阅读说明：本技术 烯烃聚合用固体催化剂成分 (Solid catalyst component for olefin polymerization ) 是由 铃木哲生 伊藤昌辉 于 2021-02-09 设计创作，主要内容包括：本发明提供一种微粉量少的烯烃聚合用固体催化剂成分。一种烯烃聚合用固体催化剂成分,其包含钛原子、镁原子、卤素原子和内给电子体,并且所述烯烃聚合用固体催化剂成分的峰顶(1)与峰顶(2)的结合能之差的绝对值为73.50eV～75.35eV,所述峰顶(1)为通过对利用X射线光电子能谱测定的归属于钛原子的2p轨道的峰进行波形分离而得到的峰成分中的、结合能在457.00eV～459.00eV的范围内的峰顶,所述峰顶(2)为通过对利用X射线光电子能谱测定的归属于氧原子的1s轨道的峰进行波形分离而得到的峰成分中的、结合能在532.50eV～534.50eV的范围内的峰顶。(The present invention provides a solid catalyst component for olefin polymerization having a small amount of fine powder. A solid catalyst component for olefin polymerization, which contains a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, and which has an absolute value of a difference in binding energy between a peak top (1) and a peak top (2) of 73.50eV to 75.35eV, wherein the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating a peak ascribed to a 2p orbital of the titanium atom as measured by X-ray photoelectron spectroscopy, and the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV among peak components obtained by waveform-separating a peak ascribed to a 1s orbital of the oxygen atom as measured by X-ray photoelectron spectroscopy.)

1. A solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, and which is characterized by containing

The absolute value of the difference in binding energy between the peak top (1) and the peak top (2) of the solid catalyst component for olefin polymerization is 73.50eV to 75.35eV,

the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating peaks ascribed to the 2p orbital of a titanium atom measured by X-ray photoelectron spectroscopy,

the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV in a peak component obtained by waveform-separating a peak ascribed to the 1s orbital of an oxygen atom measured by X-ray photoelectron spectroscopy.

2. The solid catalyst component for olefin polymerization according to claim 1, wherein the absolute value of the difference between the binding energies is 75.05eV or 75.35 eV.

3. The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the internal electron donor is at least one selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, an aromatic dicarboxylic acid ester compound, a diol diester compound, a β -alkoxy ester compound, and an ether compound.

4. The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the internal electron donor is a β -alkoxy ester compound.

5. The solid catalyst component for olefin polymerization according to claim 1 or 2, wherein the internal electron donor is ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate.

6. A catalyst for olefin polymerization, which comprises an organoaluminum compound and the solid catalyst component for olefin polymerization according to any one of claims 1 to 5.

7. A process for producing an olefin polymer, which comprises a step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 6.

8. A process for producing a solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, wherein,

the process for producing a solid catalyst component for olefin polymerization comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), A is calculated by the following formula (1)₁Is in the range of 0.3 to 1.6,

A₁＝n₁/60×d₁ ^0.85 (1)

in the formula, n₁Indicating mixing bladeRotational speed (rpm), d₁The blade diameter (m) of the stirring blade is shown.

9. The process for producing a solid catalyst component for olefin polymerization according to claim 8, wherein the process for producing a solid catalyst component for olefin polymerization further comprises the step (II): an internal electron donor is added to the slurry containing the solid product obtained in the step (I).

10. The process for producing a solid catalyst component for olefin polymerization according to claim 8 or 9, wherein in the step (II), A calculated by the following formula (2)₂Is in the range of 0.3 to 1.6,

A₂＝n₂/60×d₂ ^0.85 (2)

in the formula, n₂Indicates the rotational speed (rpm) of the stirring blade, d₂The blade diameter (m) of the stirring blade is shown.

11. The process for producing a solid catalyst component for olefin polymerization according to any one of claims 8 to 10, wherein,

the absolute value of the difference in binding energy between the peak top (1) and the peak top (2) of the solid catalyst component for olefin polymerization is 73.50eV to 75.35eV,

the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating peaks ascribed to the 2p orbital of a titanium atom measured by X-ray photoelectron spectroscopy,

the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV in a peak component obtained by waveform-separating a peak ascribed to the 1s orbital of an oxygen atom measured by X-ray photoelectron spectroscopy.

12. The process for producing a solid catalyst component for olefin polymerization according to claim 11, wherein the absolute value of the difference in binding energy is from 75.05eV to 75.35 eV.

13. The method for producing a solid catalyst component for olefin polymerization according to any one of claims 8 to 12, wherein the internal electron donor is at least one selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, an aromatic dicarboxylic acid ester compound, a diol diester compound, a β -alkoxy ester compound, and an ether compound.

14. The process for producing a solid catalyst component for olefin polymerization according to any one of claims 8 to 13, wherein the magnesium compound is dialkoxymagnesium.

15. The process for producing a solid catalyst component for olefin polymerization according to claim 14, wherein the magnesium dialkoxide is magnesium diethoxide.

16. A precursor of a solid catalyst component for olefin polymerization, wherein the precursor of a solid catalyst component for olefin polymerization contains a titanium atom, a magnesium atom and a halogen atom, and the precursor of a solid catalyst component for olefin polymerization has a mechanical strength of 3.50MPa to 7.00 MPa.

17. A process for producing a precursor of a solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom and a halogen atom and has a mechanical strength of from 3.50MPa to 7.00MPa,

the method for producing a precursor of a solid catalyst component for olefin polymerization comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), A is calculated by the following formula (1)₁Is in the range of 0.3 to 1.6,

A₁＝n₁/60×d₁ ^0.85 (1)

in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown.

Technical Field

The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing an olefin polymer, a method for producing a solid catalyst component for olefin polymerization, a precursor of a solid catalyst component for olefin polymerization, and a method for producing a precursor of a solid catalyst component for olefin polymerization.

Background

Conventionally, various solid catalyst components containing a titanium atom, a magnesium atom, a halogen atom and an internal electron donor have been proposed as catalyst components for olefin polymerization. In the polymerization of olefins, it is desirable that the amount of fine particles of the solid catalyst component for olefin polymerization is small from the viewpoint of reducing clogging of a polymerization apparatus and adhesion of a polymer to a wall surface of the polymerization apparatus.

For example, patent document 1 describes a solid catalyst component for olefin polymerization, which is produced by: in the step of contacting a titanium halide compound solution containing a titanium halide compound and a solvent with a magnesium compound to obtain a slurry containing a solid product, the titanium halide compound and the solvent contained in the titanium halide compound solution and the solvent contained in the slurry containing the solid product are used in a volume ratio within a specific range.

Documents of the prior art

Patent document

[ patent document 1] WO2018/025862 publication

Disclosure of Invention

Problems to be solved by the invention

However, although the solid catalyst component for olefin polymerization described in patent document 1 can produce a polymer having a high stereoregularity, the amount of fine powder of the solid catalyst component for olefin polymerization is still unsatisfactory from the viewpoint of reducing clogging of a polymerization apparatus and adhesion of a polymer to a wall surface of the polymerization apparatus.

The present invention has been made in view of the above problems, and an object thereof is to provide a solid catalyst component for olefin polymerization having a small amount of fine powder, a method for producing the same, and the like.

Means for solving the problems

The present invention provides the following aspects.

[1]

A solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, and which is characterized by containing

The absolute value of the difference in binding energy between the peak top (1) and the peak top (2) of the solid catalyst component for olefin polymerization is 73.50eV to 75.35eV,

the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating peaks ascribed to the 2p orbital of a titanium atom measured by X-ray photoelectron spectroscopy,

the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV in a peak component obtained by waveform-separating a peak ascribed to the 1s orbital of an oxygen atom measured by X-ray photoelectron spectroscopy.

[2]

The solid catalyst component for olefin polymerization according to [1], wherein the absolute value of the difference in binding energy is 75.05eV or more and 75.35eV or less.

[3]

The solid catalyst component for olefin polymerization according to [1] or [2], wherein the internal electron donor is at least one selected from the group consisting of a monoester compound, an aliphatic dicarboxylic acid ester compound, an aromatic dicarboxylic acid ester compound, a diol diester compound, a β -alkoxy ester compound, and an ether compound.

[4]

The solid catalyst component for olefin polymerization according to [1] or [2], wherein the internal electron donor is a β -alkoxy ester compound.

[5]

The solid catalyst component for olefin polymerization according to [1] or [2], wherein the internal electron donor is ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate.

[6]

An olefin polymerization catalyst comprising an organoaluminum compound and the solid catalyst component for olefin polymerization described in any one of [1] to [5 ].

[7]

A process for producing an olefin polymer, which comprises the step of polymerizing an olefin in the presence of the olefin polymerization catalyst according to [6 ].

[8]

A process for producing a solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, wherein,

the process for producing a solid catalyst component for olefin polymerization comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), A is calculated by the following formula (1)₁Is in the range of 0.3 to 1.6,

A₁＝n₁/60×d₁ ^0.85 (1)

(in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown. )

[9]

The process for producing a solid catalyst component for olefin polymerization according to [8], wherein the process for producing a solid catalyst component for olefin polymerization further comprises the step (II): an internal electron donor is added to the slurry containing the solid product obtained in the step (I).

[10]

Such as [8]]Or [9 ]]The process for producing a solid catalyst component for olefin polymerization, wherein in the step (II), A is calculated by the following formula (2)₂Is in the range of 0.3 to 1.6,

A₂＝n₂/60×d₂ ^0.85 (2)

(in the formula, n₂Indicates the rotational speed (rpm) of the stirring blade, d₂The blade diameter (m) of the stirring blade is shown. )

[11]

The process for producing a solid catalyst component for olefin polymerization according to any one of [8] to [10], wherein,

the absolute value of the difference in binding energy between the peak top (1) and the peak top (2) of the solid catalyst component for olefin polymerization is 73.50eV to 75.35eV,

the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating peaks ascribed to the 2p orbital of a titanium atom measured by X-ray photoelectron spectroscopy,

the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV in a peak component obtained by waveform-separating a peak ascribed to the 1s orbital of an oxygen atom measured by X-ray photoelectron spectroscopy.

[12]

The process for producing a solid catalyst component for olefin polymerization according to [11], wherein the absolute value of the difference in binding energy is from 75.05eV to 75.35 eV.

[13]

The process for producing a solid catalyst component for olefin polymerization according to any one of [8] to [12], wherein the internal electron donor is at least one selected from the group consisting of monoester compounds, aliphatic dicarboxylic acid ester compounds, aromatic dicarboxylic acid ester compounds, diol diester compounds, β -alkoxy ester compounds, and ether compounds.

[14]

The process for producing a solid catalyst component for olefin polymerization according to any one of [8] to [13], wherein the magnesium compound is dialkoxymagnesium.

[15]

The process for producing a solid catalyst component for olefin polymerization according to [14], wherein the magnesium dialkoxide is a magnesium diethoxide.

[16]

A precursor of a solid catalyst component for olefin polymerization, wherein the precursor of a solid catalyst component for olefin polymerization contains a titanium atom, a magnesium atom and a halogen atom, and the precursor of a solid catalyst component for olefin polymerization has a mechanical strength of 3.50MPa to 7.00 MPa.

[17]

A process for producing a precursor of a solid catalyst component for olefin polymerization, which comprises a titanium atom, a magnesium atom and a halogen atom and has a mechanical strength of from 3.50MPa to 7.00MPa,

the method for producing a precursor of a solid catalyst component for olefin polymerization comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), the calculation is performed by the following formula (1)A of (A)₁Is in the range of 0.3 to 1.6,

A₁＝n₁/60×d₁ ^0.85 (1)

(in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown. )

Effects of the invention

According to the present invention, a solid catalyst component for olefin polymerization having a small amount of fine powder can be provided. When the amount of the fine powder is small, clogging of a polymerization apparatus and adhesion of a polymer to a wall surface of the polymerization apparatus are improved when an olefin is polymerized.

Drawings

FIG. 1 is a graph showing the results of X-ray photoelectron spectroscopy measurement of the solid catalyst component for olefin polymerization 1 obtained in example 1, in which the peak ascribed to the 2p orbital of titanium atom was separated into waveforms. The binding energy at the peak top (1) was 458.47 eV.

FIG. 2 is a graph showing the results of X-ray photoelectron spectroscopy measurement of the solid catalyst component for olefin polymerization 1 obtained in example 1, in which the peak of the 1s orbital ascribed to an oxygen atom is separated into waveforms. The binding energy at the peak top (2) was 533.76 eV.

Detailed Description

< solid catalyst component for olefin polymerization >

Method for producing solid catalyst component for olefin polymerization

The solid catalyst component for olefin polymerization of the present invention is a solid catalyst component for olefin polymerization as follows:

the solid catalyst component for olefin polymerization contains a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, and

the absolute value of the difference in binding energy between the peak top (1) and the peak top (2) of the solid catalyst component for olefin polymerization is 73.50eV to 75.35eV,

the peak top (1) is a peak top having a binding energy in the range of 457.00eV to 459.00eV among peak components obtained by waveform-separating peaks ascribed to the 2p orbital of a titanium atom measured by X-ray photoelectron spectroscopy,

the peak top (2) is a peak top having a binding energy in the range of 532.50eV to 534.50eV in a peak component obtained by waveform-separating a peak ascribed to the 1s orbital of an oxygen atom measured by X-ray photoelectron spectroscopy.

The absolute value of the difference in binding energy is preferably 75.05eV or more and 75.35eV or less. The X-ray photoelectron spectroscopy was carried out according to the method described in the following examples.

The process for producing a solid catalyst component for olefin polymerization according to the present invention is a process for producing a solid catalyst component for olefin polymerization containing a titanium atom, a magnesium atom, a halogen atom and an internal electron donor, wherein,

the process for producing a solid catalyst component for olefin polymerization comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), A is calculated by the following formula (1)₁0.3 to 1.6.

A₁＝n₁/60×d₁ ^0.85 (1)

(in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown. )

In the present specification, the "solid catalyst component for olefin polymerization" refers to a component which is present in a solid form at least in toluene and becomes a catalyst for olefin polymerization by being combined with a cocatalyst for olefin polymerization such as an organoaluminum compound.

The titanium halide compound means a compound containing a halogen atom and a titanium atom and at least one halogen atom is bonded to the titanium atom. Specific examples thereof include: titanium tetrahalides such as titanium trichloride, titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide; monoalkoxy trihalogenated titanium such as methoxytitanium trichloride, ethoxytitanium trichloride, n-propoxytitanium trichloride, n-butoxytitanium trichloride and ethoxytitanium tribromide; dialkoxy titanium dihalides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride and diethoxytitanium dibromide; trialkoxymonotitanium halides such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride and tri-n-butoxytitanium chloride. Preferred are titanium tetrahalides and monoalkoxytitanium trihalides, more preferred are titanium tetrahalides, and still more preferred is titanium tetrachloride. The titanium halide compounds may be used alone or in combination of two or more.

A part or all of titanium atoms in the solid catalyst component for olefin polymerization are derived from a titanium halide compound. A part or all of the halogen atoms in the solid catalyst component for olefin polymerization are derived from a titanium halide compound.

The magnesium compound may be any compound containing a magnesium atom, and specific examples thereof include compounds represented by the following formulas (i) to (iii).

MgR¹ _kX_2-k……(i)

Mg(OR¹)_mX_2-m……(ii)

MgX₂·nR¹OH……(iii)

(wherein k is a number satisfying 0. ltoreq. k.ltoreq.2, m is a number satisfying 0. ltoreq. m.ltoreq.2, n is a number satisfying 0. ltoreq. n.ltoreq.3, and R¹Is a hydrocarbon group having 1 to 20 carbon atoms; x is a halogen atom. )

As R in formulae (i) to (iii)¹Examples thereof include: alkyl groups, aralkyl groups, aryl groups, alkenyl groups, and the like, and some or all of the hydrogen atoms contained in these groups may be substituted with halogen atoms, hydrocarbyloxy groups, nitro groups, sulfonyl groups, silyl groups, and the like. As R¹Examples of the alkyl group of (1) include: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, and preferably a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms. As R¹As the aralkyl group of (2), there can be enumerated: benzyl and phenethyl, preferably aralkyl having 7 to 20 carbon atoms. As R¹As the aryl group of (1), there may be mentioned: phenyl, naphthyl, tolyl, and the like, preferably an aryl group having 6 to 20 carbon atoms. As R¹The alkenyl group of (a) may be exemplified by: linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as an isobutylene group and a 4-methyl-3-pentenyl group; the cyclic alkenyl group such as 2-cyclohexenyl group and 3-cyclohexenyl group is preferably a linear alkenyl group having 2 to 20 carbon atoms or a branched alkenyl group having 3 to 20 carbon atoms. Plural R¹May be the same or different.

Examples of X in the formulae (i) to (iii) include: chlorine atom, bromine atom, iodine atom and fluorine atom, preferably chlorine atom. The plurality of xs may be the same or different.

Specific examples of the magnesium compound of the formulae (i) to (iii) include: dialkylmagnesium such as dimethylmagnesium, diethylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, dioctylmagnesium, ethylbutylmagnesium, dicyclohexylmagnesium and butyloctylmagnesium; dialkoxymagnesiums such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, and dicyclohexyloxymagnesium; alkyl magnesium halides such as methyl magnesium chloride, ethyl magnesium chloride, isopropyl magnesium chloride, n-butyl magnesium chloride, tert-butyl magnesium chloride, hexyl magnesium chloride, isobutyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, ethyl magnesium bromide, isopropyl magnesium bromide, n-butyl magnesium bromide, tert-butyl magnesium bromide, hexyl magnesium bromide, isobutyl magnesium bromide, benzyl magnesium bromide, methyl magnesium iodide, ethyl magnesium iodide, isopropyl magnesium iodide, n-butyl magnesium iodide, tert-butyl magnesium iodide, hexyl magnesium iodide, isobutyl magnesium iodide, and benzyl magnesium iodide; alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, and hexyloxy magnesium chloride; aryloxy magnesium halides such as phenoxymagnesium chloride; magnesium halides such as magnesium fluoride, magnesium chloride, magnesium bromide, and magnesium iodide.

Among them, preferred are magnesium halides and dialkoxymagnesiums, and particularly preferred is a dialkoxymagnesium. The magnesium halide is preferably magnesium chloride. The dialkoxymagnesium is preferably a dialkoxymagnesium having an alkyl group with 1 to 20 carbon atoms, more preferably a dialkoxymagnesium having an alkyl group with 1 to 10 carbon atoms, particularly preferably dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, diisopropoxymagnesium, or dibutoxymagnesium, and more particularly preferably diethoxymagnesium.

As the magnesium halide, commercially available magnesium halide may be used as it is, or commercially available magnesium halide may be dissolved in alcohol to obtain a solution, the solution may be added dropwise to a hydrocarbon liquid to generate a precipitate, and the precipitate and the liquid may be separated and used, or magnesium halide produced by the method described in U.S. patent No. 6825146, international publication No. 1998/044009, international publication No. 2003/000754, international publication No. 2003/000757, or international publication No. 2003/085006 may be used.

Examples of the method for producing dialkoxymagnesium include a method in which magnesium metal is brought into contact with an alcohol in the presence of a catalyst (for example, jp-a-4-368391, jp-a-3-74341, jp-a-8-73388, and international publication No. 2013/058193). Examples of the alcohol include: methanol, ethanol, propanol, butanol and octanol. As the catalyst, there may be mentioned: halogens such as iodine, chlorine and bromine; magnesium halides such as magnesium iodide and magnesium chloride, and iodine is preferred.

The magnesium compound may be supported on a carrier material. Examples of carrier materials include: SiO 2₂、Al₂O₃、MgO、TiO₂And ZrO₂Isoporous inorganic oxides; organic porous polymers such as polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol dimethacrylate copolymer, polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyethylene, and polypropylene. Among these, porous inorganic oxides are preferable, and SiO is more preferable₂。

As the carrier material, from the viewpoint of effectively immobilizing the magnesium compound on the carrier material, it is preferablePorous support material, more preferably according to standard ISO 15901-1: 2005 Total volume of pores having pore radii of 10nm to 780nm, determined by mercury intrusion method, of 0.3cm³A porous carrier material having a pore radius of 10 to 780nm, and a total volume of pores is preferably 0.4cm³A porous carrier material per gram or more. The porous support material preferably has a pore radius of 2 to 100 μm of a total volume of pores and a pore radius of 10 to 780nm of a total volume of 25% or more, and more preferably has a pore radius of 10 to 780nm of a total volume of pores and a pore radius of 2 to 100 μm of a total volume of pores and a pore radius of 30% or more.

The magnesium compounds may be used alone or in combination of two or more. The magnesium compound may be contacted with the titanium halide compound in the form of a magnesium compound slurry containing the magnesium compound and a solvent, preferably in the form of a solvent-free slurry, and more preferably in the form of a powder, within the range in which the effects of the present invention can be obtained.

A part or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from metallic magnesium or a magnesium compound. In addition, a part of the halogen atoms in the solid catalyst component for olefin polymerization may be derived from a magnesium compound.

The internal electron donor refers to an organic compound capable of donating an electron pair to one or more metal atoms contained in the solid catalyst component for olefin polymerization, and specifically, there can be mentioned: monoester compounds, dicarboxylic acid ester compounds (aliphatic dicarboxylic acid ester compounds, aromatic dicarboxylic acid ester compounds), diol diester compounds, β -alkoxy ester compounds, ether compounds, and the like.

The monoester compound means an organic compound having one ester bond (-CO-O-) in the molecule, and is preferably an aromatic carboxylic acid ester compound and an aliphatic carboxylic acid ester compound. As the aromatic carboxylic acid ester compound, there may be mentioned: methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, pentyl benzoate, hexyl benzoate, octyl benzoate, methyl benzoate, ethyl methyl benzoate, propyl methyl benzoate, butyl methyl benzoate, pentyl methyl benzoate, hexyl methyl benzoate, octyl methyl benzoate and the like. As the aliphatic carboxylic acid ester compound, there may be mentioned: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, octyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, octyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, pentyl butyrate, hexyl butyrate, octyl butyrate, methyl valerate, ethyl valerate, propyl valerate, butyl valerate, pentyl valerate, octyl valerate, methyl hexanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, pentyl hexanoate, hexyl hexanoate, octyl hexanoate, methyl heptanoate, ethyl heptanoate, propyl heptanoate, butyl heptanoate, pentyl heptanoate, hexyl heptanoate, octyl heptanoate, methyl octanoate, ethyl octanoate, propyl octanoate, butyl octanoate, pentyl octanoate, hexyl octanoate, octyl octanoate, methyl nonanoate, ethyl nonanoate, propyl nonanoate, Butyl pelargonate, pentyl pelargonate, hexyl pelargonate, octyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, pentyl caprate, hexyl caprate, octyl caprate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, hexyl laurate, octyl laurate, methyl myristate, ethyl myristate, propyl myristate, butyl myristate, pentyl myristate, hexyl myristate, octyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, butyl palmitate, pentyl palmitate, hexyl palmitate, octyl palmitate, methyl heptadecanoate, ethyl heptadecanoate, propyl heptadecanoate, butyl heptadecanoate, pentyl heptadecanoate, hexyl heptadecanoate, octyl heptadecanoate, methyl stearate, ethyl stearate, propyl stearate, butyl stearate, hexyl palmitate, octyl heptadecanoate, methyl heptadecanoate, octyl heptadecanoate, ethyl stearate, propyl stearate, butyl stearate, Amyl stearate, hexyl stearate, octyl stearate, and the like.

The dicarboxylic acid ester compound is a compound having two ester bonds (-CO-O-) in the molecule and having a structure in which two carboxyl groups of a dicarboxylic acid are esterified with a monohydric alcohol, and is preferably an aromatic dicarboxylic acid ester compound and an aliphatic dicarboxylic acid ester compound. The aromatic dicarboxylic acid ester compound is, for example, a compound which can be synthesized from an aromatic dicarboxylic acid or an aromatic dicarboxylic acid dihalide and a monohydric alcohol, and specifically, there can be mentioned: dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisodecyl phthalate, dicyclohexyl phthalate, diphenyl phthalate, and the like. The aliphatic dicarboxylic acid ester compound is, for example, a compound which can be synthesized from an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid dihalide and a monohydric alcohol, and specifically, there can be mentioned: dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dipentyl oxalate, dihexyl oxalate, dioctyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, dipentyl malonate, dihexyl malonate, dioctyl malonate, dimethyl succinate, diethyl succinate, dipropyl succinate, dipentyl succinate, dihexyl succinate, dioctyl succinate, dimethyl succinate, diethyl glutarate, dipropyl glutarate, dibutyl glutarate, dipentyl glutarate, dihexyl glutarate, dioctyl glutarate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dipentyl adipate, dihexyl adipate, dioctyl adipate, dimethyl fumarate, diethyl fumarate, dioctyl phthalate, and the like, Dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, dioctyl fumarate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dioctyl maleate, dimethyl cyclohexane-1, 2-dicarboxylate, diethyl cyclohexane-1, 2-dicarboxylate, dipropyl cyclohexane-1, 2-dicarboxylate, dibutyl cyclohexane-1, 2-dicarboxylate, dipentyl cyclohexane-1, 2-dicarboxylate, dihexyl cyclohexane-1, 2-dicarboxylate, dioctyl cyclohexane-1, 2-dicarboxylate, dimethyl 1, 2-dicarboxylate, diethyl 1, 2-cyclohexene-1, 2-dicarboxylate, 1, 2-cyclohexene-1, 2-dicarboxylic acid dipropyl ester, 1, 2-cyclohexene-1, 2-diformyl dibutyl ester, 1, 2-cyclohexene-1, 2-diformyl dipentyl ester, 1, 2-cyclohexene-1, 2-diformyl dihexyl ester, 1, 2-cyclohexene-1, 2-diformyl dioctyl ester, 3-methylcyclohexane-1, 2-diformyl dimethyl ester, 3-methylcyclohexane-1, 2-diformyl diethyl ester, 3-methylcyclohexane-1, 2-diformyl dipropyl ester, 3-methylcyclohexane-1, 2-diformyl dibutyl ester, 3-methylcyclohexane-1, 2-diformyl dipentyl ester, 3-methylcyclohexane-1, dihexyl-2-dicarboxylate, dioctyl-3-methylcyclohexane-1, 2-dicarboxylate, dimethyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, diethyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dipropyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dibutyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dipentyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dihexyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, dioctyl-3, 6-dimethylcyclohexane-1, 2-dicarboxylate, and the like.

The diol diester compound is a compound having two ester bonds (-CO-O-) in the molecule and having a structure in which two hydroxyl groups of a diol each esterify a carboxyl group of a monocarboxylic acid or a dicarboxylic acid, and specifically, there can be mentioned: 1, 2-propanediol dibenzoate, 1, 2-propanediol diacetate, 1, 2-butanediol dibenzoate, 1, 2-butanediol diacetate, 1, 2-cyclohexanediol dibenzoate, 1, 2-cyclohexanediol diacetate, 1, 3-propanediol dibenzoate, 1, 3-propanediol diacetate, 2, 4-pentanediol dibenzoate, 2, 4-pentanediol diacetate, 1, 2-cyclopentanediol dibenzoate, 1, 2-cyclopentanediol diacetate, 4-tert-butyl-6-methylcatechol dibenzoate, 4-tert-butyl-6-methylcatechol diacetate, 4-tert-butyl-6-methylresorcinol dibenzoate, and 4-tert-butyl-6-methylresorcinol diacetate, and the like.

The β -alkoxy ester compound is a compound having an alkoxycarbonyl group and an alkoxy group at a position β to the alkoxycarbonyl group, and specifically, there can be mentioned: methyl 2-methoxymethyl-3, 3-dimethylbutyrate, ethyl 2-methoxymethyl-3, 3-dimethylbutyrate, propyl 2-methoxymethyl-3, 3-dimethylbutyrate, butyl 2-methoxymethyl-3, 3-dimethylbutyrate, pentyl 2-methoxymethyl-3, 3-dimethylbutyrate, hexyl 2-methoxymethyl-3, 3-dimethylbutyrate, octyl 2-methoxymethyl-3, 3-dimethylbutyrate, methyl 3-methoxy-2-phenylpropionate, ethyl 3-methoxy-2-phenylpropionate, propyl 3-methoxy-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, ethyl 2-methoxymethyl-3, 3-methoxymethyl-2-phenylpropionate, ethyl 3-methoxymethyl-2-phenylpropionate, butyl 3-methoxy-2-phenylpropionate, ethyl 2-methoxypropionate, ethyl 2-propionate, ethyl 2-methyl-methoxybutyrate, ethyl-ethoxypropyl-3-methoxybutyl acetate, ethyl-3-methoxypropionate, and ethyl-3-ethoxymethyl-3-2-phenylbutyrate, Pentyl 3-methoxy-2-phenylpropionate, hexyl 3-methoxy-2-phenylpropionate, octyl 3-methoxy-2-phenylpropionate, methyl 2-ethoxymethyl-3, 3-dimethylbutyrate, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate, propyl 2-ethoxymethyl-3, 3-dimethylbutyrate, butyl 2-ethoxymethyl-3, 3-dimethylbutyrate, pentyl 2-ethoxymethyl-3, 3-dimethylbutyrate, hexyl 2-ethoxymethyl-3, 3-dimethylbutyrate, octyl 2-ethoxymethyl-3, 3-dimethylbutyrate, methyl 3-ethoxy-2-phenylpropionate, Ethyl 3-ethoxy-2-phenylpropionate, propyl 3-ethoxy-2-phenylpropionate, butyl 3-ethoxy-2-phenylpropionate, pentyl 3-ethoxy-2-phenylpropionate, hexyl 3-ethoxy-2-phenylpropionate, octyl 3-ethoxy-2-phenylpropionate, methyl 2-propoxymethyl-3, 3-dimethylbutyrate, ethyl 2-propoxymethyl-3, 3-dimethylbutyrate, propyl 2-propoxymethyl-3, 3-dimethylbutyrate, butyl 2-propoxymethyl-3, 3-dimethylbutyrate, pentyl 2-propoxymethyl-3, 3-dimethylbutyrate, 2-propoxymethyl-3, hexyl 3-dimethylbutyrate, octyl 2-propoxymethyl-3, 3-dimethylbutyrate, methyl 3-propoxy-2-phenylpropionate, ethyl 3-propoxy-2-phenylpropionate, propyl 3-propoxy-2-phenylpropionate, butyl 3-propoxy-2-phenylpropionate, pentyl 3-propoxy-2-phenylpropionate, hexyl 3-propoxy-2-phenylpropionate, octyl 3-propoxy-2-phenylpropionate, methyl 2-methoxybenzoate, ethyl 2-methoxybenzoate, propyl 2-methoxybenzoate, butyl 2-methoxybenzoate, pentyl 2-methoxybenzoate, hexyl 3-propoxy-2-phenylpropionate, ethyl 3-propoxy-2-phenylpropionate, propyl 3-propoxy-2-phenylpropionate, octyl 2-methoxybenzoate, butyl 2-methoxybenzoate, hexyl 2-methoxybenzoate, octyl 2-methoxybenzoate, methyl 2-methoxybenzoate, hexyl 2-methoxybenzoate, methyl propionate, ethyl propionate, propyl p-hydroxybenzoate, n-propoxide, n-propoxyphyllate, n-2-propionate, n, 2-methoxy octyl benzoate, 2-ethoxy methyl benzoate, 2-ethoxy ethyl benzoate, 2-ethoxy propyl benzoate, 2-ethoxy butyl benzoate, 2-ethoxy pentyl benzoate, 2-ethoxy hexyl benzoate, 2-ethoxy octyl benzoate and the like.

Specific examples of the ether compound include: 1, 2-dimethoxypropane, 1, 2-diethoxypropane, 1, 2-dipropoxypropane, 1, 2-dibutoxypropane, 1, 2-di-tert-butoxypropane, 1, 2-diphenoxypropane, 1, 2-dibenzyloxypropane, 1, 2-dimethoxybutane, 1, 2-diethoxybutane, 1, 2-dipropoxybutane, 1, 2-dibutoxybutane, 1, 2-di-tert-butoxybutane, 1, 2-diphenoxybutane, 1, 2-dibenzyloxybutane, 1, 2-dimethoxycyclohexane, 1, 2-diethoxycyclohexane, 1, 2-dipropoxycyclohexane, 1, 2-dibutoxycyclohexane, 1, 2-di-tert-butoxycyclohexane, 1, 2-diphenoxycyclohexane, 1, 2-dibenzyloxycyclohexane, 1, 3-dimethoxypropane, 1, 3-diethoxypropane, 1, 3-dipropoxypropane, 1, 3-dibutoxypropane, 1, 3-di-tert-butoxypropane, 1, 3-diphenoxypropane, 1, 3-dibenzyloxypropane, 2, 4-dimethoxypentane, 2, 4-diethoxypentane, 2, 4-dipropoxypentane, 2, 4-dibutoxypentane, 2, 4-di-tert-butoxypentane, 2, 4-diphenoxypentane, 2, 4-dibenzyloxypentane, 1, 2-dimethoxycyclopentane, 1, 2-diethoxycyclopentane, 1, 2-dipropoxycyclopentane, 1, 2-dibutoxycyclopentane, 1, 3-dimethoxypropane, 1, 3-diethoxypropane, 2-diethoxypentane, and the like, 1, 2-di-tert-butoxycyclopentane, 1, 2-diphenoxycyclopentane, 1, 2-dibenzyloxycyclopentane, 9-bis (methoxymethyl) fluorene, 9-bis (ethoxymethyl) fluorene, 9-bis (propoxymethyl) fluorene, 9-bis (butoxymethyl) fluorene, 9-bis (tert-butoxymethyl) fluorene, 9-bis (phenoxymethyl) fluorene, 9-bis (benzyloxymethyl) fluorene, 1, 2-dimethoxybenzene, 1, 2-diethoxybenzene, 1, 2-dipropoxybenzene, 1, 2-dibutoxybenzene, 1, 2-di-tert-butoxybenzene, 1, 2-diphenoxybenzene, 1, 2-dibenzyloxybenzene, tetrahydrofuran, dibutyl ether, diethyl ether, and the like.

Further, an internal electron donor described in Japanese patent application laid-open No. 2011-246699 can be exemplified.

Among them, dicarboxylic acid ester compounds, diol diester compounds and β -alkoxy ester compounds are preferable. In one example, the internal electron donor is more preferably a β -alkoxy ester compound, and still more preferably ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate. The internal electron donor may be used alone or in combination of two or more.

The amount of the titanium halide compound used in the step (I) is usually 0.01 to 100 moles, preferably 0.03 to 50 moles, and more preferably 0.05 to 30 moles per 1 mole of the total magnesium atoms in the metal magnesium or magnesium compound used in the step (I).

The solvent in the step (I) is preferably inert to the solid product formed in the step (I) and the solid catalyst component for olefin polymerization. As the solvent, there may be mentioned: aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane, cyclopentane, methylcyclohexane, and decalin; halogenated hydrocarbons such as 1, 2-dichloroethane and monochlorobenzene; and ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether and tetrahydrofuran. Among them, aromatic hydrocarbons or halogenated hydrocarbons are preferable, and toluene is more preferable. The solvents may be used alone or in combination of two or more.

In the present invention, the contacting of the titanium halide compound solution with the metallic magnesium or magnesium compound is usually carried out in an inert gas atmosphere such as nitrogen and argon. As a method of contacting a titanium halide compound solution with magnesium metal or a magnesium compound to obtain a slurry containing a solid product, a method of adding magnesium metal or a magnesium compound to a titanium halide compound solution can be exemplified.

In the above method of adding metallic magnesium or a magnesium compound to a titanium halide compound solution, the addition of the metallic magnesium or the magnesium compound may be carried out at once or may be carried out in any number of times. Further, metallic magnesium or a magnesium compound may be continuously added. The magnesium metal or magnesium compound is preferably a powder, and may be a mixture of the magnesium metal or magnesium compound and a solvent within a range in which the effects of the present invention can be obtained.

Examples of the method of bringing the components into contact with each other include known methods such as a slurry method and a mechanical pulverization method (for example, a method of bringing the components into contact with each other while pulverizing the components by a ball mill).

The amount of the titanium halide compound in the titanium halide compound solution is usually 0.001 mL-50 mL, preferably 0.01 mL-25 mL, more preferably 0.05 mL-10 mL, and still more preferably 0.1 mL-5.0 mL, based on 1mL of the solvent contained in the titanium halide compound solution.

The temperature at which the titanium halide compound solution and the magnesium metal or magnesium compound are brought into contact with each other is usually from-20 ℃ to 50 ℃, preferably from-5 ℃ to 20 ℃. The contact time is usually 0.01 to 48 hours, preferably 0.1 to 36 hours, and more preferably 1 to 24 hours.

In the step (I) of the method for producing a solid catalyst component for olefin polymerization of the present invention, a calculated by the following formula (1)₁0.3 to 1.6.

A₁＝n₁/60×d₁ ^0.85 (1)

(in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown. )

The process for producing a solid catalyst component for olefin polymerization of the present invention preferably further comprises the step (II): an internal electron donor is added to the slurry containing the solid product obtained in the aforementioned step (I).

Preferably, in the step (II), A is calculated by the following formula (2)₂0.3 to 1.6.

A₂＝n₂/60×d₂ ^0.85 (2)

(in the formula, n₂Indicates the rotational speed (rpm) of the stirring blade, d₂The blade diameter (m) of the stirring blade is shown. )

In the above-mentioned step (I) and step (II), the number of revolutions n of the stirring blade₁(rpm) and n₂(rpm) is not particularly limited, and is, for example, each independently in the range of 10rpm to 10000 rpm. In addition, the blade diameter d of the stirring blade₁(m) and d₂(m) is not particularly limited, and is, for example, in the range of 0.01m to 1m independently of each other. The shape of the stirring blade is not particularly limited, and examples thereof include a paddle blade, a propeller blade, a turbine blade, and an anchor blade.

The shape of the reaction vessel used in the steps (I) and (II) is not particularly limited, and examples thereof include a cylindrical shape having a circular bottom (also referred to as a disk shape) and an elliptical cylindrical shape having an elliptical bottom. The reaction tank may have a baffle plate, and the shape of the baffle plate is not particularly limited, and may be, for example, a shape having 1 to 6 flat plates. The ratio of the blade diameter of the stirring blade to the inner diameter of the reaction vessel is not particularly limited, and is, for example, 0.3 to 0.9, preferably 0.7 to 0.9.

The timing of the addition of the internal electron donor is arbitrary. For example, the titanium halide compound may be added to the reactor in advance before the step (I), may be mixed with the titanium halide compound solution, may be mixed with the magnesium metal or the magnesium compound, may be added during the step (I), may be added to the slurry containing the solid product after the step (I), or may be a combination of these.

In the production method of the present invention, the amount of the internal electron donor used is usually 0.001 to 100 moles, preferably 0.01 to 10 moles, per 1 mole of the total magnesium atoms in the metallic magnesium or magnesium compound used in the step (I).

In one embodiment, it is preferable to add an internal electron donor to the slurry containing the solid product after the step (I) from the viewpoint of improving the particle properties. That is, in one embodiment, the production method of the present invention preferably includes the step (II): an internal electron donor is added to the slurry containing the solid product. Each of the step (I) and the step (II) is usually carried out while stirring.

Regardless of the timing of adding the internal electron donor, the temperature for the reaction between the solid product and the internal electron donor is usually-30 ℃ to 150 ℃, preferably-20 ℃ to 135 ℃, and more preferably-10 ℃ to 120 ℃. The reaction time is usually 0.1 to 12 hours, preferably 0.5 to 10 hours. The reaction of the solid product with the internal electron donor is usually carried out under an inert gas atmosphere such as nitrogen and argon.

The precursor of the solid catalyst component for olefin polymerization of the present invention contains titanium atoms, magnesium atoms and halogen atoms, and has a mechanical strength of 3.50 to 7.00 MPa.

The mechanical strength is preferably 4.00MPa to 7.00 MPa.

The mechanical strength was measured by the method described in the following examples.

The method for producing the precursor of the solid catalyst component for olefin polymerization of the present invention comprises the step (I): obtaining a slurry containing a solid product by contacting a solution containing a titanium halide compound and a solvent with magnesium metal or a magnesium compound, and

in the step (I), A is calculated by the following formula (1)₁0.3 to 1.6.

A₁＝n₁/60×d₁ ^0.85 (1)

(in the formula, n₁Indicates the rotational speed (rpm) of the stirring blade, d₁The blade diameter (m) of the stirring blade is shown. )

This step (I) may be the same as the step (I) in the above-described method for producing a solid catalyst component for olefin polymerization.

After the reaction is completed, the obtained solid may be used as a solid catalyst component for olefin polymerization, or the obtained solid may be used as a precursor, and the solid may be further contacted with at least one of a titanium halide compound, a metallic magnesium or magnesium compound, and an internal electron donor to obtain a solid, and the solid may be used as a solid catalyst component for olefin polymerization. In one embodiment, the production method of the present invention includes step (III): the obtained precursor is contacted with one or more of a titanium halide compound, a metallic magnesium or magnesium compound, and an internal electron donor.

In order to remove unnecessary substances, it is preferable to wash the solid catalyst component for olefin polymerization or the precursor with a solvent. The solvent is preferably inert to the precursor or the solid catalyst component for olefin polymerization, and examples of the solvent include: aliphatic hydrocarbons such as pentane, hexane, heptane and octane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; and halogenated hydrocarbons such as 1, 2-dichloroethane and monochlorobenzene. Among them, aromatic hydrocarbons or halogenated hydrocarbons are particularly preferable. The amount of the solvent used for washing in each step of the contacting is, for example, 0.1mL to 1000mL per 1g of the solid catalyst component or precursor for olefin polymerization. The amount of the solvent used for washing is preferably 1mL to 100mL per 1g of the solid catalyst component or precursor for olefin polymerization. In each contact step, washing is usually carried out 1 to 10 times. The washing temperature is usually-50 ℃ to 150 ℃, preferably 0 ℃ to 140 ℃, and more preferably 20 ℃ to 135 ℃. The washing time is preferably 1 minute to 300 minutes, and more preferably 2 minutes to 150 minutes.

The step (III) is preferably carried out in a solvent. The description of the solvent in the step (III) is the same as that of the solvent in the step (I). In the step (III), when contacting the titanium halide compound, the amount of the titanium halide compound is usually 0.001mL/mL to 50mL/mL of the solvent, preferably 0.01mL/mL to 25mL/mL of the solvent, more preferably 0.05mL/mL to 10mL/mL of the solvent, and still more preferably 0.1mL/mL to 5.0mL/mL of the solvent. In the step (III), when contacting with metallic magnesium or a magnesium compound, the amount of the metallic magnesium or the magnesium compound is usually 0.01g/mL to 10g/mL, preferably 0.1g/mL to 1.0 g/mL. In the step (III), when contacting with an internal electron donor, the amount of the internal electron donor is usually 0.001 to 100 moles, preferably 0.01 to 10 moles, per 1 mole of total magnesium atoms in the metal magnesium or magnesium compound used in the steps (I) and (III).

The titanium halide compound, the metallic magnesium or magnesium compound, and the internal electron donor in the step (III) may be the same as or different from those in the step (I) or (II).

The temperature in the step (III) is usually from-30 ℃ to 150 ℃, preferably from-20 ℃ to 130 ℃, and more preferably from-10 ℃ to 120 ℃. The contact time is usually 0.1 to 12 hours, preferably 1 to 8 hours. In the present invention, the precursor is usually contacted with one or more of a titanium halide compound, a metallic magnesium or magnesium compound, and an internal electron donor in an inert gas atmosphere such as nitrogen or argon. The step (III) may be performed once or may be repeated a plurality of times.

After the reaction is completed, the obtained solid can be used as a solid catalyst component for olefin polymerization. The solid catalyst component for olefin polymerization is preferably washed with a solvent in the same manner as described above. In addition, drying (e.g., heat drying) may be performed after washing.

In one example, the titanium atom content in the solid catalyst component for olefin polymerization is usually 0.1 to 10% by weight, preferably 0.5 to 5.0% by weight.

In one example, the content of the internal electron donor in the solid catalyst component for olefin polymerization is usually 1 to 50% by weight, preferably 5 to 40% by weight.

In one example, the content of the alkoxy group in the solid catalyst component for olefin polymerization is usually 10% by weight or less, and preferably 5% by weight or less.

< catalyst for olefin polymerization >

In one embodiment, the catalyst for olefin polymerization can be produced by, for example, contacting the solid catalyst component for olefin polymerization of the present invention with an organoaluminum compound by a known method. In another embodiment, the catalyst for olefin polymerization can be produced by contacting the solid catalyst component for olefin polymerization of the present invention, an organoaluminum compound, and an external electron donor.

Accordingly, in one embodiment, the catalyst for olefin polymerization of the present invention comprises the solid catalyst component for olefin polymerization of the present invention and an organoaluminum compound. In another embodiment, the catalyst for olefin polymerization of the present invention comprises the solid catalyst component for olefin polymerization of the present invention, an organoaluminum compound, and an external electron donor.

The organoaluminum compound used in the present invention is a compound having one or more carbon-aluminum bonds, and specifically, a compound described in Japanese patent application laid-open No. 10-212319 can be exemplified. Among them, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldialumoxane is more preferable.

Examples of the external electron donor used in the present invention include compounds described in Japanese patent No. 2950168, Japanese patent application laid-open No. 2006-96936, Japanese patent application laid-open No. 2009-173870, and Japanese patent application laid-open No. 2010-168545. Among them, oxygen-containing compounds or nitrogen-containing compounds are preferable. Examples of the oxygen-containing compound include silicon alkoxides, ethers, esters, and ketones. Among them, silicon alkoxide and ether are preferable.

The silicon alkoxide as the external electron donor is preferably a compound represented by any one of the following formulas (iv) to (vii).

R² _hSi(OR³)_4-h……(iv)

Si(OR⁴)₃(NR⁵R⁶)……(v)

Si(OR⁴)₃(NR⁷)……(vi)

Si(OR⁴)₂(NR⁷)₂……(vii)

[ in the formula, R²Is a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms; r³Is a hydrocarbon group having 1 to 20 carbon atoms; h is an integer satisfying 0-4. At R²And R³In the case where there are two or more of them, R's are present²And R³May be the same as or different from each other. R⁴Is a hydrocarbon group having 1 to 6 carbon atoms; r⁵And R⁶Is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; NR (nitrogen to noise ratio)⁷Is a cyclic amino group having 5 to 20 carbon atoms.]

As R in the above formula (iv)²And R³Examples of the hydrocarbon group of (1) include: alkyl, aralkyl, aryl, alkenyl, etc., as R²And R³Examples of the alkyl group of (1) include: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, and 2-ethylhexyl groups; the cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms. As R²And R³As the aralkyl group of (2), there can be enumerated: benzyl and phenethyl, preferably aralkyl having 7 to 20 carbon atoms. As R²And R³As the aryl group of (1), there may be mentioned: phenyl, tolyl, and xylyl groups, preferably aryl having 6 to 20 carbon atomsAnd (4) a base. As R²And R³The alkenyl group of (a) may be exemplified by: linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as an isobutylene group and a 5-methyl-3-pentenyl group; the cyclic alkenyl group such as 2-cyclohexenyl and 3-cyclohexenyl is preferably an alkenyl group having 2 to 10 carbon atoms.

Specific examples of the silicon alkoxide represented by the above formula (iv) include: cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, diisopropyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, dicyclobutyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, isobutyltriethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, cyclopentyltriethoxysilane.

As R in the above formulae (v), (vi) and (vii)⁴Examples of the hydrocarbon group of (2) include an alkyl group and an alkenyl group, and R is⁴Examples of the alkyl group of (1) include: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, and neopentyl; the cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group is preferably a linear alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group. As R⁴The alkenyl group of (a) may be exemplified by: linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl; branched alkenyl groups such as an isobutylene group and a 5-methyl-3-pentenyl group; the cyclic alkenyl group such as 2-cyclohexenyl and 3-cyclohexenyl is preferably a linear alkenyl group having 2 to 6 carbon atoms.

As R in the above formula (v)⁵And R⁶Examples of the hydrocarbon group of (2) include an alkyl group and an alkenyl group, and R is⁵And R⁶Examples of the alkyl group of (1) include: straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl; branched alkyl groups such as isopropyl, isobutyl, tert-butyl, isopentyl, and neopentyl; cyclopropyl, cyclobutylThe cyclic alkyl group such as a phenyl group, a cyclopentyl group, or a cyclohexyl group is preferably a linear alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group or an ethyl group. As R⁵And R⁶Examples of the alkenyl group of (a) include a straight-chain alkenyl group such as a vinyl group, an allyl group, a 3-butenyl group and a 5-hexenyl group; branched alkenyl groups such as an isobutylene group and a 5-methyl-3-pentenyl group; the cyclic alkenyl group such as 2-cyclohexenyl and 3-cyclohexenyl is preferably a linear alkenyl group having 2 to 6 carbon atoms.

Specific examples of the silicon alkoxide represented by the above formula (v) include: dimethylaminotrimethoxysilane, diethylaminotrimethoxysilane, di-n-propylaminotrimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, di-n-propylaminotriethoxysilane, methylethylaminotriethoxysilane, methyl-n-propylaminotriethoxysilane, tert-butylaminotriethoxysilane, diisopropylaminotriethoxysilane, methylisopropylaminotriethoxysilane.

As NR in the above formulae (vi) and (vii)⁷The cyclic amino group of (b) includes: perhydroquinolinyl, perhydroisoquinolinyl, 1,2,3, 4-tetrahydroquinolinyl, 1,2,3, 4-tetrahydroisoquinolinyl, octamethyleneimino.

Specific examples of the silicon alkoxides represented by the above formulae (vi) and (vii) include: perhydroquinolinyltriethoxysilane, perhydroisoquinolinyltriethoxysilane, 1,2,3, 4-tetrahydroquinolinyltriethoxysilane, 1,2,3, 4-tetrahydroisoquinolinyltriethoxysilane, octamethyleneiminotriethoxysilane.

The ether as the external electron donor is preferably a cyclic ether compound. The cyclic ether compound means a heterocyclic compound having at least one-C-O-C-bond in the ring structure, more preferably a cyclic ether compound having at least one-C-O-C-bond in the ring structure, and particularly preferably 1, 3-dioxolane or 1, 3-dioxane.

The external electron donor may be used alone or in combination of two or more.

The method for contacting the solid catalyst component for olefin polymerization, the organoaluminum compound and the external electron donor is not particularly limited as long as the catalyst for olefin polymerization is produced. The contacting is carried out in the presence or absence of a solvent. The solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donor may be supplied to the polymerization vessel as a contact mixture, or each component may be supplied to the polymerization vessel separately and brought into contact with the polymerization vessel, or any two components of the contact mixture and the remaining components may be supplied to the polymerization vessel separately and brought into contact with each other in the polymerization vessel.

The amount of the organoaluminum compound used is usually 0.01 to 1000. mu. mol, preferably 0.1 to 500. mu. mol, based on 1mg of the solid catalyst component for olefin polymerization.

The amount of the external electron donor used is usually 0.0001 to 1000. mu. mol, preferably 0.001 to 500. mu. mol, and more preferably 0.01 to 150. mu. mol, based on 1mg of the solid catalyst component for olefin polymerization.

< Process for producing olefin Polymer >

In the process for producing an olefin polymer of the present invention, an olefin is polymerized in the presence of the olefin polymerization catalyst of the present invention.

Examples of the olefin include ethylene and an α -olefin having 3 or more carbon atoms. As the α -olefin, there can be exemplified: linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-decene; branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more thereof. Among these, homopolymerization of ethylene or propylene or copolymerization of plural kinds of olefins mainly composed of ethylene or propylene is preferable. The combination of the plurality of olefins may include a combination of two or more kinds of olefins, and may also include a combination of a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene and an olefin.

The olefin polymer produced by the method for producing an olefin polymer of the present invention is preferably an ethylene homopolymer, a propylene homopolymer, a butene-1 homopolymer, a pentene-1 homopolymer, a hexene-1 homopolymer, an ethylene-propylene copolymer, an ethylene-butene-1 copolymer, an ethylene-hexene-1 copolymer, a propylene-butene-1 copolymer, a propylene-hexene-1 copolymer, an ethylene-propylene-butene-1 copolymer, an ethylene-propylene-hexene-1 copolymer, or a polymer obtained by polymerizing these in multiple stages.

In one embodiment, a method of forming the catalyst for olefin polymerization of the present invention may preferably be a method comprising the following steps:

(i) the process comprises the following steps: in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, a small amount of an olefin (the same as or different from the olefin used in the conventional polymerization (usually referred to as main polymerization)) is polymerized (a chain transfer agent such as hydrogen or an external electron donor may be used to adjust the molecular weight of the olefin polymer to be produced), thereby producing a catalyst component whose surface is covered with the olefin polymer (the polymerization is usually referred to as prepolymerization, and therefore the catalyst component is usually referred to as a prepolymerization catalyst component)

(ii) The process comprises the following steps: the prepolymerized catalyst component is contacted with an organoaluminum compound and an external electron donor.

The prepolymerization is preferably a slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene as a solvent.

The amount of the organoaluminum compound used in the step (i) is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, and particularly preferably 1 to 200 mol, per 1 mol of the titanium atom in the solid catalyst component used in the step (i).

The amount of the olefin to be prepolymerized is usually 0.01g to 1000g, preferably 0.05g to 500g, particularly preferably 0.1g to 200g, per 1g of the solid catalyst component for olefin polymerization used in the step (i).

The slurry concentration of the solid catalyst component for olefin polymerization in the slurry polymerization in the step (i) is preferably 1g to 500g, particularly preferably 3g to 300g, of the solid catalyst component for olefin polymerization per liter of the solvent.

The temperature of the prepolymerization is preferably from-20 ℃ to 100 ℃, particularly preferably from 0 ℃ to 80 ℃. The partial pressure of the olefin in the gas phase during the preliminary polymerization is preferably 0.01MPa to 2MPa, particularly preferably 0.1MPa to 1MPa, and the olefin which is liquid at the pressure and temperature of the preliminary polymerization is not limited thereto. The time for the prepolymerization is preferably 2 minutes to 72 hours.

As a method for supplying the solid catalyst component for olefin polymerization, the organoaluminum compound and the olefin to the polymerization vessel in the preliminary polymerization, the following method (1) and method (2) can be exemplified:

(1) a method of supplying an olefin after supplying a solid catalyst component for olefin polymerization and an organoaluminum compound;

(2) a method of supplying an organoaluminum compound after supplying the solid catalyst component for olefin polymerization and the olefin.

As a method of supplying an olefin to a polymerization vessel in the preliminary polymerization, the following method (1) and method (2) can be exemplified:

(1) a method of sequentially supplying olefins to a polymerization vessel so as to maintain the pressure in the polymerization vessel at a predetermined pressure;

(2) a method of supplying a total amount of a predetermined amount of an olefin to a polymerization vessel at once.

The amount of the external electron donor used in the preliminary polymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, and particularly preferably 0.03 to 100 mol, based on 1 mol of the titanium atom contained in the solid catalyst component for olefin polymerization, and the amount of the external electron donor used in the preliminary polymerization is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol, based on 1 mol of the organoaluminum compound.

Examples of the method for supplying the external electron donor to the polymerization vessel in the preliminary polymerization include the following methods (1) and (2):

(1) a method of separately supplying an external electron donor to a polymerization vessel;

(2) a method of feeding a contact product of an external electron donor and an organoaluminum compound to a polymerization vessel.

The amount of the organoaluminum compound used in the main polymerization is usually 1 to 1000 moles, and particularly preferably 5 to 600 moles per 1 mole of the titanium atom in the solid catalyst component for olefin polymerization.

The amount of the external electron donor used in the case where the external electron donor is used in the main polymerization is usually 0.1 to 2000 moles, preferably 0.3 to 1000 moles, and particularly preferably 0.5 to 800 moles per 1 mole of the titanium atom contained in the solid catalyst component for olefin polymerization, and the amount of the external electron donor used in the case where the external electron donor is used in the main polymerization is usually 0.001 to 5 moles, preferably 0.005 to 3 moles, and particularly preferably 0.01 to 1 mole per 1 mole of the organoaluminum compound.

The temperature of the main polymerization is usually from-30 ℃ to 300 ℃ and preferably from 20 ℃ to 180 ℃. The polymerization pressure is not particularly limited, but is usually from normal pressure to 10MPa, preferably from about 200kPa to about 5MPa, from the industrial and economical viewpoints. The polymerization is a batch type or a continuous type, and examples of the polymerization method include: a slurry polymerization method or a solution polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, hexane, heptane, octane, or the like as a solvent, a bulk polymerization method using an olefin which is liquid at a polymerization temperature as a medium, and a gas phase polymerization method using a fluidized bed.

In order to adjust the molecular weight of the polymer obtained in the main polymerization, a chain transfer agent (for example, hydrogen, alkyl zinc such as dimethyl zinc and diethyl zinc) may be used.

According to the present invention, clogging of a polymerization apparatus and adhesion of a polymer to a wall surface of the polymerization apparatus are reduced when an olefin is polymerized.

Hereinafter, embodiments of the present invention will be described in more detail by way of examples.

[ examples ]

The present invention will be described more specifically below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

< determination of solid catalyst component for olefin polymerization by X-ray photoelectron spectroscopy >

The peak of the solid catalyst component for olefin polymerization, which is assigned to the 2p orbital of the titanium atom, and the peak assigned to the 1s orbital of the oxygen atom, are according to standard ISO 15472: 2001 and measured by X-ray photoelectron spectroscopy. The peak was obtained under the following measurement conditions using Quantera SXM (manufactured by ULVAC PHI corporation) as a measurement device. In the measurement of the peak, charge compensation was performed so that the binding energy of the carbon 1s orbital of the C-C bond was 284.6 eV.

< measurement Condition >

Light source: monochromatic AlK alpha ray (1486.6eV)

Tube current: 3mA

Tube voltage: 15kV

Among the measured peaks ascribed to the 2p orbitals of titanium atoms, the peak components having peak tops with a binding energy in the range of 457.00eV or more and 459.00eV or less and the peak components having peak tops with a binding energy in the range of more than 459.00eV and 460.00eV or less were subjected to waveform separation using a plurality of Gaussian (Gaussian) lines and Lorentzian (Lorentzian) lines with the half-peak width and intensity as fitting parameters. The binding energy of the peak top (1) was determined, which had a binding energy in the range of 457.00eV or more and 459.00eV or less, among the peak components of the 2p orbital derived from the titanium atom.

Among the measured peaks attributed to the 1s orbitals of oxygen atoms, the peak components having peak tops with binding energies in the range of 532.50eV or more and 534.50eV or less and the peak components having peak tops with binding energies in the range of 530.00eV or more and less than 532.50eV were subjected to waveform separation using a plurality of Gaussian (Gaussian) lines and Lorentzian (Lorentzian) lines with the half-peak width and intensity as fitting parameters. The binding energy of the peak top (2) having a binding energy in the range of 532.50eV or more and 534.50eV or less was determined for the peak component of the 1s orbital assigned to the oxygen atom.

The absolute value of the difference in binding energy was obtained by subtracting the binding energy of peak (1) from the binding energy of peak (2).

< amount of fine powder (cm) of solid catalyst component for olefin polymerization²Measurement of/g) >

The amount of the fine powder of the solid catalyst component for olefin polymerization was measured by the gravity sedimentation method. The solid catalyst component for olefin polymerization was dispersed in toluene, followed by shaking and then standing. The amount of the fine powder was determined from the difference between the specific absorbances at the time 100 seconds elapsed and the time 600 seconds elapsed after the standing (wavelength: 500nm, specific absorbance at the time 100 seconds elapsed-specific absorbance at the time 600 seconds elapsed). The specific absorbance was calculated according to the following formula.

Specific absorbance/(weight (g) of the solid catalyst component for olefin polymerization)/volume (cm) of toluene at each time³) Length of optical path (cm)

For the measurement of specific absorbance, an ultraviolet-visible near-infrared spectrophotometer manufactured by japan spectrophotometers: v-650.

When the amount of the fine powder of the solid catalyst component for olefin polymerization is small, clogging of the polymerization apparatus and adhesion of the polymer to the wall surface of the polymerization apparatus are improved (reduced) when the olefin is polymerized.

< method for measuring mechanical Strength (MPa) of precursor of solid catalyst component for olefin polymerization >

The mechanical strength (MPa) was calculated from the following formula using a force p (mn) when the particles were broken (fractured) by applying a load to the particles and a particle diameter d (μm).

Mechanical strength 2.48 XP/(π × d × d)

A micro compression tester MCT-210 series manufactured by Shimadzu corporation was used as a device for measuring mechanical strength. Using a microscope, 1 particle of a precursor of the solid catalyst component for olefin polymerization was taken as a test particle, and the particle diameter d of the test particle was measured. The mechanical strength was measured under a nitrogen atmosphere at a dew point of-40 ℃ or lower with the loading rate set at 4.44 mN/sec. The measurement was performed on 10 or more precursors of the solid catalyst component for olefin polymerization, and the average value of the mechanical strength was determined. Note that a value exceeding 2 σ from the average value is excluded as an abnormal value.

< example 1 >

< Synthesis of catalyst component 1 for olefin polymerization >

A step (I):

the gas in the flask with the stirrer was replaced with nitrogen. Then, toluene (171mL) and titanium tetrachloride (108mL) were added to the flask and stirred to obtain a toluene solution of titanium tetrachloride. Then, the temperature in the flask was adjusted to 0 ℃ and then at n₁：230rpm、d₁：0.054m、A₁: while stirring under the condition of 0.32, diethoxymagnesium (8.9g) was added to the flask in 4 portions every 30 minutes. Then, the temperature in the flask was maintained at 0 ℃ for 90 minutes. Then, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (2.7mL) and toluene (32mL) were added to the flask. The temperature in the flask was adjusted to 60 ℃, then ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (14.1mL) was added to the flask, the temperature in the flask was adjusted to 110 ℃, and then stirred at 110 ℃ for 3 hours. The obtained slurry was subjected to solid-liquid separation to obtain a solid. The obtained solid was washed with toluene at 100 ℃ to obtain a solid product.

Step (II):

the flask equipped with a stirrer was replaced with nitrogen, and the solid product obtained in step (I) and toluene (143mL) were added, followed by stirring₂：230rpm、d₂：0.054m、A₂: the mixture was stirred at room temperature under the condition of 0.32, thereby obtaining a slurry. The temperature in the flask was adjusted to 70 ℃, and then titanium tetrachloride (71mL) was added to the flask, followed by ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (3.4 mL). The temperature in the flask was adjusted to 105 ℃ and then stirred at 105 ℃ for 1 hour. The resulting mixture was subjected to solid-liquid separation using a filter having a mesh size of 20 μm to 30 μm (G3 filter in accordance with JIS R3503-1994), thereby obtaining a solid. The resulting solid was washed with toluene at 60 ℃ and then hexane at room temperature. The obtained solid was dried to obtain a solid catalyst component 1 for olefin polymerization. The yield of the obtained solid catalyst component 1 for olefin polymerization was 100% based on the amount of magnesium charged. The results are shown in table 1.

As a result of performing X-ray photoelectron spectroscopy measurement of the obtained solid catalyst component for olefin polymerization 1, the binding energy of the peak top (1) obtained by waveform-separating the peak ascribed to the 2p orbital of the titanium atom was 458.47eV (see fig. 1), the binding energy of the peak top (2) obtained by waveform-separating the peak ascribed to the 1s orbital of the oxygen atom was 533.76eV (see fig. 2), and the absolute value of the difference between the binding energies was 75.29 eV. The results are shown in table 1.

The amount of the fine powder obtained from the specific absorbance of the toluene suspension of the obtained solid catalyst component 1 for olefin polymerization was 2cm²(ii) in terms of/g. The results are shown in table 1.

< example 2 >

< Synthesis of solid catalyst component 2 for olefin polymerization >

Except that it is changed to n₁：266rpm、d₁：0.054m、A₁：0.37、n₂：266rpm、d₂：0.054m、A₂: a solid catalyst component 2 for olefin polymerization was obtained in the same manner as in example 1 except for the condition of 0.37. The yield of the obtained solid catalyst component 2 for olefin polymerization was 100% based on the amount of magnesium charged. The results are shown in table 1.

< example 3 >

< Synthesis of solid catalyst component 3 for olefin polymerization >

Except that it is changed to n₁：1025rpm、d₁：0.054m、A₁：1.43、n₂：1025rpm、d₂：0.054m、A₂: 1.43 except for the conditions, a solid catalyst component 3 for olefin polymerization was obtained in the same manner as in example 1. The yield of the obtained solid catalyst component 3 for olefin polymerization was 80% based on the amount of magnesium charged. The results are shown in table 1.

< comparative example 1 >

< Synthesis of solid catalyst component C1 for olefin polymerization >

Except that it is changed to n₁：190rpm、d₁：0.054m、A₁：0.26、n₂：190rpm、d₂：0.054m、A₂: a solid catalyst component C1 for olefin polymerization was obtained in the same manner as in example 1 except that the conditions were changed to 0.26. The olefins obtainedThe yield of the solid catalyst component C1 for polymerization was 60% based on the amount of magnesium charged. The results are shown in table 1.

< comparative example 2 >

< Synthesis of solid catalyst component C2 for olefin polymerization >

Except that it is changed to n₁：1220rpm、d₁：0.054m、A₁：1.70、n₂：1220pm，d₂：0.054m、A₂: 1.70 under the same conditions as in example 1, a solid catalyst component C2 for olefin polymerization was obtained. The yield of the obtained solid catalyst component C2 for olefin polymerization was 90% based on the amount of magnesium charged. The results are shown in table 1.

[ Table 1]

< example 4 >

< Synthesis of precursor 4 of catalyst component for olefin polymerization >

A step (I):

the inside of a stainless steel vessel having a stirrer was replaced with nitrogen gas. Then, toluene (52.8L) and titanium tetrachloride (33.3L) were added to the vessel and stirred, thereby obtaining a toluene solution of titanium tetrachloride. Then, the temperature in the container is adjusted to 0 ℃ or lower, and then n₁：100rpm、d₁：0.36m、A₁: while stirring under the condition of 0.70, diethoxymagnesium (11kg) was added to the vessel at 6 times every 72 minutes. Then, the temperature inside the container was maintained so as not to exceed 2 ℃ for 120 minutes. Then, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (0.77kg) was added to the vessel, and the temperature in the vessel was adjusted to 10 ℃ or lower and maintained for 90 minutes. The obtained slurry was subjected to solid-liquid separation to obtain a solid. The resulting solid was washed with toluene at room temperature. The obtained solid was dried to obtain a solid product (precursor 4 of the solid catalyst component for olefin polymerization). The mechanical strength of the solid product obtained was 4.4 MPa. The results are shown in Table 2In (1).

< example 5 >

< Synthesis of precursor of catalyst component for olefin polymerization 5 >

A step (I):

the inside of a stainless steel vessel having a stirrer was replaced with nitrogen gas. Then, toluene (52.8L) and titanium tetrachloride (33.3L) were added to the vessel and stirred, thereby obtaining a toluene solution of titanium tetrachloride. Then, the temperature in the container is adjusted to 0 ℃ or lower, and then n₁：140rpm、d₁：0.36m、A₁: while stirring under the condition of 0.98, diethoxymagnesium (11kg) was added to the vessel at 6 times every 72 minutes. Then, the temperature inside the container was maintained so as not to exceed 2 ℃ for 120 minutes. The obtained slurry was subjected to solid-liquid separation to obtain a solid. The resulting solid was washed with toluene at room temperature. The obtained solid was dried to obtain a solid product (precursor 5 of the solid catalyst component for olefin polymerization).

< example 6 >

< Synthesis of precursor of catalyst component for olefin polymerization 6 >

A step (I):

the inside of a stainless steel vessel having a stirrer was replaced with nitrogen gas. Then, toluene (52.8L) and titanium tetrachloride (33.3L) were added to the vessel and stirred, thereby obtaining a toluene solution of titanium tetrachloride. Then, the temperature in the container is adjusted to 0 ℃ or lower, and then n₁：100rpm、d₁：0.36m、A₁: while stirring under the condition of 0.70, diethoxymagnesium (11kg) was added to the vessel at 6 times every 72 minutes. Then, the temperature inside the container was maintained so as not to exceed 3 ℃ and maintained for 210 minutes. Then, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (0.76kg) was added to the vessel, and the temperature in the vessel was adjusted to 12 ℃ or lower and maintained for 2 hours. The obtained slurry was subjected to solid-liquid separation to obtain a solid. The resulting solid was washed with toluene at room temperature. The obtained solid was dried to obtain a solid product (precursor 6 of the solid catalyst component for olefin polymerization). ObtainedThe mechanical strength of the solid product was 6.8 MPa. The results are shown in table 2.

< example 7 >

< Synthesis of precursor of catalyst component for olefin polymerization 7 >

A step (I):

the inside of a stainless steel vessel having a stirrer was replaced with nitrogen gas. Then, toluene (52.8L) and titanium tetrachloride (33.3L) were added to the vessel and stirred, thereby obtaining a toluene solution of titanium tetrachloride. Then, the temperature in the container is adjusted to 0 ℃ or lower, and then n₁：72rpm、d₁：0.36m、A₁: while stirring under the condition of 0.50, diethoxymagnesium (11kg) was added to the vessel at 6 times every 72 minutes. Then, the temperature inside the container was maintained so as not to exceed 3 ℃ for 110 minutes. Then, ethyl 2-ethoxymethyl-3, 3-dimethylbutyrate (0.76kg) was added to the vessel, and the temperature in the vessel was adjusted to 11 ℃ or lower and maintained for 2 hours. The obtained slurry was subjected to solid-liquid separation to obtain a solid. The resulting solid was washed with toluene at room temperature. The obtained solid was dried to obtain a solid product (precursor 7 of the solid catalyst component for olefin polymerization). The mechanical strength of the solid product obtained was 5.4 MPa. The results are shown in table 2.

[ Table 2]

	A1	Mechanical Strength (MPa)
			Example 4	0.70	4.4
Example 5	0.98	3.9
			Example 6	0.70	6.8
Example 7	0.50	5.4

The present invention can be used for the production of olefin polymers.