoic acid [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-butylbenzoic acid [3- (4-isobutylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-butylbenzoic acid [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-butylbenzoic acid (3-acetoxycarbonyl-3-phenyl) propyl ester, diacetyl carbonate, dipropyl carbonate, dibutyryl carbonate, dibenzoyl carbonate, bis (4-methylbenzoyl) carbonate, bis (4-ethylbenzoyl) carbonate, di (4-, Bis (4-propylbenzoyl) carbonate, bis (4-butylbenzoyl) carbonate, N-acetoxycarbonyl-aminomethyl benzoate, (N-methyl-N-acetoxycarbonyl) -aminomethyl benzoate, (N-ethyl-N-acetoxycarbonyl) -aminomethyl benzoate, (N-propyl-N-acetoxycarbonyl) -aminomethyl benzoate, (N-benzoyloxycarbonyl) -aminomethyl benzoate, (N-methyl-N-benzoyloxycarbonyl) -aminomethyl benzoate, (N-ethyl-N-benzoyloxycarbonyl) -aminomethyl benzoate, (N-propyl-N-benzoyloxycarbonyl) aminomethyl benzoate, [2- (N-benzoyloxycarbonyl) amino ] ethyl benzoate, [3- (N-benzoyloxycarbonyl) amino ] propyl benzoate, [3- (N-benzoyloxycarbonyl) amino ] butyl benzoate, [ N-ethyl-N-benzoyloxycarbonyl) aminomethyl 4-methylbenzoate, [ N-propyl-N-benzoyloxycarbonyl) aminomethyl 4-methylbenzoate, [2- (N-benzoyloxycarbonyl) amino ] ethyl 4-ethylbenzoate, [3- (N-benzoyloxycarbonyl) amino ] propyl 4-ethylbenzoate, [3- (N-benzoyloxycarbonyl) amino ] butyl 4-ethylbenzoate, [2- (N-benzoyloxycarbonyl) amino ] ethyl 4-propylbenzoate, [3- (N-benzoyloxycarbonyl) amino ] propyl 4-propylbenzoate, One or more of [3- (N-benzoyloxycarbonyl) amino ] butyl 4-propylbenzoate, [2- (N-benzoyloxycarbonyl) amino ] ethyl 4-butylbenzoate, [3- (N-benzoyloxycarbonyl) amino ] propyl 4-butylbenzoate and [3- (N-benzoyloxycarbonyl) amino ] butyl 4-butylbenzoate.

Among the above compounds, the fact that a normal or abnormal compound is not indicated means that the normal or abnormal group is included.

In some embodiments, the compound of general structural formula I described in step 1) is added during or after mixing.

According to some preferred embodiments of the present invention, the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines, preferably from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds, and more preferably comprises one or more of benzoate compounds, phthalate compounds, malonate compounds, succinate compounds and glutarate compounds. In some specific embodiments, the second internal electron donor compound comprises di-n-butyl phthalate, diisobutyl phthalate, 2, 4-diphenylmethylcarboxylpentane, 2, 4-di (methylbenzocarboxyl) pentane, 2, 4-di (ethylbenzylcarboxyl) pentane, 2, 4-di (n-propylbenzylcarboxyl) pentane, 2, 4-di (isopropylbenzylcarboxyl) pentane, 2, 4-di (n-butylbenzylcarboxyl) pentane, 2, 4-di (isobutylbenzylcarboxyl) pentane, 2, 4-di (tert-butylbenzylcarboxyl) pentane, 9-dimethoxymethylfluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxyfluorene, 1, 8-diphenylcarboxynaphthol, 3-tert-butyl-1, one or more of 2-dibenzyl carboxyl phenol and 2, 3-diisopropyl diethyl succinate.

According to a preferred embodiment of the present invention, the compound of formula I is used in an amount of 0.01 to 6 moles, preferably 0.01 to 2 moles, more preferably 0.02 to 1 mole per mole of magnesium.

According to a preferred embodiment of the present invention, the internal electron donor compound is used in an amount of 0.001 to 15 moles, preferably 0.005 to 10 moles, more preferably 0.05 to 5 moles, per mole of magnesium.

According to some embodiments of the present invention, the magnesium compound comprises at least one of magnesium dihalide, a hydrate of magnesium dihalide, a water or alcohol complex of magnesium dihalide, alkyl magnesium halide, alkoxy magnesium and alkoxy magnesium halide, the halogen being selected from at least one of fluorine, chlorine, bromine and iodine, preferably chlorine and/or bromine. In some specific embodiments, the magnesium compound preferably includes at least one of magnesium dichloride, magnesium dibromide, phenoxymagnesium chloride, isopropoxymagnesium chloride, butoxymagnesium chloride, ethoxymagnesium, and ethoxymagnesium chloride.

According to some embodiments of the present invention, the organic alcohol compound is not particularly limited, and an organic alcohol compound commonly used in the art may be selected; according to a preferred embodiment of the present invention, the organic alcohol compound includes at least one of aliphatic alcohol, alicyclic alcohol and aromatic alcohol. Wherein the fatty alcohol is preferably C₁-C₁₀Of straight-chain fatty alcohols or C₃-C₁₀The branched fatty alcohol of (1). The alicyclic alcohol is preferably C₃-C₁₂The fatty alcohol of (1). The aromatic alcohol is preferably C₆-C₂₀Of aryl alcohol or C₇-C₂₀An alkyl aromatic alcohol of (1). In some specific embodiments, the alcohol compound suitable for the present invention preferably includes at least one of ethanol, propanol, butanol, 2-ethylhexanol, isooctanol, benzyl alcohol, and phenethyl alcohol.

According to a preferred embodiment of the invention, the titanium compound comprises a compound of formula Ti (OR)₆)_aM_4-aAnd/or derivatives thereof, wherein R₆Is C₁-C₂₀Is preferably C₁-C₁₀Alkyl groups of (a); m is halogen, preferably chlorine, bromine or iodine; a is 1 to 4. In some specific embodiments, the titanium compound preferably comprises at least one of a titanium tetrahalide, an alkoxy titanium trihalide, a dialkoxy titanium trihalide, and a trialkoxy titanium halide; more preferably, it comprises one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetraethoxyide, titanium tetrabutoxide, titanium monochlorotriethoxyide, titanium dichlorodiethoxylate and titanium trichloroethoxylate. According to one embodiment of the invention, the titanium compound is preferably titanium tetrachloride.

According to a preferred embodiment of the present invention, the magnesium compound is preferably mixed with the organic alcohol compound and the inert solvent at 30 to 150 ℃ for 0.5 to 10 hours in the step 1) until the magnesium compound is completely dissolved; then adding the compound shown in the structural general formula I, and continuously reacting for 0.5-3h at the temperature of 30-150 ℃ to obtain the alcohol compound.

In some specific examples, the organic alcohol compound is used in an amount of 0.2 to 10 moles, preferably 0.5 to 5 moles, per mole of magnesium.

According to a preferred embodiment of the present invention, in the step 2), the alcohol hydrate is preferably cooled to room temperature, added to a titanium compound at a temperature of-40 to 0 ℃ for contacting for 0.5 to 5 hours, then heated to 50 to 150 ℃, added with an internal electron donor compound for reacting for 0.5 to 6 hours at a temperature of 20 to 120 ℃, and filtered to separate out the first solid particles.

According to a preferred embodiment of the present invention, the first solid particles obtained in step 2) are preferably added to a solution of titanium compound in step 3), reacted at a temperature of 50 to 150 ℃ for 1 to 6 hours, and then filtered to separate the second solid particles.

According to a preferred embodiment of the present invention, the second solid particles obtained in step 3) are preferably washed in step 4) with an inert solvent and dried to obtain the catalyst component.

The catalyst component for olefin polymerization obtained according to the present invention can be used for preparing an olefin polymerization catalyst system.

According to another aspect of the present invention, there is provided a catalyst system for the polymerization of olefins comprising the reaction product of:

a. the above catalyst component for olefin polymerization;

b. an organoaluminum compound;

c. optionally, an organosilicon compound.

According to a preferred embodiment of the invention, the molar ratio of component b to component a, calculated as aluminium/titanium, is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500):1, preferably (0.01-100): 1.

According to some embodiments of the present invention, the alkylaluminum compound is not particularly limited, and an alkylaluminum compound that can be used in a ziegler-natta type catalyst, which is commonly used in the art, may be selected.

The alkyl aluminum compounds suitable for use in the present invention,preferably of the formula AlR'_n'X'_3-n'The alkyl aluminum compound is shown in the specification, wherein R' is selected from hydrogen and C₁-C₂₀Alkyl and C₆-C₂₀Aryl of (a); x 'is halogen, and n' is an integer of 1 to 3.

In some specific embodiments, as a specific example of the alkylaluminum compound, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride can be selected.

According to a particular embodiment of the invention, said component c being optionally an organosilicon compound means that the catalyst system for the polymerization of olefins may or may not contain organosilicon compounds. According to a preferred embodiment of the present invention, the external electron donor compound is not particularly limited, and an external electron donor compound that can be used in a ziegler-natta type catalyst, which is generally used in the art, may be selected.

The external electron donor compounds suitable for use in the present invention are preferably of the general formula R "_m'Si(OR”')_4-m'The organic silicon compound is shown in the specification, wherein R' is selected from hydrogen, halogen and C₁-C₂₀Alkyl of (C)₃-C₂₀Cycloalkyl of, C₆-C₂₀Aryl and C₁-C₂₀A haloalkyl group of (a); m' is an integer of 1 to 3.

In some specific examples, as specific examples of the organosilicon compound, at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-t-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, diisopropyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, etc., preferably at least one of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane and diphenyldimethoxysilane.

According to another aspect of the present invention there is provided the use of a catalyst system as described above in the polymerisation of olefins.

According to another aspect of the present invention, there is provided an olefin polymerization process comprising carrying out an olefin polymerization reaction using one or more olefins in the presence of the above catalyst component or the above catalyst system.

According to a preferred embodiment of the invention, at least one of said olefins is of formula CH₂Olefins represented by ═ CHR, where R is hydrogen or C₁-C₇Alkyl group of (1).

The olefin polymerization process of the invention can be used for the polymerization of olefins of the general formula CH₂Homopolymerization of olefins represented by ═ CHR, can also be used for the preparation of the compound of formula CH₂Olefins represented by ═ CHR are copolymerized with various olefins. R is hydrogen or C₁-C₇Alkyl group of (1). Said general formula is CH₂Specific examples of olefins represented by ═ CHR include one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene.

According to the olefin polymerization process of the present invention, the olefin polymerization conditions are not particularly limited, and the conditions conventional in the art may be selected; the amount of the catalyst to be used is not particularly limited, and the amount of each catalyst to be used in the olefin polymerization of the prior art can be selected.

According to the invention, a compound with a special structure is introduced in the preparation process of the catalyst component as a precipitation aid, so that the use of a phthalic anhydride compound is omitted or reduced, the obtained catalyst component has high catalytic activity and slow activity decay, and the obtained polymer has high melt index, wide molecular weight distribution and high isotacticity. The catalyst provided by the invention has the advantages of excellent comprehensive catalytic activity performance, higher activity, adjustable orientation capability, good hydrogen regulation sensitivity, adjustable isotactic index of the prepared polymer and wider molecular weight distribution.

Detailed Description

The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.

In the following examples, the evaluation and testing methods involved are as follows:

1. polymer isotacticity (%): determination by heptane extraction: a2 g sample of the dried polymer was extracted with boiling heptane in an extractor for 6 hours and the residue was dried to constant weight, the ratio of the weight of the polymer (g) to 2g being the isotacticity.

2. Polymer melt index (g/10 min): measured according to ASTM D1238-99.

3. Polymer molecular weight distribution (Mw/Mn): measuring with gel permeation chromatograph manufactured by Waters company, and using 1,2, 4-trichlorobenzene and styrene as standard sample as solvent; nuclear magnetic analysis of the Compounds the 1H-NMR of the polymer was determined with a Bruke dmx 300MHz NMR spectrometer, solvent: deuterated chloroform with TMS as internal standard and temperature 275K.

Synthesis of Compound (I)

EXAMPLE 1 Synthesis of (benzoyloxycarbonyl) (phenyl) methyl benzoate, Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.04 g of triethylamine were added and stirred uniformly. 2.80 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then refluxed for 6 hours. And (3) cooling, adding 2.10 g of triethylamine, slowly dropwise adding 2.80 g of benzoyl chloride dissolved in 40 ml of tetrahydrofuran solution, stirring for reacting for 4 hours, and then carrying out reflux reaction for 8 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted with ether three times. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 4.12 g of a product (yield 62%).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.21～8.19(2H,m,ArH),8.06～8.03(2H,m,ArH),7.80～7.78(1H,m,ArH)7.68-7.66 (3H, m, ArH), 7.56-7.54 (2H, m, ArH), 7.38-7.36 (5H, m, ArH), 6.10-6.08 (1H, s, CH); mass Spectrometry, FD-mass spectrometry: 360.

EXAMPLE 2 Synthesis of 4-n-propylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, Compound No. 2

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 4.10 g of triethylamine were added and stirred at room temperature. 7.28 g of 4-n-propylbenzoyl chloride dissolved in 50 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, stirred for 6 hours and then refluxed for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted with ether three times. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether and ethanol (1:20) to isolate a pale yellow liquid, which was then dried under vacuum to obtain 4.65 g of a product (yield: 50%).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.16～8.14(2H,m,ArH),7.99～7.97(2H,m,ArH),7.38～7.35(5H,m,ArH),7.04～7.02(2H,m,ArH),6.94～6.92(2H,m,ArH),6.08～6.06(1H,s,CH),2.64～2.62(4H,m,CH₂),1.66～1.63(4H,m,CH₂),0.96～0.94(3H,m,CH₃),0.92～0.90(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 444.

EXAMPLE 3 Synthesis of 4-n-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 4.15 g of triethylamine were added and stirred uniformly. 7.84 g of 4-n-butylbenzoyl chloride dissolved in 60 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, stirred at room temperature for 6 hours and then refluxed for 20 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. Extracted with ether three times. The organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to separate a pale yellow viscous liquid, which was then dried under vacuum to obtain 4.90 g of a product (yield: 52%).

Subjecting the product toThe detection, test methods and results are as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.16～8.14(2H,m,ArH),7.98～7.96(2H,m,ArH),7.38～7.36(5H,m,ArH),7.04～7.02(2H,m,ArH),6.94～6.92(2H,m,ArH),6.08～6.06(1H,s,CH),2.63～2.61(4H,m,CH₂),1.58～1.56(4H,m,CH₂),1.32～1.30(4H,m,CH₂),0.96～0.94(3H,m,CH₃),0.92～0.90(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 472.

EXAMPLE 4 Synthesis of 4-n-butylbenzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester, Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.02 g of triethylamine were added and stirred uniformly. 3.92 g of 4-n-butylbenzoyl chloride dissolved in 40 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, stirred at room temperature for 4 hours and then reacted for 6 hours under reflux. And (3) cooling, adding 2.05 g of triethylamine, slowly dropwise adding 2.80 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution, reacting at room temperature for 5 hours, and then carrying out warm reflux reaction for 12 hours. The reaction solution was cooled to room temperature, and the solvent was removed. 200 ml of anhydrous ether was added thereto, and the mixture was stirred for 1 hour to remove the precipitate. After removal of the low boilers, chromatography on a column with diethyl ether/ethanol (1:20) gives a pale yellow liquid which is dried in vacuo to give 3.49 g of product (42% yield).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.21～8.19(2H,m,ArH),7.99～7.97(2H,m,ArH),7.79～7.77(1H,m,ArH),7.66～7.64(2H,m,ArH),7.38～7.35(5H,m,ArH),6.92～6.90(2H,m,ArH),6.07～6.06(1H,s,CH),2.63～2.61(2H,m,CH₂),1.58～1.56(2H,m,CH₂),1.33～1.31(2H,m,CH₂),0.94～0.92(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 416.

EXAMPLE 5 Synthesis of (Cyclohexanecarbonyloxycarbonyl) (phenyl) methyl benzoate as Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.02 g of triethylamine were added and stirred uniformly. 2.80 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 2 hours and then refluxed for 6 hours. And (3) cooling, adding 2.10 g of triethylamine, slowly dropwise adding 2.92 g of cyclohexyl formyl chloride dissolved in 20ml of tetrahydrofuran solution, stirring at room temperature for reaction for 4 hours, and then carrying out reflux reaction for 12 hours. The reaction solution was cooled to room temperature, and the solvent was removed. 200 ml of anhydrous ether was added thereto, and after stirring for 1 hour, the precipitate was removed by filtration. After removal of the low boilers, the residue was isolated by column chromatography using a mixture of ether/ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 3.07 g of product (42% yield).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.07～8.05(2H,m,ArH),7.66～7.64(1H,m,ArH),7.57～7.55(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),2.26～2.25(1H,m,CH),1.80～1.77(2H,m,CH₂),1.56～1.54(4H,m,CH₂),1.49～1.47(2H,m,CH₂),1.43～1.41(2H,m,CH₂) (ii) a Mass Spectrometry, FD-mass spectrometry: 366.

EXAMPLE 6 Synthesis of (butyryloxycarbonyl) (phenyl) methyl benzoate, a Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.05 g of triethylamine were added and stirred uniformly. 1.40 g of benzoyl chloride dissolved in 20ml of tetrahydrofuran solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 2 hours and then refluxed for 6 hours. And (3) cooling, adding 2.10 g of triethylamine, slowly dropwise adding 1.08 g of butyryl chloride dissolved in 20ml of tetrahydrofuran solution at room temperature, stirring for reaction for 4 hours, and then carrying out reflux reaction for 12 hours. Cooled to room temperature and the solvent removed. 200 ml of anhydrous ether was added thereto, and after stirring for 1 hour, the precipitate was removed by filtration. After removal of the low boilers, the mixture was isolated by column chromatography using a mixture of ether/ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 2.60 g of product (40% yield).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.06～8.04(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),2.30～2.28(2H,m,CH₂),1.68～1.66(2H,m,CH₂),0.94～0.92(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 326.

EXAMPLE 7 Synthesis of 4-chlorobenzoic acid (4-chlorobenzoyloxycarbonyl) (phenyl) methyl ester, Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.02 g of triethylamine were added and stirred uniformly. 3.48 g of 4-chlorobenzoyl chloride dissolved in 40 ml of tetrahydrofuran solution is slowly added dropwise at low temperature, and the mixture is stirred at room temperature for 4 hours and then refluxed for 8 hours. And (3) cooling, adding 2.05 g of triethylamine, slowly dropwise adding 3.47 g of 4-chlorobenzoyl chloride dissolved in 30 ml of tetrahydrofuran solution at room temperature, stirring for reaction for 4 hours, and then heating for reflux reaction for 12 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. The ether was extracted three times, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give pale yellow crystals, which were dried under vacuum to give 6.16 g of a product (yield: 72%).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃) 8.08 to 8.06(2H, m, ArH),7.90 to 7.88(2H, m, ArH),7.71 to 7.69(2H, m, ArH),7.60 to 7.68(2H, m, ArH),7.38 to 7.35(5H, m, ArH),6.10 to 6.08(1H, s, CH); mass Spectrometry, FD-mass spectrometry: 428.

EXAMPLE 8 Synthesis of 3-chlorobenzoic acid (3-chlorobenzoyloxycarbonyl) (phenyl) methyl ester as Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 4.10 g of triethylamine were added and stirred uniformly. 6.94 g of 3-chlorobenzoyl chloride dissolved in 50 ml of tetrahydrofuran solution is slowly added dropwise at low temperature, and the mixture is stirred at room temperature for 8 hours and then refluxed for 16 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. The ether was extracted three times, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 5.82 g of a product (yield 68%).

Testing the product, methods and results such asThe following:¹H-NMR(δ,ppm,TMS,CDCl₃) 8.14 to 8.13(1H, m, ArH),8.10 to 8.09(1H, m, ArH),7.98 to 7.97(1H, m, ArH),7.94 to 7.92(1H, m, ArH),7.84 to 7.82(1H, m, ArH),7.70 to 7.68(1H, m, ArH),7.60 to 7.58(1H, m, ArH),7.48 to 7.46(1H, m, ArH),7.38 to 7.35(5H, m, ArH),6.10 to 6.08(1H, s, CH); mass Spectrometry, FD-mass spectrometry: 428.

EXAMPLE 9 Synthesis of (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl benzoate, Compound

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 2.02 g of triethylamine were added and stirred uniformly. 2.80 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, and the mixture was stirred at room temperature for 4 hours and then refluxed for 6 hours. And (3) cooling, adding 2.10 g of triethylamine, slowly dropwise adding 3.82 g of 4-n-butylbenzoyl chloride dissolved in 40 ml of tetrahydrofuran solution at room temperature, stirring for reacting for 4 hours, and then carrying out reflux reaction for 12 hours. The reaction solution was cooled to room temperature, and the solvent was removed. 200 ml of anhydrous ether was added thereto, and after stirring for 2 hours, the precipitate was removed by filtration. Column chromatography of the combined ether/ethanol (1:20) solution afforded a pale yellow liquid which was dried under vacuum to give 3.49 g of product (42% yield).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.16～8.14(2H,m,ArH),8.07～8.05(2H,m,ArH),7.66～7.64(1H,m,ArH),7.56～7.54(2H,m,ArH),7.38～7.34(5H,m,ArH),7.03～7.01(2H,m,ArH),6.07～6.05(1H,s,CH),2.63～2.61(2H,m,CH₂),1.59～1.57(2H,m,CH₂),1.32～1.30(2H,m,CH₂),0.94～0.92(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 416.

EXAMPLE 10 Synthesis of the Compound 4-isopropylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 4.10 g of triethylamine were added and stirred uniformly. 7.28 g of 4-isopropylbenzoyl chloride dissolved in 60 ml of tetrahydrofuran solution was slowly added dropwise at a low temperature, and the mixture was stirred at room temperature for 8 hours and then refluxed for 18 hours. Cool to room temperature and add the appropriate amount of water to dissolve the precipitate. The ether was extracted three times, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether/ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 6.21 g of a product (yield 70%).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.14～8.12(2H,m,ArH),7.97～7.95(2H,m,ArH),7.52～7.50(2H,m,ArH),7.43～7.41(2H,m,ArH),7.38～7.35(5H,m,ArH),6.08～6.06(1H,s,CH),2.87～2.85(2H,m,CH),1.26～1.24(6H,m,CH₃),1.22～1.20(6H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 444.

EXAMPLE 11 Synthesis of 4-tert-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, Compound No. 11

In a 250 ml three-necked flask after purging with nitrogen, 3.04 g of mandelic acid, 80 ml of tetrahydrofuran and 4.10 g of triethylamine were added and stirred uniformly. 7.86 g of 4-tert-butylbenzoyl chloride dissolved in 60 ml of tetrahydrofuran solution was slowly added dropwise at low temperature, stirred at room temperature for 8 hours and then refluxed for 24 hours. The reaction solution was cooled to room temperature, and an appropriate amount of water was added to dissolve the precipitate. The ether was extracted three times, the organic phases were combined and dried over anhydrous magnesium sulfate overnight. After concentration under reduced pressure, the mixture was subjected to column chromatography using a mixed solution of ether and ethanol (1:20) to give a pale yellow liquid, which was dried under vacuum to give 6.13 g of a product (yield 65%).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.14～8.12(2H,m,ArH),7.98～7.96(2H,m,ArH),7.54～7.52(2H,m,ArH),7.43～7.40(2H,m,ArH),7.38～7.35(5H,m,ArH),6.10～6.08(1H,s,CH),1.38～1.35(6H,m,CH₃),1.32～1.30(6H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 472.

EXAMPLE 12 Synthesis of (3-benzoyloxycarbonyl) propyl benzoate, Compound

2.08 g of 2-hydroxybutyric acid, 80 ml of tetrahydrofuran and 2.02 g of triethylamine were added to a 250 ml three-necked flask purged with nitrogen and stirred uniformly. 2.80 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution is slowly added dropwise at low temperature, stirred at room temperature for reaction for 4 hours, and then heated to reflux for reaction for 8 hours. And (3) cooling, adding 2.10 g of triethylamine, slowly dropwise adding 2.40 g of benzoyl chloride dissolved in 30 ml of tetrahydrofuran solution at room temperature, stirring for reacting for 4 hours, and then carrying out reflux reaction for 12 hours. Cooled to room temperature and the solvent removed. 200 ml of anhydrous ether was added thereto, and after stirring for 1 hour, the precipitate was removed by filtration. Column chromatography of the combined ether/ethanol (1:20) solution afforded a pale yellow liquid which was dried under vacuum to give 3.49 g of product (42% yield).

The product was tested, the test methods and results were as follows:¹H-NMR(δ,ppm,TMS,CDCl₃):8.21～8.19(2H,m,ArH),8.05～8.03(2H,m,ArH),7.79～7.77(1H,m,ArH),7.66～7.64(3H,m,ArH),7.56～7.54(2H,m,ArH),4.78～4.76(1H,m,CH),2.14～2.12(2H,m,CH₂),1.30～1.27(3H,m,CH₃) (ii) a Mass Spectrometry, FD-mass spectrometry: 312.

Preparation of component in catalyst and propylene polymerization

Example 13

(1) Preparation of solid catalyst component

4.8g of anhydrous magnesium chloride, 19.5g of isooctanol and 19.5g of decane solvent were added to a 500ml reactor equipped with a stirrer under nitrogen protection, heated to 130 ℃ and reacted for 1.5 hours until the magnesium chloride was completely dissolved. The compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester (8mmol) was added and the reaction was continued at 130 ℃ for 1 hour to obtain an alcohol compound. The alcohol hydrate was cooled to room temperature. Under the protection of nitrogen, the alcohol compound is added dropwise into 120ml titanium tetrachloride solution which is precooled to minus 22 ℃, slowly heated to 100 ℃, 6mmol of 2, 4-dibenzyl carboxyl pentane compound is added, and the temperature is raised to 110 ℃ and maintained for 2 hours. Filtering while the solution is hot, adding 120ml of titanium tetrachloride, heating to 110 ℃, reacting for 2 hours, and filtering. The solid particles were washed 4 times with anhydrous hexane and dried to obtain a solid catalyst.

(2) Polymerization of propylene

The stainless steel reaction kettle with the volume of 5L is fully replaced by gaseous propylene, and then AlEt is added₃2.5mL of methylcyclohexyldimethoxysilane (CHMMS)0.1mol, and the product of the above example was addedThe prepared solid component 10mg and 1.2NL hydrogen were introduced into 2.3L of liquid propylene, heated to 70 ℃ and maintained at this temperature for 1 hour, and then cooled and depressurized to obtain PP powder, the results of which are shown in Table 1.

Example 14

In example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with 4-n-butylbenzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester.

Example 15

In the same manner as in example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with 4-n-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester.

Example 16

In example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with 4-isopropylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester.

Example 17

In the same manner as in example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with 4-tert-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester.

Example 18

In the same manner as in example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with benzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester.

Example 19

In example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with benzoic acid (cyclohexanecarbonyloxycarbonyl) (phenyl) methyl ester.

Example 20

In example 13, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester was replaced with benzoic acid (3-benzoyloxycarbonyl) propyl ester.

Example 21

In example 13, only the compound 2, 4-diphenylmethylcarboxypentane was replaced by DNBP (di-n-butyl phthalate).

Example 22

In example 13, only the compound 2, 4-dibenzylcarboxypentane was replaced by 2, 4-di (n-butylbenzocarboxypentane).

Example 23

In the same manner as in example 13, only the compound 2, 4-dibenzylcarboxypentane therein was replaced by 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane.

Example 24

In example 13, only the compound 2, 4-diphenylcarboxypentane was replaced by 9, 9-dimethoxymethylfluorene.

Example 25

In the same manner as in example 13, only the compound 2, 4-diphenylmethylcarboxypentane therein was replaced with diethyl 2, 3-diisobutylsuccinate.

Example 26

As in example 13, only benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester (8mmol) was changed to benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester (4mmol) and phthalic anhydride (0.7 g).

Example 27

The same as example 21 except that the amount of hydrogenation in example was changed to 7.2NL, the results are shown in Table 1.

Comparative example 1

In the same manner as in example 21, only the compound benzoic acid (benzoyloxycarbonyl) (phenyl) methyl ester (8mmol) was replaced with phthalic anhydride (1.4 g).

Comparative example 2

The same as in comparative example 1, except that the amount of hydrogen added at the time of polymerization was changed to 7.2 NL. The polymerization data are shown in Table 1.

TABLE 1

As can be seen from Table 1, the catalyst component prepared by using the precipitation aid and the polymer prepared by using the catalyst both have isotacticity and melt index which reach or even exceed the level of the prior art, and under the same conditions, compared with the catalyst component and the catalyst prepared by using phthalic anhydride as the precipitation aid, the catalyst component and the catalyst prepared by using the precipitation aid have higher catalytic activity, and the obtained polymer has wider molecular weight distribution. Under the condition of high hydrogen, the catalyst component and the catalyst prepared by the auxiliary precipitator have higher melt index of the obtained polymer, which shows that the catalyst has better hydrogen regulation sensitivity.

Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims

1. A catalyst component for the polymerization of olefins prepared by a process comprising the steps of:

2) contacting the alcohol compound with a titanium compound at a temperature of between 40 ℃ below zero and 0 ℃, adding an internal electron donor compound, and separating out a first solid particle;

3) adding the first solid particles obtained in the step 2) into a titanium compound solution, stirring and reacting, and separating to obtain second solid particles;

wherein A is- (CR)₁R₂)_n-，n＝0～5；R₁～R₂Same or different, each independently selected from hydrogen, substituted or unsubstituted C₁～C₃₀And substituted or unsubstituted C₁～C₃₀Alkoxy of R₁And R₂Can be linked to form a ring; r₄And R₅Same or different, each independently selected from hydrogen and substituted or unsubstituted C₁～C₃₀A hydrocarbon group of (1).

2. The catalyst component according to claim 1 in which R is₁～R₂Same or different, each independently selected from hydrogen, substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₂₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₂₀Substituted or unsubstituted C₆～C₂₀Aryl, substituted or unsubstituted C₇～C₂₀And alkyl aryl or aralkyl and alkyl and aryl ofSubstituted or unsubstituted C₁～C₂₀Alkoxy group of (a); r₁And R₂Optionally linked to substituted or unsubstituted C₃～C₁₀Cycloalkyl, substituted or unsubstituted C₃～C₁₀Or is substituted or unsubstituted C₂～C₁₀The heterocyclic group of (1).

3. The catalyst component according to claim 2 in which R is₁～R₂Selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthyl, biphenyl, methoxy, ethoxy, and propoxy.

4. The catalyst component according to claim 2 in which R is₁And R₂Optionally linked to one or more of cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, fluorenyl and cyclopentadienyl.

5. The catalyst component according to claim 1 in which R is₄And R₅Same or different, each independently selected from hydrogen and substituted or unsubstituted C₁～C₂₀A hydrocarbon group of (1).

6. The catalyst component according to claim 5 in which R is₄And R₅Selected from substituted or unsubstituted C₁～C₂₀Linear alkyl, substituted or unsubstituted C of₃～C₂₀Branched alkyl or cycloalkyl, substituted or unsubstituted C₂～C₂₀Linear alkenyl of (A), substituted or unsubstituted C₃～C₂₀Substituted or unsubstituted C₆～C₂₀Aryl and substituted or unsubstituted C₇～C₂₀Alkylaryl or arylalkyl of。

7. The catalyst component according to claim 6, said R₄And R₅Selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, ethenyl, propenyl, butenyl, phenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, halophenyl, benzyl, phenylethyl, phenylpropyl, phenylbutyl, naphthyl, and biphenyl.

8. The catalyst component according to claim 1, wherein the compound of formula I is selected from the group consisting of (acetoxycarbonyl) (phenyl) methyl benzoate, (propionyloxycarbonyl) (phenyl) methyl benzoate, (butyryloxycarbonyl) (phenyl) methyl benzoate, (valeryloxycarbonyl) (phenyl) methyl benzoate, (benzoyloxycarbonyl) (phenyl) methyl benzoate, (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl benzoate, (4-acetoxycarbonyl) (phenyl) methyl 4-methylbenzoate, Propionyloxycarbonyl (phenyl) methyl 4-methylbenzoate, (butyryloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (valeryloxycarbonyl) (phenyl) methyl 4-methylbenzoate, (acetyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (propionyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (butyryloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (valeryloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (benzoyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (2-methylbenzoyloxycarbonyl) (phenyl) methyl 2-methylbenzoate, (acetyloxycarbonyl) (phenyl) methyl 4-ethylbenzoate, (propionyloxycarbonyl) (phenyl) methyl 4-ethylbenzoate, 4-ethylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-ethylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate [ (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl 4-isopropylbenzoate (acetyloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (propionyloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (butyryloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate (valeryloxycarbonyl) (phenyl) methyl 2-isopropylbenzoate, 2-n-propylbenzoic acid (acetoxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-n-propylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (acetoxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (4-tert-butylbenzoyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-isobutanoylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-n-butylbenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-Chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 3-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 2-Bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 2-bromobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 3-bromobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (acetyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (propionyloxycarbonyl) (phenyl) methyl ester, 4-bromobenzoic acid (butyryloxycarbonyl) (phenyl) methyl ester, 4-chlorobenzoic acid (valeryloxycarbonyl) (phenyl) methyl ester, 4-methylbenzoic acid (cyclohexylcarbonyloxycarbonyl) (phenyl) methyl ester, 4-ethylbenzoic acid (cyclohexylcarbonyloxycarbonyl) (phenyl) methyl ester, 4-n-propylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-isopropylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-n-butylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-isobutylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, 4-tert-butylbenzoic acid (cyclohexylformyloxycarbonyl) (phenyl) methyl ester, (4-isopropylbenzoyloxycarbonyl) (phenyl) methyl formate, (4-n-propylbenzoyloxycarbonyl) (phenyl) methyl acetate, (benzoyloxycarbonyl) (phenyl) methyl propionate, (4-n-butylbenzoyloxycarbonyl) (phenyl) methyl butyrate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl valerate, (4-isobutylbenzoyloxycarbonyl) (phenyl) methyl hexanoate, (2-benzoyloxycarbonyl-2-phenyl) ethyl benzoate, [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-isopropylbenzoyloxycarbonyl) 2-phenyl ] ethyl benzoate, [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl benzoate, (2-acetoxycarbonyl-2-phenyl) ethyl benzoate, (2-propionyloxycarbonyl-2-phenyl) ethyl benzoate, (2-benzoyloxycarbonyl) ethyl benzoate, ethyl (2-benzoyloxycarbonyl) ester, (2-Acetyloxycarbonyl) ethyl benzoate, (2-propionyloxycarbonyl) ethyl benzoate, (2-butyryloxycarbonyl) ethyl benzoate, (2-benzoyloxycarbonyl) ethyl 4-propylbenzoate (2-benzoyloxycarbonyl-2-phenyl) ethyl 4-propylbenzoate [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-propylbenzoate [2- (4-isopropylbenzoyloxycarbonyl) 2-phenyl ] ethyl 4-propylbenzoate [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-propylbenzoate [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-propylbenzoate [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-propylbenzoate Esters, 2-acetoxycarbonyl-2-phenyl ethyl 4-propylbenzoate, 2-propionyloxycarbonyl-2-phenyl ethyl 4-propylbenzoate, 2-benzoyloxycarbonyl ethyl 4-propylbenzoate, 2-acetoxycarbonyl ethyl 4-propylbenzoate, 2-propionyloxycarbonyl ethyl 4-propylbenzoate, 2-butyryloxycarbonyl ethyl 4-propylbenzoate, 2-benzoyloxycarbonyl-2-phenyl ethyl 4-butylbenzoate, [2- (4-n-propylbenzoyloxycarbonyl) -2-phenyl ] ethyl 4-butylbenzoate, [2- (4-isopropylphenyloxycarbonyl) 2-phenyl ] ethyl 4-butylbenzoate, 4-butylbenzoic acid [2- (4-n-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-butylbenzoic acid [2- (4-isobutylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-butylbenzoic acid [2- (4-tert-butylbenzoyloxycarbonyl) -2-phenyl ] ethyl ester, 4-butylbenzoic acid (2-acetoxycarbonyl-2-phenyl) ethyl ester, (3-benzoyloxycarbonyl-3-phenyl) propyl benzoate, [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-isobutylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl benzoate, [ 3-acetoxycarbonyl-3-phenyl) propyl benzoate, (3-propionyloxycarbonyl-3-phenyl) propyl benzoate, (3-benzoyloxycarbonyl) propyl benzoate, (3-acetoxycarbonyl) propyl benzoate, (3-propionyloxycarbonyl) propyl benzoate, (3-butyryloxycarbonyl) propyl benzoate, (3-benzoyloxycarbonyl) propyl 4-propylbenzoate, (3-benzoyloxycarbonyl-3-phenyl) propyl 4-propylbenzoate, 4-propylbenzoic acid [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid [3- (4-isobutylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl ester, 4-propylbenzoic acid (3-acetoxycarbonyl-3-phenyl) propyl ester, 4-propylbenzoic acid (3-propionyloxycarbonyl-3-phenyl) propyl ester, 4-propylbenzoic acid, 4-propylbenzoic acid (3-benzoyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-acetyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-propionyloxycarbonyl) propyl ester, 4-propylbenzoic acid (3-butyryloxycarbonyl) propyl ester, 4-butylbenzoic acid (3-benzoyloxycarbonyl-3-phenyl) propyl ester, [3- (4-n-propylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-butylbenzoate, [3- (4-isopropylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-butylbenzoate, [3- (4-n-butylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-butylbenzoate, 4-butylbenzoic acid [3- (4-isobutylbenzoyloxycarbonyl) -3-phenyloxycarbonyl ] propyl ester One or more of phenyl propyl 4-butylbenzoate [3- (4-tert-butylbenzoyloxycarbonyl) -3-phenyl ] propyl 4-butylbenzoate, (3-acetoxycarbonyl-3-phenyl) propyl 4-butylbenzoate, diacetyl carbonate, dipropionyl carbonate, dibutyryl carbonate, dibenzoyl carbonate, bis (4-methylbenzoyl) carbonate, bis (4-ethylbenzoyl) carbonate, bis (4-propylbenzoyl) carbonate, bis (4-butylbenzoyl) carbonate.

9. The catalyst component according to any one of claims 1 to 8, wherein the magnesium compound comprises at least one of a magnesium dihalide, a hydrate of a magnesium dihalide, a water or alcohol complex of a magnesium dihalide, an alkyl magnesium halide, an alkoxy magnesium and an alkoxy magnesium halide, and the halogen is selected from at least one of fluorine, chlorine, bromine and iodine.

10. The catalyst component according to claim 9, characterized in that the halogen is chlorine and/or bromine.

11. The catalyst component according to any of claims 1 to 8 wherein the internal electron donor compound is selected from one or more of esters, ethers, carboxylic acids, ketones and amines.

12. The catalyst component according to claim 11, wherein the internal electron donor compound is selected from one or more of polycarboxylic acid compounds, polycarboxylic acid ester compounds, glycol ester compounds, diphenol ester compounds and diether compounds.

13. The catalyst component according to any of claims 1 to 8 in which the compound of formula I is used in an amount of 0.01 to 6 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.001-15 mol.

14. The catalyst component according to any of claims 1 to 8 in which the compound of formula I is used in an amount of 0.01 to 2 moles per mole of magnesium; and/or the amount of the internal electron donor compound is 0.005 to 10 mol.

15. The catalyst component according to any of claims 1 to 8 in which the compound of formula I is used in an amount of 0.02 to 1 mole per mole of magnesium; and/or the amount of the internal electron donor compound is 0.05-5 mol.

16. A catalyst system for olefin polymerization comprising the reaction product of:

a. the catalyst component of any one of claims 1 to 15;

b. an organoaluminum compound;

c. optionally, an organosilicon compound.

17. The catalyst system of claim 16 wherein the molar ratio of component b to component a is (5-1000): 1; and/or the molar ratio of component c to component a, calculated as silicon/titanium, is (0-500): 1.

18. A process for the polymerization of olefins comprising the polymerization of olefins using one or more olefins in the presence of a catalyst component as claimed in any of claims 1 to 15 or a catalyst system as claimed in claim 16 or 17.