CN114507303B

CN114507303B - External electron donor for olefin polymerization, catalyst system and olefin polymerization method

Info

Publication number: CN114507303B
Application number: CN202011172025.1A
Authority: CN
Inventors: 周奇龙; 张锐; 徐秀东; 宋维玮; 尹珊珊; 于金华; 李凤奎
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: 2020-10-28
Filing date: 2020-10-28
Publication date: 2023-05-05
Anticipated expiration: 2040-10-28
Also published as: CN114507303A

Abstract

The invention discloses an external electron donor for olefin polymerization, which comprises an amino ester compound shown in a formula (I) and a siloxane compound shown in a formula (II). The invention also discloses a catalyst system for olefin polymerization, which comprises the external electron donor; a solid catalyst component B containing magnesium, titanium, halogen and an internal electron donor compound; and an alkylaluminum compound C as a cocatalyst. When the catalyst system is used for propylene polymerization, the polymerization activity is high, the hydrogen regulation sensitivity is good, the stereospecificity is high, and the catalyst system has the high-temperature self-deactivation performance.

R ₁ ” _m” R ₂ ” _n” Si(OR _3” ) _{4‑m”‑n”} (II)。

Description

External electron donor for olefin polymerization, catalyst system and olefin polymerization method

Technical Field

The invention relates to an external electron donor for olefin polymerization, a catalyst system and an olefin polymerization method.

Background

The electron-donating compound being for CH ₂ One of the indispensable ingredients in Ziegler-Natta catalyst components for CHR olefin polymerization. Typically, ziegler-Natta catalyst systems comprise the following three components: a solid titanium catalyst component having magnesium, titanium, halogen and an internal electron donor as essential components; an alkyl aluminum compound used as a cocatalyst; and an external electron donor compound for further improving the stereospecific performance of the catalyst. The use of the external electron donor compound in combination with the internal electron donor can achieve the purpose of improving the performance of the catalyst.

The olefin polymerization process is accompanied by an exotherm. Local heat removal is not timely, and temperature rise can be caused. If the polymerization rate is maintained at a higher rate with increasing temperature, localized overheating is exacerbated, thereby introducing plasticization and agglomeration of the polymer and increasing the risk of steady operation of the device. This phenomenon occurs in commercial gas phase polypropylene process units. If the Ziegler-Natta catalyst used is one whose activity decreases drastically with increasing temperature, i.e. the catalyst has the characteristic of self-deactivation at high temperatures, this will help to reduce this risk. Thus, there is a need to develop a Ziegler-Natta catalyst system that is active, directionally capable, etc., and has the characteristics of self-deactivation at high temperatures.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide an external Electron Donor (ED) containing amino ester compounds and siloxane compounds, and a corresponding Ziegler-Natta catalyst system, which has the characteristics of higher activity, good stereospecificity, good hydrogen regulation sensitivity and high-temperature self-deactivation when being used for olefin polymerization.

The first aspect of the present invention provides an external electron donor for olefin polymerization, which comprises an amino ester compound represented by formula (I) and a siloxane compound represented by formula (II),

Wherein R is ₁ A linear alkane of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms, wherein the carbon hydrogen atoms in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl groups are optionally substituted or unsubstituted with heteroatoms, alkyl, or alkoxy groups and the carbon atoms in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl backbones are optionally substituted or unsubstituted with heteroatoms;

R ₂ and R is ₃ The same or different, each independently selected from a straight chain alkyl of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms, wherein the hydrogen atoms on the carbon in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl are optionally substituted or unsubstituted with heteroatoms, alkyl, or alkoxy groups, and the carbon atoms on the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl backbone are optionally substituted or unsubstituted with heteroatoms; and R is ₂ And R is ₃ Optionally linked in a ring or not;

R ₄ and R is ₅ The same or different, each independently selected from the group consisting of linear alkanes of 1 to 20 carbon atoms, branched alkyl of 3 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, and aralkyl of 7 to 20 carbon atoms, the hydrogen atoms on the carbon in the alkyl, cycloalkyl, aryl, alkylaryl, or aralkyl being optionally substituted or unsubstituted by heteroatoms, alkyl, or alkoxy groups, the alkyl, cycloalkyl, arylThe carbon atoms on the radical, alkylaryl or arylalkyl backbone are optionally substituted with heteroatoms or not;

R ₁ ″ _m″ R ₂ ″ _n″ Si(OR _3″ ) _4-m″-n″ (II)

in the formula (II), R ₁ "and R ₂ "same or different," each independently selected from the group consisting of halogen, hydrogen atom, straight chain alkyl of 1-20 carbon atoms, branched alkyl of 3-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, aryl of 6-20 carbon atoms, and haloalkyl of 1-20 carbon atoms; r3' is selected from a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms; m 'and n' are each independently selected from integers from 0 to 3, and m '+n' <4。

According to the invention, the term "optionally substituted with a heteroatom" means that the heteroatom may or may not be substituted. The hetero atom includes a halogen atom and the like. According to the invention, when bonded to form a ring, a double bond or a heteroatom may or may not be present in the backbone of the formed ring.

According to some embodiments of the invention, in formula (I), R ₁ Selected from a linear alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, an alkylaryl group of 7 to 10 carbon atoms or an arylalkyl group of 7 to 10 carbon atoms.

According to some embodiments of the invention, R ₂ And R is ₃ Independently selected from a straight chain alkyl group of 3 to 10 carbon atoms, a branched alkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, preferably R ₂ And R is ₃ Independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms.

According to some embodiments of the invention, R ₄ And R is ₅ Independently selected from a straight chain alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or an aryl group of 6 to 10 carbon atoms, preferably ，R ₄ And R is ₅ Independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms, further preferably R ₄ And R is ₅ Independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or phenyl.

According to some embodiments of the invention, the heteroatom comprises a halogen atom.

According to some embodiments of the invention, when R ₂ And R is ₃ When connected to form a ring, the skeleton of the ring formed may or may not contain double bonds or heteroatoms.

According to some embodiments of the invention, in formula (II), R ₁ "and R ₂ "each independently selected from the group consisting of halogen, hydrogen atom, straight chain alkyl of 1-10 carbon atoms, branched alkyl of 3-10 carbon atoms, cycloalkyl of 3-10 carbon atoms, aryl of 6-10 carbon atoms, and haloalkyl of 1-10 carbon atoms; r3' is selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and haloalkyl groups having 1 to 10 carbon atoms.

According to some embodiments of the invention, the amino ester compound is selected from at least one of the following compounds: ethyl N, N-dipropionate, propyl N, N-dipropionate, butyl N, N-dipropionate, isobutyl N, N-dipropionate, 1-amyl N, N-dipropionate, 1-hexanol N, N-dipropionate, 1-heptanol N, N-dipropionate, 1-octanol N, N-dipropionate, 1-nonanol N, N-dipropionate, 1-decanol N, N-dipropionate, phenol N, N-dipropionate, o-methylphenol N, N-diallylacetic acid, butyl N, ethyl N-dibutylamino acetate, propyl N, N-dibutylamino acetate, butyl N, N-dibutylamino acetate, isobutyl N, N-dibutylamino acetate, 1-pentanol N, N-dibutylamino acetate-1-hexanol N, N-dibutylamino acetate-1-heptanol N, N-dibutylamino acetic acid-1-octanol ester, N-dibutylamino acetic acid-1-nonanol ester, N-dibutylamino acetic acid-1-decanol ester, N, phenol N-dibutylamino acetate, o-methylphenol N, N-dibutylamino acetate, ethyl N, N-dipentaminoacetate, propyl N, N-dipentaminoacetate, N, N-butyl dipentaminoacetate, N-isobutyl dipentaminoacetate, N-1-amyl alcohol dipentaminoacetate, N-1-hexanol dipentaminoacetate, N, N-dipentaminoacetic acid-1-heptanol ester, N-dipentaminoacetic acid-1-octanol ester, N-dipentaminoacetic acid-1-nonanol ester, N, N-dipentaminoacetic acid-1-heptanol ester, N-dipentaminoacetic acid-1-octanol ester, N, N-dipentaminoacetic acid-1-nonanol ester, N, N-dihexylaminoacetic acid-1-pentanol ester, N-dihexylaminoacetic acid-1-hexanol ester, N-dihexylaminoacetic acid-1-heptanol ester, N-dihexylaminoacetic acid-1-octanol ester, N-dihexylaminoacetic acid-1-nonanol ester, N-dihexylaminoacetic acid-1-decanol ester, N, phenol N-dihexylaminoacetate, o-methylphenol N, N-dihexylaminoacetate, ethyl N, N-diheptylaminoacetate, propyl N, N-diheptylaminoacetate, butyl N, N-diheptylaminoacetate, isobutyl N, N-diheptylaminoacetate, 1-pentanol N, N-diheptylaminoacetate, N, N-diheptanoacetic acid-1-hexanol ester, N-diheptanoacetic acid-1-heptanol ester, N-diheptanoacetic acid-1-octanol ester, N-diheptanoacetic acid-1-nonanol ester, N-diheptanoacetic acid-1-decanol ester, N-diheptanoacetic acid phenol ester, N, N-diheptylaminoacetic acid o-methylphenol ester, ethyl N, N-dioctyl amino acetate, propyl N, N-dioctyl amino acetate, butyl N, N-dioctyl amino acetate, isobutyl N-dioctyl amino acetate, 1-amyl N, N-dioctyl amino acetate, 1-hexanol N, N-dioctyl amino acetate and N, N-dioctyl glycine-1-heptanol ester, N-dioctyl glycine-1-octanol ester, N-dioctyl glycine-1-nonanol ester, N, N-dioctyl glycine-1-decyl alcohol ester, N-dioctyl glycine phenol ester, N-dioctyl glycine o-methyl phenol ester, N-diisooctyl glycine ethyl ester, N, propyl N-diisooctylamino acetate, butyl N, N-diisooctylamino acetate, isobutyl N, N-diisooctylamino acetate, 1-pentanol N, N-diisooctylamino acetate, 1-hexanol N, N-diisooctylamino acetate, 1-heptanol N, N-diisooctylamino acetate, N, N-diisooctylamino acetic acid-1-octanol ester, N-diisooctylamino acetic acid-1-nonanol ester, N-diisooctylamino acetic acid-1-decanol ester, N-diisooctylamino acetic acid phenol ester, N-diisooctylamino acetic acid o-methylphenol ester, N-dinonylacetic acid ethyl ester, N, propyl N-dinonylacetate, butyl N, N-dinonylacetate, isobutyl N, N-dinonylacetate, 1-pentanol N, N-dinonylacetate-1-hexanol N, N-dinonylacetate-1-heptanol N, N-dinonylacetate-1-octanol N, N-dinonylacetic acid-1-nonanol ester, N-dinonylacetic acid-1-decanol ester, N-dinonylacetic acid phenol ester, N, N-dinonylacetic acid o-methylphenol ester, N-didecylaminoethyl acetate, N-didecylaminopropyl acetate, N-didecylaminobutyl acetate, N, isobutyl N-didecylaminoacetate, 1-pentanol N, N-didecylaminoacetate, 1-hexanol N, N-didecylaminoacetate, 1-heptanol N, N-didecylaminoacetate, 1-octanol N, N-didecylaminoacetate, 1-nonanol, 1-decyl N, N-didecyl amino acetate, phenol N, N-didecyl amino acetate, o-methylphenol N, N-didecyl amino acetate.

According to some embodiments of the invention, the siloxane-based compound is selected from the group consisting of trimethylmethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, dimethoxysilane, diphenyldimethoxysilane, triethoxysilane, tetraethoxysilane, and the like.

According to some embodiments of the invention, the amino ester compound comprises 5-95mol% of the external electron donor a, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, and any value therebetween.

According to a preferred embodiment of the present invention, the amino ester compound accounts for 5 to 60mol% of the external electron donor A.

According to a further preferred embodiment of the invention, the amino ester compound represents 10-40mol% of the external electron donor a.

The inventors of the present invention have unexpectedly found that the use of Ziegler-Natta catalyst systems containing an amino ester compound and a siloxane compound as external electron donors for CH ₂ =chr olefin polymerization has the characteristic of high temperature self-deactivation.

The high-temperature self-deactivation performance of the invention means that the activity of the catalyst is greatly reduced but not reduced to an inactive state at a specific test temperature. Generally, ziegler-Natta catalysts fall off to some extent when the polymerization temperature is increased above 90 ℃. The high-temperature self-deactivation means that when the polymerization temperature is raised from 70 ℃ to 100 ℃ in general, the polymerization activity of the catalyst is reduced to less than 30% of the original activity when the change of the bulk concentration of the monomer is not considered.

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

(1) An external electron donor a;

(2) A solid catalyst component B containing magnesium, titanium, halogen and an internal electron donor compound; and

(3) An alkylaluminum compound C as a cocatalyst;

wherein the external electron donor A comprises an amino ester compound represented by the formula (I),

in the formula (I), R ₁ A linear alkane of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms, wherein the carbon hydrogen atoms in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl groups are optionally substituted or unsubstituted with heteroatoms, alkyl, or alkoxy groups and the carbon atoms in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl backbones are optionally substituted or unsubstituted with heteroatoms;

R ₄ and R is ₅ The same or different, each independently selected from a linear alkane of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms or an aralkyl of 7 to 20 carbon atoms, the alkyl, cycloalkyl, aryl, alkylaryl or aralkyl having any of the hydrogen atoms on the carbon atomsOptionally substituted or unsubstituted with heteroatoms, alkyl groups or alkoxy groups, the carbon atoms in the alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl backbone optionally being substituted or unsubstituted with heteroatoms;

R ₁ ″ _m″ R ₂ ″ _n″ Si(OR _3″ ) _4-m″-n″ (II)

According to some embodiments of the invention, R ₄ And R is ₅ Independently selected from straight chain alkyl groups of 1 to 10 carbon atoms, 3 to 10 carbon atomsBranched alkyl of 3 to 10 carbon atoms, cycloalkyl of 6 to 10 carbon atoms, preferably R ₄ And R is ₅ Independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms, further preferably R ₄ And R is ₅ Independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl or phenyl.

According to some embodiments of the invention, the internal electron donor compound is selected from at least one of phthalate compounds, glycol ester compounds, cyano succinate compounds, diether compounds, and succinate compounds; preferably at least one selected from the group consisting of glycol ester compounds, cyano succinic acid ester compounds, diether compounds and succinic acid ester compounds; more preferably selected from diethers

The catalyst solid component B according to the present invention may be prepared by a method in which a magnesium compound, a titanium compound and an internal electron donor compound are contacted under certain conditions. The amounts of the titanium compound, the magnesium compound and the internal electron donor used for preparing the solid component of the catalyst are not particularly limited, and may be conventional in the art and the amount, respectively.

According to some embodiments of the invention, in the solid catalyst component B, the content of magnesium in terms of magnesium atoms, titanium in terms of titanium atoms, halogen in terms of halogen atoms, titanium atoms is from 1.0 to 8.0% by weight, preferably from 1.6 to 6.0% by weight; the content of magnesium atoms is preferably 10 to 70wt%, preferably 15 to 40wt%; the halogen atom content is 20 to 90wt%, preferably 30 to 85%; the internal electron donor compound content is from 2 to 30% by weight, preferably from 3 to 20% by weight.

In a preferred case, the magnesium compound may be at least one of a magnesium compound represented by formula (II), a hydrate of the magnesium compound represented by formula (II) and an alcohol adduct of the magnesium compound represented by formula (II),

MgR ₁₁ R ₁₂ (II)

in the formula (II), R ₁₁ And R is ₁₂ The same or different, each independently selected from halogen, straight chain alkoxy of 1-8 carbon atoms, branched alkoxy of 3-8 carbon atoms, straight chain alkyl of 1-8 carbon atoms, or branched alkyl of 3-8 carbon atoms.

According to the preparation method of the catalyst solid component B, the hydrate of the magnesium compound shown in the formula (II) refers to MgR ₁₁ R ₁₂ ·pH ₂ O, wherein p is in the range of 0.1 to 6, preferably 2 to 3.5. In the present invention, the alcohol adduct means MgR ₁₁ R ₁₂ ·qR ₁₃ OH, wherein R is ₁₃ A hydrocarbon group selected from 1 to 18 carbon atoms, preferably an alkyl group of 1 to 8 carbon atoms, more preferably a methyl, ethyl, n-propyl or isopropyl group; q is in the range of 0.1 to 6, preferably 2 to 3.5.

In a preferred case, the magnesium compound may be at least one of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, diperoxyimagnesium, di (2-ethyl) hexyloxymagnesium, methoxymagnesium chloride, methoxymagnesium bromide, methoxymagnesium iodide, ethoxymagnesium chloride, ethoxymagnesium bromide, ethoxymagnesium iodide, propoxymagnesium chloride, propoxymagnesium bromide, propoxymagnesium iodide, butoxymagnesium chloride, butoxymagnesium bromide, butoxymagnesium iodide, methylmagnesium chloride, ethylmagnesium chloride, propylmagnesium chloride, butylmagnesium chloride, pentylmagnesium chloride, phenylmagnesium chloride, magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dibromide, and an alcohol adduct of magnesium diiodide. Most preferably, the magnesium compound contains at least one of diethoxy magnesium, butyl magnesium chloride, ethoxy magnesium chloride, and magnesium dichloride.

The preparation method of the catalyst solid component B comprises the steps of preparing a titanium compound shown in a formula (III),

TiX _m (OR ₁₄ ) _4-m (III)

in the formula (III), X is halogen, R ₁₄ Selected from hydrocarbon groups of 1 to 20 carbon atoms, m is an integer of 0 to 4. The halogen may be chlorine, bromine or iodine.

In a preferred embodiment, in formula (III), X is halogen, R ₁₄ Alkyl groups selected from 1 to 5 carbon atoms, for example: at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide. Most preferably, the titanium compound is titanium tetrachloride.

In the present invention, the catalyst solid component B can be carried out by a method for producing an olefin catalyst component which is conventional in the art. The catalyst solid component of the present invention can be prepared, for example, by the following method.

In the first method, an alkoxy magnesium or an alkoxy magnesium halide is suspended in an inert diluent to form a suspension, and the suspension is mixed and contacted with the titanium compound and the internal electron donor to obtain a solid dispersion system, which is commonly called a mother solution. Filtering mother liquor, and suspending the obtained solid matters in a solution containing titanium tetrachloride for contact treatment, which is commonly called titanium treatment; and then filtering and washing to obtain the catalyst solid component.

Specific examples of the above-mentioned alkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropylmagnesium, dibutoxymagnesium, diisobutoxymagnesium, dipentoxymagnesium, dihexoxymagnesium, di (2-ethyl) hexyloxymagnesium and the like or a mixture thereof, and preferably diethoxymagnesium or a mixture of diethoxymagnesium and other alkoxymagnesium. The preparation of the magnesium alkoxide compound may be carried out by methods known in the art, such as disclosed in patent CN101906017a by reacting magnesium metal with a fatty alcohol in the presence of a small amount of iodine.

Specific examples of the alkoxymagnesium halide include methoxymagnesium chloride, ethoxymagnesium chloride, propoxymagnesium chloride, butoxymagnesium chloride, and the like, and ethoxymagnesium chloride is preferable. The alkoxy magnesium halide compound can be prepared by methods well known in the art, such as mixing the grignard reagent butyl magnesium chloride with tetraethoxytitanium and tetraethoxysilicon to prepare magnesium ethoxychloride.

The inert diluent used in the formation of the mother liquor in the above process one may be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.

The amount of each component used for forming the mother liquor in the above-mentioned method one is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the internal electron donor compound (ID) is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.

The contacting temperature of the components in the formation of the mother liquor in the above process one is generally from-40 to 200 ℃, preferably from-20 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.

In the titanium treatment process described in the above method one, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene may be optionally added to the titanium tetrachloride-containing solution.

In the titanium treatment process in the above-mentioned method one, the amount of each component in the titanium tetrachloride-containing solution to be used is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0 to 100 mol, preferably 0 to 50 mol.

The number of titanium treatments in the above-mentioned method one is 0 to 10, preferably 1 to 5.

The electron donor compound described above may be optionally added during the titanium treatment in the above-mentioned method one, wherein the internal electron donor is used in an amount of usually 0.005 to 10 moles, preferably 0.01 to 1 mole.

The titanium treatment temperature in the above-mentioned method one is usually 0 to 200 ℃, preferably 30 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 6 hours.

Dissolving magnesium dihalide in a solvent system consisting of an organic epoxy compound, an organic phosphorus compound, a fatty alcohol compound and an inert diluent to form a uniform solution, and then carrying out contact reaction with the titanium compound and an electron donor compound to precipitate solids in the presence of a precipitation aid to form a mother solution; filtering the mother liquor, and suspending the obtained solid matters in a solution containing titanium tetrachloride for contact treatment, which is hereinafter generally referred to as titanium treatment; and then filtering and washing to obtain the catalyst solid component.

The precipitation aid used in the second method is not particularly limited as long as solid particles can be precipitated and molded. Examples which may be mentioned are: at least one of an organic acid anhydride, an organic acid, an ester, an ether, and a ketone. Specific examples of the organic acid anhydride may be at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, etc., specific examples of the organic acid may be at least one of acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, etc., specific examples of the ester may be at least one of dibutyl phthalate, 2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 2, 3-diisopropyl-1, 4-butanediol dibenzoate, 3, 5-heptanediol dibenzoate, and 4-ethyl-3, 5-heptanediol dibenzoate, specific examples of the ether may be at least one of methyl ether, diethyl ether, propyl ether, butyl ether, amyl ether, 2-isopropyl-2-isopentyl dimethoxypropane, and 9,9- (dimethoxymethyl) fluorene, and the ketone may be at least one of acetone, methyl ethyl ketone, and benzophenone.

The organic epoxy compound used in the above-mentioned method two may be at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and the like, and preferably epichlorohydrin.

The organic phosphorus compound used in the above-mentioned method II may be a hydrocarbon-based ester or halogenated hydrocarbon-based ester of orthophosphoric acid or phosphorous acid, and specific examples of the organic phosphorus compound may be given as follows: trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite or benzyl phosphite, etc., preferably tributyl orthophosphate.

The fatty alcohol compound used in the above-mentioned method II may be a linear or branched alkane of 1 to 20 carbon atoms, a monohydric or polyhydric fatty alcohol, preferably a linear or branched monohydric fatty alcohol of 1 to 10 carbon atoms, and specific examples thereof may be given: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, (2-ethyl) hexyl alcohol, octanol, nonanol, decanol, and the like, with (2-ethyl) hexyl alcohol being preferred.

The inert diluent used in the mother liquor formation in the above process II may be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.

The amount of each component used in the formation of the mother liquor in the above-mentioned method II may be 0.2 to 10 moles, preferably 0.5 to 4 moles, per mole of magnesium halide; the organophosphorus compound may be 0.1 to 3 moles, preferably 0.3 to 1.5 moles; the fatty alcohol compound may be 0.2 to 10 moles, preferably 0.5 to 3 moles; the titanium compound may be present in an amount of 0.5 to 20 moles, preferably 5 to 15 moles; the precipitation aid component may be present in an amount of 0.01 to 0.3 mole, preferably 0.02 to 0.2 mole; the total amount of the internal electron donor compound (ID) may be 0 to 10 moles, preferably 0.02 to 0.3 moles.

The contacting temperature of the components at the formation of the mother liquor in the above process two is generally from-40 to 200 ℃, preferably from-20 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.

In the titanium treatment process described in the above method II, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene may be optionally added to the titanium tetrachloride-containing solution used.

In the titanium treatment process in the above-mentioned method II, the amount of each component in the titanium tetrachloride-containing solution to be used is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0 to 100 mol, preferably 0 to 50 mol.

In the above method II, the number of titanium treatments is 0 to 10, preferably 1 to 5.

The electron donor compound described above may be optionally added during the titanium treatment in the above-mentioned method II, wherein the internal electron donor is used in an amount of usually 0.005 to 10 moles, preferably 0.01 to 1 mole.

In the above-mentioned method II, the titanium treatment temperature is usually 0 to 200 ℃, preferably 30 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 6 hours.

In a third method, an alcohol adduct of magnesium dihalide is suspended in an inert diluent to form a suspension, and the suspension is mixed and contacted with the above-mentioned titanium compound and internal electron donor (ID) to obtain a solid dispersion system, hereinafter referred to as a mother liquid. Filtering the mother liquor, and suspending the obtained solid matters in a solution containing titanium tetrachloride for contact treatment, which is hereinafter generally referred to as titanium treatment; and then filtering and washing to obtain the catalyst solid component.

The alcohol adduct of magnesium dihalide described in the above method three can be produced by the following method: mixing an alcohol (such as methanol, ethanol, propanol or isopropanol, etc.) with magnesium halide in the presence of an inert solvent (such as hexane, heptane, octane, decane, benzene, toluene, xylene, etc.) which is not miscible with the adduct to form an emulsion, and rapidly quenching and dispersing the emulsion to obtain spherical particles, namely the alcohol adduct of magnesium dihalide.

The inert diluent used in the formation of the mother liquor in the above process three may be at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.

The amount of each component used for forming the mother liquor in the above method III is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0.5 to 100 moles, preferably 1 to 50 moles; the total amount of the electron donor compound (ID) is usually 0.005 to 10 moles, preferably 0.01 to 1 mole.

The contacting temperature of the components in the formation of the mother liquor in the above process three is generally from-40 to 200 ℃, preferably from-20 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 8 hours.

In the titanium treatment process described in the third method, an inert diluent such as at least one of hexane, heptane, octane, decane, benzene, toluene and xylene may be optionally added to the titanium tetrachloride-containing solution.

In the titanium treatment process in the third method, the amount of each component in the titanium tetrachloride-containing solution used is 0.5 to 100 moles, preferably 1 to 50 moles, per mole of magnesium; the inert diluent is used in an amount of usually 0 to 100 mol, preferably 0 to 50 mol.

The number of titanium treatments in the above-mentioned method three is 0 to 10, preferably 1 to 5.

The electron donor compound (ID) described above may be optionally added during the titanium treatment in the above method III, wherein the internal electron donor is used in an amount of usually 0.005 to 10 mol, preferably 0.01 to 1 mol.

The titanium treatment temperature in the above method three is usually 0 to 200 ℃, preferably 30 to 150 ℃; the contact time is usually 1 minute to 20 hours, preferably 5 minutes to 6 hours.

According to some embodiments of the present invention, the catalyst solid component B may comprise a catalyst selected from, but not limited to, phthalate compounds selected from those represented by formula (IV),

in the formula (IV), R ₁₅ And R is ₁₆ The same or different, each independently selected from the group consisting of straight chain alkanes of 1 to 20 carbon atoms, branched alkyl of 3 to 20 carbon atoms, cycloalkyl of 3 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkylaryl of 7 to 20 carbon atoms, or aralkyl of 7 to 20 carbon atoms, said alkyl, cycloalkyl, aryl, alkane The hydrogen atom on the carbon in the aryl or aralkyl group may be optionally substituted with a heteroatom, alkyl or alkoxy group, and the carbon atom on the alkyl, cycloalkyl, aryl, alkylaryl or aralkyl backbone may be optionally substituted with a heteroatom; preferably, R ₁₅ And R is ₁₆ Each independently selected from a straight chain alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or an aryl group of 6 to 10 carbon atoms; more preferably, R ₁₅ And R is ₁₆ Each independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 1 to 6 carbon atoms; further preferably, R ₁₅ And R is ₁₆ Each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or phenyl.

Examples of suitable phthalate compounds of formula (IV) include, but are not limited to: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di (1-methyl) propyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, di (1-methyl) butyl phthalate, di (2-methyl) butyl phthalate, diisopentyl phthalate, di (1, 1' -dimethyl) propyl phthalate, dipentyl phthalate, di (1, 2-dimethyl) propyl phthalate, n-hexyl phthalate, di (1-methyl) pentyl phthalate, di (2-methyl) pentyl phthalate, di (3-methyl) pentyl phthalate, diisohexyl phthalate, di (1, 1' -dimethyl) butyl phthalate, di (2, 2' -dimethyl) butyl phthalate, di (1, 2-dimethyl) butyl phthalate, di (2, 3-dimethyl) butyl phthalate, di (1, 1' -dimethyl) butyl phthalate; 2-trimethyl) propyl phthalate, di (1, 2' -trimethyl) propyl phthalate, n-heptyl phthalate, di (1-methyl) hexyl phthalate, di (2-methyl) hexyl phthalate, di (3-methyl) hexyl phthalate, di (4-methyl) hexyl phthalate, diisoheptyl phthalate, di (1, 1' -dimethyl) pentyl phthalate, di (2, 2' -dimethyl) pentyl phthalate, di (3, 3' -dimethyl) pentyl phthalate, dithienyl phthalate, di (1, 2-dimethyl) pentyl phthalate, di (1, 3-dimethyl) pentyl phthalate, di (1, 4-dimethyl) pentyl phthalate, di (2, 3-dimethyl) pentyl phthalate, di (2, 4-dimethyl) pentyl phthalate, di (3, 4-dimethyl) pentyl phthalate, di (1, 1', 2-trimethyl) butyl phthalate, di (1, 1', 3-trimethyl) butyl phthalate, di (1, 2' -trimethyl) butyl phthalate, di (2, 2', 3-trimethyl) butyl phthalate, di (1, 3' -trimethyl) butyl phthalate, di (2, 3' -trimethyl) butyl phthalate, di (1, 1', 2' -tetramethyl) propyl phthalate, n-octyl phthalate, di (1-methyl) heptyl phthalate, di (2-methyl) heptyl phthalate, di (3-methyl) heptyl phthalate, di (4-methyl) heptyl phthalate, and, di (5-methyl) heptyl phthalate, diisooctyl phthalate, di (1, 1' -dimethyl) hexyl phthalate, di (2, 2' -dimethyl) hexyl phthalate, di (3, 3' -dimethyl) hexyl phthalate, di (4, 4' -dimethyl) hexyl phthalate, di (5, 5' -dimethyl) hexyl phthalate, di (1, 2-dimethyl) hexyl phthalate, di (1, 3-dimethyl) hexyl phthalate, di (1, 4-dimethyl) hexyl phthalate, di (1, 5-dimethyl) hexyl phthalate, di (2, 3-dimethyl) hexyl phthalate, di (2, 4-dimethyl) hexyl phthalate, di (2, 5-dimethyl) hexyl phthalate, di (3, 4-dimethyl) hexyl phthalate, di (3, 5-dimethyl) hexyl phthalate, di (4, 5-dimethyl) hexyl phthalate, di (1, 1 '; 2-trimethyl) pentyl ester, di (1, 1', 3-trimethyl) pentyl phthalate, di (1, 1', 4-trimethyl) pentyl phthalate, di (1, 2' -trimethyl) pentyl phthalate, di (2, 2', 3-trimethyl) pentyl phthalate, di (2, 2', 4-trimethyl) pentyl phthalate, bis (1, 3 '-trimethyl) pentyl phthalate, bis (2, 3' -trimethyl) pentyl phthalate, bis (3, 3', 4-trimethyl) pentyl ester, di (1, 4' -trimethyl) pentyl ester of phthalic acid, di (2, 4 '-trimethyl) pentyl ester of phthalic acid, di (3, 4' -trimethyl) pentyl ester of phthalic acid, di (1, 1', 2' -tetramethyl) butyl ester of phthalic acid, di (1, 1',3,3' -tetramethyl) butyl phthalate, di (2, 2', 3' -tetramethyl) butyl phthalate, diphenyl phthalate, di (o-methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (m-methyl) phenyl phthalate, di (o-methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate, di (m-methoxy) phenyl phthalate; preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, n-hexyl phthalate, diisohexyl phthalate, n-heptyl phthalate, isoheptyl phthalate, n-octyl phthalate, isooctyl phthalate, diphenyl phthalate, di (methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (m-methyl) phenyl phthalate, di (o-methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate; more preferably selected from the group consisting of dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-t-butyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, n-hexyl phthalate, isohexyl phthalate, diphenyl phthalate, di (methyl) phenyl phthalate, di (p-methyl) phenyl phthalate, di (methoxy) phenyl phthalate, di (p-methoxy) phenyl phthalate.

According to some embodiments of the present invention, the catalyst solid component B may comprise a catalyst selected from, but not limited to, glycol ester compounds selected from those represented by formula (V),

in the formula (V), R ₁₇ And R is ₁₈ The same or different, each is a substituted or unsubstituted straight-chain C1-C20 alkyl group, a substituted or unsubstituted branched-chain C3-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C7-C20 alkylaryl group, a substituted or unsubstituted C7-C20 aralkyl group, a substituted or unsubstituted C2-C10 alkylene group, or a substituted or unsubstituted C10-C20 fused ring aryl group; r is R ₁₉ -R ₂₄ The same or different, each is hydrogen, halogen, substituted or unsubstituted straight-chain C1-C20 alkyl, substituted or unsubstituted branched-chain C3-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 alkylaryl, substituted or unsubstituted C7-C20 aralkyl, substituted or unsubstituted C2-C10 alkenyl, or substituted or unsubstituted C10-C20 fused ring aryl; or R is ₁₉ -R ₂₂ At least one of which is together with R ₂₃ -R ₂₄ Is formed into a ring.

Examples of suitable glycol ester compounds represented by the formula (V) include, but are not limited to: at least one of 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 1, 3-butanediol dimethylbenzoate, 2-methyl-1, 3-butanediol diisochlorobenzoate, 2, 3-dimethyl-1, 3-butanediol dibenzoate, 1, 3-pentanediol pivalate, 2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic acid cinnamate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and 2-methyl-3, 5-heptanediol dibenzoate; preferably at least one of 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate and 2, 4-pentanediol dibenzoate; more preferably 3, 5-heptanediol dibenzoate.

According to some embodiments of the present invention, the catalyst solid component B may comprise a catalyst selected from, but not limited to, a cyano succinate compound represented by formula (VI),

in the formula (VI), R ₂₅ And R is ₂₆ The same or different, each independently selected from hydrogen, a straight chain alkyl of 1 to 14 carbon atoms, a branched alkyl of 3 to 14 carbon atoms, a cycloalkyl of 3 to 10 carbon atoms, an aryl of 6 to 10 carbon atoms, an alkylaryl of 7 to 10 carbon atoms, or an aralkyl of 7 to 10 carbon atoms; r is R ₂₇ And R is ₂₈ Each of which is the same or different and is independently selected from a linear alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms or an arylalkyl group of 7 to 20 carbon atoms.

Examples of suitable cyano succinic acid ester compounds of formula (VI) include, but are not limited to: 2, 3-Diisopropyl-2-cyanosuccinic acid dimethyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid diethyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid di-n-propyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid diisopropyl ester, 2, 3-Din-butyl-2, 3-Diisopropyl-2-cyanosuccinic acid diisobutyl ester, 2, 3-Diisopropyl-2-cyanosuccinic acid-1-methyl-4-ethyl ester (R) ₂₅ Methyl, R ₂₆ =ethyl), 2, 3-diisopropyl-2-cyano-butanedioic acid-1-ethyl-4-methyl ester (R ₂₅ =ethyl, R ₂₆ =methyl), 2, 3-diisopropyl-2-cyano-butanedioic acid-1-n-butyl-4-ethyl ester (R ₂₅ N-butyl, R ₂₆ =ethyl), 2, 3-diisopropyl-2-cyano-butanedioic acid 1-ethyl-4-n-butyl ester (R ₂₅ =ethyl, R ₂₆ =n-butyl), 2, 3-diisobutyl-2-cyanobuty-anedioic acid dimethyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid diethyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid di-n-propyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid di-n-butyl ester, 2, 3-diisobutyl-2-cyanobuty-anedioic acid diisobutyl ester, 2, 3-diisobutyl-2-cyanobuty-1-methyl-4-ethyl ester (R) ₂₅ Methyl, R ₂₆ =ethyl), 2, 3-diisobutyl-2-cyano-succinic acid-1-ethyl-4-methyl ester (R ₂₅ =ethyl, R ₂₆ =methyl), 2, 3-diisobutyl-2-cyanobutanedioic acid-1-n-butyl-4-ethyl ester (R ₂₅ N-butyl, R ₂₆ =ethyl), 2, 3-diisobutyl-2-cyano-butanedioic acid-1-ethyl-4-n-butyl ester (R ₂₅ =ethyl, R ₂₆ 2, 3-di-sec-butyl-2-cyanobutyanedioic acid diethyl ester, 2, 3-di-sec-butyl-2-cyanobutyanedioic acid diisopropyl ester, 2, 3-di-sec-butyl-2-cyanobutyanedioic acid di-n-butyl ester, 2, 3-di-sec-butyl-2-cyanobutyronic acid diisobutyl ester, 2, 3-di-sec-butyl-2-cyanobutyronic acid-1-methyl-4-ethyl ester (R) ₂₅ Methyl, R ₂₆ =ethyl), 2, 3-di-sec-butyl-2-cyano succinic acid-1-ethyl-4-methyl ester (R ₂₅ =ethyl, R ₂₆ Methyl), 2, 3-di-sec-butyl-2-cyano-butanedioic acid-1-n-butyl-4-ethyl ester (R ₂₅ N-butyl, R ₂₆ =ethyl), 2, 3-di-sec-butyl-2-cyano succinic acid-1-ethyl-4-n-butyl ester (R ₂₅ =ethyl, R ₂₆ =n-butyl), dimethyl 2, 3-dicyclopentyl-2-cyanobutyrate, diethyl 2, 3-dicyclopentyl-2-cyanobutyrate, di-n-propyl 2, 3-dicyclopentyl-2-cyanobutyrate, diisopropyl 2, 3-dicyclopentyl-2-cyanobutyrate, di-n-butyl 2, 3-dicyclopentyl-2-cyanobutyrate, diisobutyl 2, 3-dicyclopentyl-2-cyanobutyrate, 1-methyl 2-cyanobutyrate-4-ethyl ester (R) ₂₅ Methyl, R ₂₆ =ethyl), 2, 3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl-4-methyl ester (R ₂₅ =ethyl, R ₂₆ 2=methyl), 2, 3-dicyclopentyl-2-cyanosuccinic acid-1-n-butyl-4-ethyl ester (R) ₂₅ N-butyl, R ₂₆ =ethyl), 2, 3-dicyclopentyl-2-cyanosuccinic acid-1-ethyl-4-n-butyl ester (R ₂₅ =ethyl, R ₂₆ =n-butyl), dimethyl 2, 3-dicyclohexyl-2-cyanobutyrate, diethyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-n-propyl 2, 3-dicyclohexyl-2-cyanobutyrate, diisopropyl 2, 3-dicyclohexyl-2-cyanobutyrate, di-n-butyl 2, 3-dicyclohexyl-2-cyanobutyrate, 2, 3-di-n-butylsuccinate Cyclohexyl-2-cyanobutanedioic acid diisobutyl ester, 2, 3-dicyclohexyl-2-cyanobutanedioic acid-1-methyl ester-4-ethyl ester (R) ₂₅ Methyl, R ₂₆ =ethyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-ethyl-4-methyl ester (R ₂₅ =ethyl, R ₂₆ =methyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-n-butyl-4-ethyl ester (R ₂₅ N-butyl, R ₂₆ =ethyl), 2, 3-dicyclohexyl-2-cyanobuccinic acid-1-ethyl-4-n-butyl ester (R ₂₅ =ethyl, R ₂₆ N-butyl); preferably diethyl 2, 3-diisopropyl-2-cyanobuccinate, di-n-propyl 2, 3-diisopropyl-2-cyanobuccinate, di-isopropyl 2, 3-diisopropyl-2-cyanobuccinate, di-n-butyl 2, 3-diisopropyl-2-cyanobuccinate, diisobutyl 2, 3-diisopropyl-2-cyanobuccinate; more preferably diethyl 2, 3-diisopropyl-2-cyano succinate.

According to some embodiments of the present invention, the catalyst solid component B may comprise a catalyst selected from, but not limited to, diethers selected from those represented by formula (VII),

in the formula (VII), R ₂₉ And R is ₃₀ The same or different, each independently selected from a straight chain of 1 to 10 carbon atoms or a branched alkyl of 3 to 10 carbon atoms; r is R ₃₂ And R is ₃₃ The same or different, each independently selected from a straight chain of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, a substituted or unsubstituted aryl of 6 to 20 carbon atoms, or an alkylaryl of 7 to 20 carbon atoms; r is R ₃₁ And R is ₃₄ The same or different, each independently selected from hydrogen, a straight chain alkyl group of 1 to 10 carbon atoms, or a branched alkyl group of 3 to 10 carbon atoms.

Examples of suitable diether compounds of formula (VII) include, but are not limited to: 2-isopropyl-2-isopentyl-1, 3-dimethoxysilane, 9-bis (methoxymethyl) fluorene, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2-dicyclopentyl dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxysilane, 9-bis (methoxymethyl) fluorene are preferred.

According to some embodiments of the present invention, the catalyst solid component B may comprise a catalyst selected from, but not limited to, succinate compounds selected from those represented by formula (VIII),

in the formula (VIII), R ₃₅ And R is ₃₆ The same or different, each independently selected from a straight chain alkyl of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, an alkenyl of 2 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an aralkyl of 7 to 20 carbon atoms, or an alkylaryl of 7 to 20 carbon atoms; r is R ₃₇ -R ₄₀ Are identical or different from each other and are each independently selected from the group consisting of hydrogen, a linear alkyl group of 1 to 20 carbon atoms, a branched alkyl group of 3 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, and an alkylaryl group of 7 to 20 carbon atoms; the R is ₃₅ And R is ₃₆ Optionally containing heteroatoms.

Examples of suitable succinic acid ester compounds represented by the formula (VIII) include, but are not limited to: diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropyl succinate, diethyl 2, 3-diisopropyl succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2,3- (bistrimethylsilyl) succinate, diethyl 2- (, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2, 3-methylsuccinate, diethyl 2, 3-tetraethyl succinate, diethyl 2, 3-tetrapropyl succinate, diethyl 2, 3-diethyl-2, 3-diisopropyldisuccinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2,3- (bistrimethylsilyl) succinate, 2- (, 3-trifluoropropyl) -3-methylsuccinic acid diisobutyl ester, 2, 3-diisoamyl succinic acid diisobutyl ester, 2,3- (1-trifluoromethyl-ethyl) succinic acid diisobutyl ester, 2-isopropyl-3-isobutyl succinic acid diisobutyl ester, 2-tert-butyl-3-isopropyl succinic acid diisobutyl ester, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2, 3-methylsuccinate, diisobutyl 2, 3-tetraethyl succinate, diisobutyl 2, 3-tetrapropyl succinate, diisobutyl 2, 3-diethyl-2, 3-diisopropyldisuccinate; preferably diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-diisopropylsuccinate; 2, 3-diisopropylsuccinate.

According to the present invention, in the catalyst solid component B, the compound of the internal electron donor may be used alone or two or more internal electron donor compounds may be used in combination.

In a preferred case, the aluminum alkyl compound may be a compound represented by the formula (IX),

AlR' _n 'X' _3-n' (IX)

wherein R' is one of the following: hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms; x 'is halogen, and n' is an integer of 1-3.

The alkyl aluminum compound is preferably at least one selected from the following compounds: at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride. More preferably triethylaluminum and/or triisobutylaluminum.

The amount of the alkyl aluminum compound may be conventional in the art. Generally, the molar ratio of aluminum in the alkyl aluminum compound C to titanium in the solid catalyst composition is from 5 to 5000:1, a step of; preferably 20-1000:1, a step of; more preferably 50-500:1.

according to some embodiments of the invention, the total molar ratio of aluminum in the alkyl aluminum compound C to the external electron donor a is from 0.5-1 to 50:1, preferably 1-30:1, more preferably 1-20:1.

In a third aspect the present invention provides a process for the polymerisation of olefins comprising contacting one or more olefins with a catalyst system according to the second aspect to obtain a polymer. Wherein at least one of the olefins is represented by the general formula CH ₂ An alkene represented by CHR, wherein R is selected from hydrogen or alkyl of 1-6 carbon atoms.

The olefin polymerization method of the present invention can be used for homo-polymerization of olefins, and can also be used for copolymerizing a plurality of olefins.

According to some embodiments of the invention, the olefin is preferably at least one selected from ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene; more preferably at least one selected from ethylene, propylene and 1-butene.

The olefin polymerization process according to the present invention, the olefin polymerization conditions comprising: the temperature of the olefin polymerization is 0 to 150 ℃, preferably 60 to 130 ℃; the time is 0.1-5 hours, preferably 0.5-4 hours, and the pressure is 0.01-10MPa, preferably 0.5-5MPa. The amount of catalyst may be any of the various catalysts of the prior art.

The catalyst with excellent comprehensive performance can be obtained by adopting the novel external electron donor, and has high polymerization activity, good hydrogen regulation sensitivity and higher stereospecificity when being used for propylene polymerization. Meanwhile, the high-temperature self-deactivation performance is achieved.

Detailed Description

The following examples are given to illustrate the invention without limiting it.

The testing method comprises the following steps:

1. titanium content in the catalyst: according to 721 spectrophotometer testing.

2. Catalyst particle size distribution: measured according to the Markov 2000 n-hexane dispersant laser diffraction method.

3. Determination of the melt index of the polymers: measured according to GB/T3682-2000.

4. The isotacticity of the polymer was determined using heptane extraction: after 2 g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, the residue was dried to constant weight and the ratio of the weight (g) of the polymer to 2 (g) was isotacticity.

Examples:

1. synthesis of electron donor compounds:

compound a 1N, N-di-N-butylaminoacetic acid ethyl ester

Into a 1000mL three-necked flask, di-n-butylamine (77.4 g, 0.6 mol) and K were added ₂ CO ₃ (82.8 g, 60 mmol), KI (1.8 g, 12 mmol) and acetonitrile 400mL. Ethyl bromoacetate (85.8 g, 0.51 mmol) was added dropwise. The reaction was refluxed for 8 hours. And (5) finishing the reaction. And (3) cooling the system. Filtering and desalting. The solid was washed with 2X 100mL of dichloromethane. The organic phase was washed with 2X 100mL of saturated brine. The organic phase was dried over anhydrous sodium sulfate and filtered. The solvent was distilled off under reduced pressure, and the product was obtained by rectification (5 mmHg,64 ℃ C.).

¹ HNMR(CDCl ₃ /TMS,300MHz)δ(ppm):0.67-0.88(t,6H,-N CH ₂ CH ₂ CH ₂ CH ₃ ),1.05-1.17(q,4H,-NCH ₂ CH ₂ CH ₂ CH ₃ ),1.20-1.29(tetra,3H,-COOCH ₂ CH ₃ )，1.20-1.49(m,4H,-NCH ₂ CH ₂ CH ₂ CH ₃ ),2.30-2.70(m,4H,-NCH ₂ CH ₂ CH ₂ CH ₃ ),3.30(s,2H,-NCH ₂ COOEt)，4.13(tetra,2H,-COOCH ₂ CH ₃ )。

Compound a 2N, N-di-N-octyl amino acetic acid ethyl ester

N, N-di-N-octylamino ethyl acetate was prepared using a similar method to compound a 1.

¹ H NMR(CDCl ₃ /TMS,300MHz)0.86-0.93(m,6H,-N C ₇ H ₁₄ CH ₃ ),1.27(tetra,3H,-COOCH ₂ CH ₃ )，1.27(m,20H,-NCH ₂ CH ₂ C ₅ H ₁₀ CH ₃ ),1.49(m,4H,-NCH ₂ CH ₂ C ₅ H ₁₀ CH ₃ )，2.30-2.60(m,4H,-NCH ₂ C ₇ H ₁₅ ),3.30(s,2H,-NCH ₂ COOEt)，4.13(tetra,2H,-COOCH ₂ CH ₃ )。

Compound a 3N, N-diisooctylamino ethyl acetate

N, N-diisooctylamino ethyl acetate was prepared using a similar method to compound a 1.

¹ H NMR(CDCl ₃ /TMS,300MHz)0.89-0.93(m,6H,-NCH ₂ CH(CH ₂ CH ₃ )C ₄ H ₈ CH ₃ ),1.27(m,3H,-COOCH ₂ CH ₃ )，1.27(m,16H,-NCH ₂ CH(CH ₂ CH ₃ )C ₄ H ₈ CH ₃ ),1.53(m,4H,-NCH ₂ CH(CH ₂ CH ₃ )C ₄ H ₁₆ CH ₃ )，1.71(m,2H,-NCH ₂ CH(CH ₂ CH ₃ )C ₄ H ₁₆ CH ₃ )，2.30-2.60(m,4H,-NCH ₂ C ₇ H ₁₅ ),3.30(s,2H,-NCH ₂ COOEt)，4.13(tetra,2H,-COOCH ₂ CH ₃ )。

Compound a 4N, N-diallylaminobutyl acetate

Using a similar method to compound a1, starting material was butyl chloride to produce N, N-diallylaminobutyl acetate.

¹ H NMR(CDCl ₃ /TMS,300MHz)0.86-0.91(t,3H,-OCH ₂ CH ₂ CH ₂ CH ₃ ),1.37-1.50(m,2H,-OCH ₂ CH ₂ CH ₂ CH ₃ )，1.57-1.66(m,2H,-OCH ₂ CH ₂ CH ₂ CH ₃ ),3.23-3.25(d,2H,-NCH ₂ CH＝CH ₂ )，3.31(s,2H,-NCH ₂ COO-)，4.03-4.07(t,2H,--OCH ₂ CH ₂ CH ₂ CH ₃ ),5.11-5.17(m,2H,2H,-NCH ₂ CH＝CH ₂ )，5.79-5.93(m,1H,-NCH ₂ CH＝CH ₂ )。

2. Preparation of solid catalyst component

Preparative example 1

After a 16L pressure-resistant reactor equipped with a stirrer was sufficiently replaced with nitrogen, 10L of ethanol, 300ml of 2-ethylhexanol, 11.2g of iodine, 8g of magnesium chloride and 640g of magnesium powder were added to the reactor. Stirring and simultaneously allowing the system to reflux and react until no more hydrogen is discharged. The reaction was stopped, washed three times with 3L ethanol, filtered and dried. The obtained alkoxy magnesium carrier. The obtained alkoxymagnesium carrier d50=30.2 um, span value 0.81, m value 0.015.

Preparation of solid catalyst Components 1-4:

10g of the magnesium alkoxide carrier prepared in the preparation example and 50mL of toluene were added to 10mmol of the electron donor compound shown in Table 1 to prepare a suspension; adding 40mL of toluene and 60mL of titanium tetrachloride into a 300mL reaction kettle repeatedly replaced by high-purity nitrogen, adding the prepared suspension into the kettle, heating to 80 ℃, keeping the temperature for 1 hour, continuously heating to 115 ℃, keeping the temperature for 2 hours, and press-filtering the liquid (mother liquor) to be clean. Adding 90mL of toluene and 60mL of titanium tetrachloride to the mixture, heating to 110 ℃ and stirring for 1 hour (titanium treatment), filtering and pressing the liquid (mother liquor), adding 120mL of toluene and 30mL of titanium tetrachloride to the mixture, heating to 110 ℃ and stirring for 2 hours (titanium treatment), filtering the liquid, washing the obtained solid with 150mL of n-hexane for 3 times at 55 ℃, washing the solid with n-hexane at room temperature, filtering the liquid and drying to obtain the solid catalyst component.

Preparation of catalyst solid component 5:

3.150mol (300.0 g) anhydrous magnesium chloride, 19.68mol (2.1L) toluene and 8.4mol (1.1L) 2-ethylhexanol are sequentially added into a reaction kettle subjected to high-purity nitrogen repeated replacement, and the mixture is reacted for 3.0 hours under the conditions of stirring rotation speed of 450rpm and temperature of 115 ℃ to obtain stable and uniform alkoxide solution; 84mmol (42 ml) of 3, 5-heptanediol dibenzoate and 260mmol (60 ml) of diphenyldimethoxysilane were added thereto, and the mixture was stirred for 60 minutes and cooled to room temperature.

The above homogeneous solution of the above-mentioned alcohol compound containing 84mmol (42 ml) of 3, 5-heptanediol dibenzoate and 260mmol (60 ml) of diphenyldimethoxysilane was charged into a reactor containing 60mol (6.6L) of titanium tetrachloride and 11.4mol (1.2L) of toluene at-20℃and fully replaced with nitrogen gas, and they were brought into contact with each other by stirring at-20℃for 5 hours, after which a solid precipitate was precipitated by heating to 100℃during the heating, 138.6mmol (30 g) of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was added, and after the reaction was completed for 1 hour, the liquid was filtered; then, the solid was further contacted with 40.8mol (4.32L) of toluene, 26.2mol (2.88 ml) of titanium tetrachloride and 193.8mmol (42 g) of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane at 100℃for 1.5 hours, and after the completion of the reaction, the liquid was filtered; the solid was then contacted with 40.8mol (4.32L) toluene and 26.2mol (2.88 ml) titanium tetrachloride at 110℃for a further 0.5 hour; after the reaction, the liquid was filtered, and then 40.8mol (4.32L) of toluene and 26.2mol (2.88 ml) of titanium tetrachloride were repeatedly contacted with the solid at 110℃for one more reaction. The obtained solid was washed 5 times with 55.14mol (7.2L) of hexane and then dried to obtain an olefin polymerization catalyst solid component 5.

TABLE 1 internal electron donor species and amounts in different examples

Examples 1 to 24

After sufficient displacement of propylene in the gas phase in a 5L autoclave, 1L of liquid propylene, 5mL of a hexane solution of triethylaluminum (triethylaluminum concentration: 0.5 mmol/mL) were added at room temperature, the temperature was raised to 50℃and 2mL of a hexane solution of an external electron donor (concentration: 0.10 mmol/mL) shown in Table 2, 10mL of anhydrous hexane and 10mg of a solid catalyst component, 0.9 standard liter of hydrogen and 2L of liquid propylene were added; the temperature was raised to the corresponding polymerization temperature of Table 2 with stirring for 10 minutes, and after polymerization at this temperature for 1 hour, stirring was stopped to remove the unpolymerized propylene monomer and collect the polymer.

Comparative examples 1 to 12

The specific procedure is as in examples 1-10, except that the external electron donor is replaced by methylcyclohexyldimethoxy silane.

TABLE 2 catalyst Performance

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As can be seen from the data in Table 2, the catalyst has good high-temperature self-inactivating property and is beneficial to the application of the catalyst in industrial devices when the amino ester compound and the siloxane compound are used as external electron donors for propylene polymerization, and high polymerization activity, good hydrogen regulation sensitivity and stereotactic capability can be obtained.

Any numerical value recited in this disclosure includes all values incremented by one unit from the lowest value to the highest value if there is only a two unit interval between any lowest value and any highest value. For example, if the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is stated to be 50-90, it is meant in this specification that values such as 51-89, 52-88 … …, and 69-71, and 70-71 are specifically recited. For non-integer values, 0.1, 0.01, 0.001 or 0.0001 units may be considered as appropriate. This is only a few examples of the specific designations. 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-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.

Claims

1. An external electron donor for olefin polymerization, which comprises an amino ester compound shown in a formula (I) and a siloxane compound shown in a formula (II),

wherein R is ₁ Selected from the group consisting of linear alkyl groups of 1 to 20 carbon atoms, branched alkyl groups of 3 to 20 carbon atoms, cycloalkyl groups of 3 to 20 carbon atoms, wherein the hydrogen atoms on the carbon atoms in the alkyl, cycloalkyl groups are optionally substituted or unsubstituted with heteroatoms, alkyl groups or alkoxy groups, and the carbon atoms on the alkyl, cycloalkyl backbone are optionally substituted or unsubstituted with heteroatoms;

R ₂ and R is ₃ Each of which is the same or different and is independently selected from a straight chain alkyl group of 1 to 20 carbon atoms, a branched chain alkyl group of 3 to 20 carbon atoms, and a cycloalkyl group of 3 to 20 carbon atoms, wherein the hydrogen atoms on the carbon in the alkyl, cycloalkyl groups are optionally substituted or unsubstituted with heteroatoms, alkyl groups, or alkoxy groups, and the carbon atoms on the alkyl, cycloalkyl main chain are optionally substituted or unsubstituted with heteroatoms; and R is ₂ And R is ₃ Optionally linked in a ring or not;

R ₄ and R is ₅ Each of which is the same or different and is independently selected from a straight chain alkyl group of 1 to 20 carbon atoms, a branched chain alkyl group of 3 to 20 carbon atoms, and a cycloalkyl group of 3 to 20 carbon atoms, wherein the hydrogen atoms on the carbon atoms in the alkyl and cycloalkyl groups are optionally substituted or unsubstituted by heteroatoms, alkyl groups, or alkoxy groups, and the carbon atoms on the alkyl and cycloalkyl main chains are optionally substituted or unsubstituted by heteroatoms;

R ₁ ” _m” R ₂ ” _n” Si(OR _3” ) _4-m”-n” (II)

In the formula (II), R ₁ "and R ₂ "same or different," each independently selected from the group consisting of halogen, hydrogen atom, straight chain alkyl of 1-20 carbon atoms, branched alkyl of 3-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, aryl of 6-20 carbon atoms, and haloalkyl of 1-20 carbon atoms; r3' is selected from a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms; m 'and n' are each independently selected from integers from 0 to 3, and m '+n'.<4；

The amino ester compound accounts for 5-95mol% of the external electron donor A.

2. A catalyst system for olefin polymerization comprising

(1) An external electron donor a;

(3) An alkylaluminum compound C as a cocatalyst;

in the formula (I), R ₁ Selected from the group consisting of linear alkyl groups of 1 to 20 carbon atoms, branched alkyl groups of 3 to 20 carbon atoms, cycloalkyl groups of 3 to 20 carbon atoms, wherein the hydrogen atoms on the carbon atoms in the alkyl, cycloalkyl groups are optionally substituted or unsubstituted with heteroatoms, alkyl groups or alkoxy groups, and the carbon atoms on the alkyl, cycloalkyl backbone are optionally substituted or unsubstituted with heteroatoms;

R ₂ And R is ₃ Are identical or different and are each independently selected from a linear alkyl group of 1 to 20 carbon atoms, a branched alkyl group of 3 to 20 carbon atoms, 3Cycloalkyl of up to 20 carbon atoms, wherein the hydrogen atom on a carbon in the alkyl, cycloalkyl is optionally substituted or unsubstituted with a heteroatom, alkyl or alkoxy, and the carbon atom on the alkyl, cycloalkyl backbone is optionally substituted or unsubstituted with a heteroatom; and R is ₂ And R is ₃ Optionally linked in a ring or not;

R ₁ ” _m” R ₂ ” _n” Si(OR _3” ) _4-m”-n” (II)

in the formula (II), R ₁ "and R ₂ "same or different," each independently selected from the group consisting of halogen, hydrogen atom, straight chain alkyl of 1-20 carbon atoms, branched alkyl of 3-20 carbon atoms, cycloalkyl of 3-20 carbon atoms, aryl of 6-20 carbon atoms, and haloalkyl of 1-20 carbon atoms; r3' is selected from a straight chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a haloalkyl group having 1 to 20 carbon atoms; m 'and n' are each independently selected from integers from 0 to 3, and m '+n'. <4；

The amino ester compound accounts for 5-95mol% of the external electron donor A;

the internal electron donor compound is at least one selected from phthalate compounds, glycol esters compounds, cyano succinic acid esters, diethers and succinic acid esters

The phthalate compound is selected from phthalate compounds shown in a formula (IV),

in the formula (IV), R ₁₅ And R is ₁₆ The same or different, each independently selected from a straight chain alkyl of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, an aryl of 6 to 20 carbon atoms, an alkylaryl of 7 to 20 carbon atoms, or an arylalkyl of 7 to 20 carbon atoms, the hydrogen atoms on the carbon in the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl being optionally substituted with heteroatoms, alkyl, or alkoxy groups, the carbon atoms on the alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl backbone being optionally substituted with heteroatoms;

the glycol ester compound is selected from glycol ester compounds shown in a formula (V),

in the formula (V), R ₁₇ And R is ₁₈ The same or different, each is a substituted or unsubstituted straight chain alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted branched chain alkyl group of 3 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group of 7 to 20 carbon atoms, a substituted or unsubstituted aralkyl group of 7 to 20 carbon atoms, a substituted or unsubstituted alkylene group of 2 to 10 carbon atoms, or a substituted or unsubstituted fused ring aryl group of 10 to 20 carbon atoms; r is R ₁₉ -R ₂₄ The same or different, each independently is hydrogen, halogen, substituted or unsubstituted straight chain alkyl of 1 to 20 carbon atoms, substituted or unsubstituted branched alkyl of 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 20 carbon atoms, substituted or unsubstituted aryl of 6 to 20 carbon atoms, substituted or unsubstituted alkylaryl of 7 to 20 carbon atoms, substituted or unsubstituted aralkyl of 7 to 20 carbon atoms, substituted or unsubstituted alkenyl of 2 to 10 carbon atoms, or substituted or unsubstituted fused ring aryl of 10 to 20 carbon atoms; or R is ₁₉ -R ₂₂ At least one of which is together with R ₂₃ -R ₂₄ Is formed into a ring;

the cyano succinic acid ester compound is selected from cyano succinic acid ester compounds shown in a formula (VI),

in the formula (VI), R ₂₅ And R is ₂₆ The same or different, each independently selected from hydrogen, a straight chain alkyl of 1 to 14 carbon atoms, a branched alkyl of 3 to 14 carbon atoms, a cycloalkyl of 3 to 10 carbon atoms, an aryl of 6 to 10 carbon atoms, an alkylaryl of 7 to 10 carbon atoms, or an aralkyl of 7 to 10 carbon atoms; r is R ₂₇ And R is ₂₈ The same or different, each independently selected from a straight chain alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms or an arylalkyl group of 7 to 20 carbon atoms;

The diether compound is selected from diether compounds shown in a formula (VII),

in the formula (VII), R ₂₉ And R is ₃₀ The same or different, each independently selected from a straight chain alkyl group of 1 to 10 carbon atoms or a branched alkyl group of 3 to 10 carbon atoms; r is R ₃₂ And R is ₃₃ The same or different, each independently selected from a straight chain alkyl of 1 to 20 carbon atoms, a branched alkyl of 3 to 20 carbon atoms, a cycloalkyl of 3 to 20 carbon atoms, a substituted or unsubstituted aryl of 6 to 20 carbon atoms, or an alkylaryl of 7 to 20 carbon atoms; r is R ₃₁ And R is ₃₄ The same or different, each independently selected from hydrogen, a straight chain alkyl group of 1 to 10 carbon atoms, or a branched alkyl group of 3 to 10 carbon atoms;

the succinate compound is selected from succinate compounds shown in a formula (VIII),

3. The catalyst system of claim 2, wherein R ₁₅ And R is ₁₆ Each independently selected from a straight chain alkyl group of 1 to 10 carbon atoms, a branched alkyl group of 3 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or an aryl group of 6 to 10 carbon atoms.

4. A catalyst system according to claim 3, characterized in that R ₁₅ And R is ₁₆ Each independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms.

5. The catalyst system of claim 4 wherein R ₁₅ And R is ₁₆ Each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

6. The external electron donor according to claim 1 or the catalyst system according to any of claims 2 to 5, characterized in that in formula (I), R ₁ Selected from the group consisting of straight chain alkyl groups of 1 to 10 carbon atoms, branched alkyl groups of 3 to 10 carbon atoms, cycloalkanes of 3 to 10 carbon atomsA base;

R ₂ and R is ₃ Independently selected from the group consisting of straight chain alkyl of 3 to 10 carbon atoms, branched alkyl of 3 to 10 carbon atoms, cycloalkyl of 3 to 10 carbon atoms;

R ₄ and R is ₅ Independently selected from the group consisting of straight chain alkyl of 1 to 10 carbon atoms, branched alkyl of 3 to 10 carbon atoms, cycloalkyl of 3 to 10 carbon atoms; and/or

The heteroatom includes a halogen atom; and/or when R ₂ And R is ₃ When connected to form a ring, the skeleton of the ring formed may or may not contain double bonds or heteroatoms.

7. The external electron donor or catalyst system as claimed in claim 6, wherein R ₂ And R is ₃ Independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms;

R ₄ and R is ₅ Independently selected from a straight chain alkyl group of 1 to 6 carbon atoms or a branched alkyl group of 3 to 6 carbon atoms.

8. The external electron donor or catalyst system as claimed in claim 7, wherein R ₄ And R is ₅ Independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl.

9. The external electron donor according to claim 1 or the catalyst system according to any of claims 2 to 5, characterized in that in formula (II), R ₁ "and R ₂ "each independently selected from halogen, hydrogen atom, straight chain alkyl of 1 to 10 carbon atoms, branched alkyl of 3 to 10 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, aryl of 6 to 10 carbon atoms, or haloalkyl of 1 to 10 carbon atoms; r3' is selected from the group consisting of straight chain alkyl groups having 1 to 10 carbon atoms, branched alkyl groups having 3 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, and haloalkyl groups having 1 to 10 carbon atoms.

10. The external electron donor according to claim 1 or the catalyst system according to any of claims 2 to 5, characterized in that the amino ester compound is selected from at least one of the following compounds: ethyl N, N-dipropionate, propyl N, N-dipropionate, butyl N, N-dipropionate, isobutyl N, N-dipropionate, 1-amyl N, N-dipropionate, 1-hexanol N, N-dipropionate, 1-heptanol N, N-dipropionate-1-octanol ester, N-dipropionate-1-nonanol ester, N-dipropionate-1-decanol ester, N, N-diallylaminobutyl acetate, N-dibutylamino ethyl acetate, N-dibutylamino propyl acetate, N-dibutylamino butyl acetate, N, isobutyl N-dibutylamino acetate, 1-pentanol N, N-dibutylamino acetate, 1-hexanol N, N-dibutylamino acetate, 1-heptanol N, N-dibutylamino acetate, 1-octanol N, N-dibutylamino acetate, 1-nonanol N, N-dibutylamino acetic acid-1-decyl ester, N-dipentaminoacetic acid ethyl ester, N-dipentaminoacetic acid propyl ester, N-dipentaminoacetic acid butyl ester, N, isobutyl N-dipentaminoacetate, 1-pentanol N, N-dipentaminoacetate, 1-hexanol N, N-dipentaminoacetate, N, N-dipentaminoacetic acid-1-heptanol ester, N-dipentaminoacetic acid-1-octanol ester, N-dipentaminoacetic acid-1-nonanol ester, N, N-dipentaminoacetic acid-1-decyl ester, N-dihexylaminoacetic acid ethyl ester, N-dihexylaminoacetic acid propyl ester, N-dihexylaminoacetic acid butyl ester, N, isobutyl N-dihexylaminoacetate, 1-pentanol N, N-dihexylaminoacetate, 1-hexanol N, N-dihexylaminoacetate, 1-heptanol N, N-dihexylaminoacetate, 1-octanol N, N-dihexylaminoacetate, 1-nonanol N, N-dihexylaminoacetic acid-1-decanol ester, N-diheptylaminoacetic acid ethyl ester, N-diheptylaminoacetic acid propyl ester, N-diheptylaminoacetic acid butyl ester, N, isobutyl N-diheptylaminoacetate, 1-pentanol N, N-diheptylaminoacetate, 1-hexanol N, N-diheptylaminoacetate, N, N-diheptanoacetic acid-1-heptanol ester, N-diheptanoacetic acid-1-octanol ester, N-diheptanoacetic acid-1-nonanol ester, N-diheptanoacetic acid-1-decanol ester, N-dioctyl glycine ethyl ester, N-dioctyl glycine propyl ester, N, N-dioctyl-amino-acetic acid butyl ester, N-dioctyl-amino-acetic acid isobutyl ester, N-dioctyl-amino-acetic acid-1-amyl alcohol ester, N-dioctyl-amino-acetic acid-1-hexyl ester, N, N-dioctyl glycine-1-heptanol ester, N-dioctyl glycine-1-octanol ester, N-dioctyl glycine-1-nonanol ester, N, N-dioctyl glycine-1-decyl alcohol ester, N-diisooctyl glycine ethyl ester, N-diisooctyl glycine propyl ester, N-diisooctyl glycine butyl ester, N-diisooctyl glycine isobutyl ester, N-diisooctyl glycine-1-amyl alcohol ester, N, N-diisooctylamino-acetic acid-1-hexanol ester, N-diisooctylamino-acetic acid-1-heptanol ester, N-diisooctylamino-acetic acid-1-octanol ester, N-diisooctylamino-acetic acid-1-nonanol ester, N-diisooctylamino-acetic acid-1-decanol ester, N-dinonylacetic acid ethyl ester, N, propyl N-dinonylacetate, butyl N, N-dinonylacetate, isobutyl N, N-dinonylacetate, 1-pentanol N, N-dinonylacetate-1-hexanol N, N-dinonylacetate-1-heptanol N, n-dinonylacetic acid-1-octanol ester, N-dinonylacetic acid-1-nonanol ester, N-dinonylacetic acid-1-decanol ester, N, ethyl N-didecylaminoacetate, propyl N, N-didecylaminoacetate, butyl N, N-didecylaminoacetate, isobutyl N, N-didecylaminoacetate, N, N-didecyl amino acetic acid-1-pentanol ester, N-didecyl amino acetic acid-1-hexanol ester, N-didecyl amino acetic acid-1-heptanol ester, N-didecyl amino acetic acid-1-octanol ester, N-didecyl amino acetic acid-1-nonanol ester, N-didecyl amino acetic acid-1-decanol ester.

11. The external electron donor according to claim 1 or the catalyst system according to any of claims 2 to 5, the siloxane compound is selected from trimethylmethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, pentyltrimethoxysilane, isopentyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, tetramethoxysilane, at least one of tetraethoxysilane and tetrabutoxysilane.

12. The external electron donor according to claim 1 or the catalyst system according to any of claims 2 to 5, characterized in that the amino ester compound comprises 5 to 60mol% of the external electron donor a.

13. The external electron donor or catalyst system according to claim 12, wherein the amino ester compound comprises 10-40mol% of the external electron donor a.

14. The catalyst system of any of claims 2-5, wherein the internal electron donor compound is selected from at least one of glycol ester compounds, cyano succinate compounds, diether compounds, and succinate compounds.

15. The catalyst system of claim 14, wherein the internal electron donor compound is selected from diethers.

16. The catalyst system of any of claims 2-5, wherein the alkyl aluminum compound is selected from the group consisting of compounds of formula (IX),

AlR' _n 'X' _3-n' (IX)

in formula (IX), R' is selected from hydrogen, alkyl of 1 to 20 carbon atoms or aryl of 6 to 20 carbon atoms; x 'is selected from halogen, and n' is an integer from 1 to 3.

17. The catalyst system of claim 16, wherein the alkyl aluminum compound is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, and ethylaluminum dichloride.

18. Catalyst system according to claim 17, characterized in that the alkyl aluminium compound is selected from triethylaluminium and/or triisobutylaluminium.

19. The catalyst system according to any of claims 2-5, characterized in that the total molar ratio of aluminium in the alkyl aluminium compound C to the external electron donor a is from 1 to 50:1, a step of; and/or the number of the groups of groups,

in the solid catalyst component B, magnesium is calculated as magnesium atom, titanium is calculated as titanium atom, halogen is calculated as halogen atom, and the content of titanium atom is 1.0-8.0wt%; the content of magnesium atoms is 10-70wt%; the halogen atom content is 20-90wt%; the content of the internal electron donor compound is 2-30wt%; and/or

The molar ratio of aluminum in the alkyl aluminum compound C to titanium in the catalyst system is from 5 to 5000:1.

20. the catalyst system according to claim 19, wherein the total molar ratio of aluminum in the alkyl aluminum compound C to the external electron donor a is from 1 to 30:1, a step of; and/or the number of the groups of groups,

in the solid catalyst component B, magnesium is calculated as magnesium atom, titanium is calculated as titanium atom, halogen is calculated as halogen atom, and the content of titanium atom is 1.6-6.0wt%; the content of magnesium atoms is 15-40wt%; the halogen atom content is 30-85%; 3-20wt% of internal electron donor compound; and/or

The molar ratio of aluminum in the alkyl aluminum compound C to titanium in the catalyst system is from 20 to 1000:1.

21. the catalyst system according to claim 20, wherein the total molar ratio of aluminum in the alkyl aluminum compound C to the external electron donor a is from 1 to 20:1, a step of; and/or the number of the groups of groups,

the molar ratio of aluminum in the alkyl aluminum compound C to titanium in the catalyst system is 50-500:1.

22. a process for the polymerization of olefins comprising contacting one or more olefins with the catalyst system of any of claims 2-21 to obtain a polymer.

23. The process for the polymerization of olefins according to claim 22 wherein said olefins are of the formula CH ₂ =chr, R is selected from hydrogen or alkyl of 1-6 carbon atoms.

24. The olefin polymerization process of claim 23 wherein said olefin is selected from at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene.

25. The olefin polymerization process of claim 24 wherein said olefin is selected from at least one of ethylene, propylene and 1-n-butene.