JP2018188505A - Manufacturing method of olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having excellent polymerization activity and hydrogen resistance during polymerization, excellent MFR and rigidity, wide molecular weight distribution, and high stereoregularity when homopolymerizing or copolymerizing olefins. Provided is a manufacturing method that can be manufactured under sustainability. SOLUTION: A first step of contacting, reacting with a magnesium compound, a tetravalent titanium halogen compound, and a specific first internal electron donating compound and washing is performed, and the obtained product is subjected to a first step. A solid catalyst component for olefin polymerization obtained by performing a second step of contacting, reacting, and washing a tetravalent titanium halogen compound with a second internal electron donating compound, and a specific organic aluminum compound. Using a catalyst for olefin polymerization in contact with an external electron donating compound, one or more polymerization reactions selected from the homopolymerization reaction of propylene and the copolymerization reaction of propylene and other α-olefins are different. This is a method for producing an olefin compound, which is carried out a plurality of times under the concentration of a molecular weight modifier. [Selection diagram] None

Description

  The present invention relates to a method for producing an olefin polymer.

  Conventionally, olefins such as propylene have been polymerized using an olefin polymerization catalyst, and the resulting propylene polymer is melted and then molded by various molding machines or stretching machines. In addition to molded products such as automobile parts and home appliance parts, they are used for various applications such as containers and films.

  Solid catalyst components containing magnesium, titanium, an electron donating compound and halogen atoms as essential components are known as constituents of the olefin polymerization catalyst. The solid catalyst component, the organoaluminum compound and the organosilicon compound Many olefin polymerization catalysts comprising:

  By the way, as a propylene polymer, a polymer having a high crystallinity and a wide molecular weight distribution is required when it is molded by various molding machines, stretching machines, and the like.

  The molecular weight distribution of a propylene-based polymer varies depending on the amount of olefin polymer having a high molecular weight and an olefin polymer having a low molecular weight, and the molecular weight is generally controlled by a molecular weight regulator. The controllability depends on the solid catalyst component used, the external electron donating compound, the polymerization method, and the like, and the stereoregularity of the resulting polymer also depends on the solid catalyst, the external electron donating compound and the like.

  In recent years, in products such as large home appliance parts and automobile parts, particularly bumpers, in addition to high MFR and stereoregularity, olefin polymers are thin and have high physical strength, that is, excellent rigidity. It has come to be required. On the other hand, in order to maintain the flow unevenness at the time of molding and the homogeneity of the film or sheet, it is necessary to appropriately control the molecular weight distribution.

Under such circumstances, the present applicant previously described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-107462) an internal electron donating compound composed of a magnesium compound, a tetravalent titanium halogen compound, and malonic acid diesters, and Proposed a catalyst for olefin polymerization consisting of a solid catalyst component obtained by contacting an internal electron donating compound consisting of phthalic diesters, an organoaluminum compound and an organosilicon compound, and polymerization of olefins using the polymerization catalyst Proposed method.
As another method, an olefin polymerization catalyst comprising a solid catalyst component obtained from an internal electron donating compound comprising a magnesium compound, a tetravalent titanium halogen compound, and a phthalic acid diester, and an organoaluminum compound and an organosilicon compound is provided. And proposed to improve activity, improve stereoregularity, and broaden the molecular weight distribution (see Patent Document 2 (Japanese Patent Laid-Open No. 2006-169283)).

JP 2004-107462 A JP 2006-169283 A

  The olefin polymerization catalyst described in Patent Document 1 exhibits good hydrogen-to-hydrogen activity as compared with conventional polymerization catalysts, and the olefin polymer obtained using such a solid catalyst component is a molten polymer. It has a high fluidity (MFR) and is particularly useful when producing large molded articles by injection molding or the like.

  However, when the present inventors further examined, in order to simultaneously contact and react two or more different internal electron donating compounds to contain a desired amount of the internal electron donating compound in the solid catalyst component, It is necessary to set a large amount of each additive. For this reason, it becomes easy to form a complex of an excess internal electron donating compound and a tetravalent titanium halogen compound, and when used as a constituent component of an olefin polymerization catalyst, polymerization activity during polymerization and olefins obtained are obtained. It has been found that the stereoregularity of the polymer tends to decrease.

  Further, a catalyst capable of producing an olefin polymer having a wider molecular weight distribution and exhibiting excellent rigidity has been demanded as an olefin polymerization catalyst.

By the way, when producing a large molded article by injection molding or the like, not only a homopolymer composed of a single olefin such as propylene, but also a copolymer of two or more α-olefins such as propylene and ethylene. May be required.
In this case, for example, when a block copolymer is produced by first carrying out a homopolymerization reaction using propylene and subsequently carrying out a copolymerization reaction using propylene and ethylene, the proportion of the copolymerization part is increased. Since the rigidity of the polymer is lowered, it is necessary to form a polypropylene having higher rigidity in the homopolymerization in the previous stage.

  However, as a result of studies by the present inventors, a conventionally known catalyst is used to produce a polymer with high stereospecificity, for example, in the first stage propylene polymerization stage (homopolymerization stage), and a predetermined copolymer is produced in the subsequent stage. It was found that even if the copolymer was produced, a copolymer having a significantly reduced rigidity could not be produced.

  Under such circumstances, the present invention provides excellent polymerization activity of olefins and hydrogenation activity during polymerization, excellent MFR and rigidity, wide molecular weight distribution, and stericity when homopolymerizing or copolymerizing olefins. It is an object of the present invention to provide a novel production method capable of producing a polymer having high regularity under high polymerization activity sustainability.

  As a result of intensive studies by the present inventors in order to solve the above technical problem, a method for producing an olefin polymer comprising a magnesium compound, a tetravalent titanium halogen compound, and a specific aromatic dicarboxylic acid The first internal electron-donating compound comprising a diester is brought into contact with, reacted with, and then subjected to a first step of washing, and the resulting product is subjected to a tetravalent titanium halogen compound and one or more first compounds. A solid catalyst component for polymerizing olefins, a specific organoaluminum compound, and an external electron donating compound obtained by subjecting the second internal electron donating compound to contact, reaction, and the second step of washing Is used, and the propylene homopolymerization reaction and the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms are 5% by weight or less. To produce an olefin polymer by performing at least one polymerization reaction selected from copolymerization reactions of propylene and an α-olefin having 2 or 4 to 10 carbon atoms at different molecular weight regulator concentrations. As a result, it has been found that the above object can be achieved, and the present invention has been completed based on this finding.

That is, the present invention
(1) A method for producing an olefin polymer,
Magnesium compound, tetravalent titanium halogen compound, and the following general formula (I)
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and when a plurality of R ¹ are present, they may be the same as or different from each other, and R ² and R ³ may have 1 to 1 carbon atoms. 12 alkyl groups, which may be the same or different, and the number j of substituents R ¹ is 0, 1 or 2, and when j is 2, each R ¹ is the same And the first internal electron donating compound selected from the aromatic dicarboxylic acid diesters represented by the following formula: For the resulting product,
A solid catalyst component for olefin polymerization obtained by subjecting a tetravalent titanium halogen compound and one or more second internal electron donating compounds to contact, reacting, and then performing a second step of washing;
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other; Q is a hydrogen atom or a halogen atom; When present, they may be the same or different, and p is a real number of 0 <p ≦ 3.)
An organoaluminum compound represented by:
Using an olefin polymerization catalyst formed by contacting an external electron donating compound,
A homopolymerization reaction of propylene and a copolymerization reaction of propylene with an α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by weight or less. One or more polymerization reactions selected from: a method for producing an olefin polymer, wherein the polymerization reaction is performed a plurality of times under different molecular weight regulator concentrations;
(2) The method for producing an olefin polymer according to (1), wherein the homopolymerization reaction of propylene is performed a plurality of times under different molecular weight regulator concentrations,
(3) In the polymerization reaction performed a plurality of times,
The amount of the molecular weight regulator used in the first polymerization reaction is 0 to 5 × 10 ⁻³ (mol / mol) in a ratio represented by the molar amount of the molecular weight regulator / the molar amount of propylene used.
The amount of the molecular weight regulator used in the second polymerization reaction is 1 × 10 ⁻² (mol / mol) or more in a ratio represented by the molar amount of the molecular weight regulator / the molar amount of propylene used. (1) A method for producing the olefin polymer according to (2),
(4) The method for producing an olefin polymer according to the above (1) or (2), wherein the molecular weight regulator is hydrogen,
(5) The external electron donating compound is represented by the following general formula (III):
R ⁵ _q Si (OR ⁶ ) _4-q (III)
(However, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, a linear or branched alkylamino group, or a polycyclic amino group, and R ⁵ R ⁶ may be the same as or different from each other when R ² is present, and R ⁶ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, A vinyl group, an allyl group or an aralkyl group, and when a plurality of R ⁶ are present, they may be the same or different from each other, q is an integer of 0 ≦ q ≦ 3.
An organosilicon alkoxy compound represented by the following general formula (IV):
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are each a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. A group selected from an alkyl group and an aryl group, which may be the same or different from each other; R ⁷ and R ⁸ may be bonded to each other to form a ring; and the R ⁷ R ⁸ N group is When there are a plurality of them, they may be the same or different from each other, and R ⁹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or 1 carbon atom. linear or branched alkoxy group to 20, vinyloxy group, a group selected from aryloxy group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group or an aryloxy group, if R ⁹ there are a plurality, more of ^{R 9} Optionally be the same or different .s is an integer from 1 to 3.)
The method for producing an olefin polymer according to the above (1) or (2), which is at least one selected from aminosilane compounds represented by:
(6) The solid catalyst component for polymerizing olefins comprises the first internal electron donating compound and the second internal electron donating compound.
The molar amount of the first internal electron-donating compound> the molar amount of the second internal electron-donating compound obtained by contact so as to satisfy the relationship of (1) or (2) Production method of olefin polymers,
(7) Propylene homopolymerization reaction and copolymerization of propylene and α-olefin having 2 or 4 to 10 carbon atoms so that the content of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less After performing one or more polymerization reactions selected from the reaction multiple times under different molecular weight regulator concentrations,
For the obtained polymer, a copolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms has a content ratio of 2 to 4 or 10 to α-olefin of 20 to 80% by mass or less. The method for producing the olefin polymer according to the above (1) or (2),
Is to provide.

  According to the present invention, when performing homopolymerization or copolymerization of olefins, the polymerization activity of olefins and the hydrogen activity during polymerization are excellent, the MFR and rigidity are excellent, the molecular weight distribution is wide, and the stereoregularity is high. It is possible to provide a novel production method capable of producing a polymer under a high polymerization activity persistence.

The method for producing an olefin polymer according to the present invention is a method for producing an olefin polymer,
Magnesium compound, tetravalent titanium halogen compound, and the following general formula (I)
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and when a plurality of R ¹ are present, they may be the same as or different from each other, and R ² and R ³ may have 1 to 1 carbon atoms. 12 alkyl groups, which may be the same or different, and the number j of substituents R ¹ is 0, 1 or 2, and when j is 2, each R ¹ is the same And the first internal electron donating compound selected from the aromatic dicarboxylic acid diesters represented by the following formula: For the resulting product,
A solid catalyst component for olefin polymerization obtained by subjecting a tetravalent titanium halogen compound and one or more second internal electron donating compounds to contact, reacting, and then performing a second step of washing;
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other; Q is a hydrogen atom or a halogen atom; When present, they may be the same or different, and p is a real number of 0 <p ≦ 3.)
An organoaluminum compound represented by:
Using an olefin polymerization catalyst obtained by contacting an external electron donating compound,
A homopolymerization reaction of propylene and a copolymerization reaction of propylene with an α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by weight or less. One or more polymerization reactions selected from the above are performed a plurality of times under different molecular weight regulator concentrations.

First, the solid catalyst component for olefin polymerization used in the present invention will be described.
The solid catalyst component for olefin polymerization used in the present invention includes a magnesium compound, a tetravalent titanium halogen compound, and the following general formula (I):
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, R ² and R ³ are alkyl groups having 1 to 12 carbon atoms, which may be the same or different, The number j of the substituent R ¹ is 0, 1 or 2, and when j is 2, each R ¹ may be the same or different.) The first internal electron donating compound to be contacted, reacted, and then subjected to a first step of washing, and the resulting product,
A tetravalent titanium halogen compound and one or more second internal electron donating compounds are brought into contact with each other, reacted, and then subjected to a second step of washing.
Since the solid catalyst component for olefin polymerization is defined by the production method, the solid catalyst component for olefin polymerization will be described below based on the production method.

(First step)
In the solid catalyst component for olefin polymerization used in the present invention, examples of the magnesium compound include one or more selected from dialkoxymagnesium, magnesium dihalides, alkoxymagnesium halides, and the like.

  Among the above magnesium compounds, dialkoxymagnesium or magnesium dihalide is preferable, and specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, magnesium dichloride. , Magnesium dibromide, magnesium diiodide and the like, and diethoxymagnesium and magnesium dichloride are particularly preferable.

  Of the magnesium compounds, dialkoxymagnesium may be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

  In the solid catalyst component for olefin polymerization used in the present invention, dialkoxymagnesium is preferably in the form of granules or powder, and the shape may be indefinite or spherical.

  When a spherical one is used as dialkoxymagnesium, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution is obtained, and the handling operability of the polymer powder produced during the polymerization operation is improved. It can improve and can suppress generation | occurrence | production of the obstruction | occlusion etc. resulting from the fine powder contained in the produced polymer powder.

The spherical dialkoxymagnesium does not necessarily have a true spherical shape, and an elliptical shape or a potato shape can also be used. Specifically, the circularity of the particles is preferably 3 or less, more preferably 1 or 2, and further preferably 1 to 1.5.
In the present application documents, the circularity of dialkoxymagnesium particles refers to the area of each particle obtained by photographing 500 or more dialkoxymagnesium particles with a scanning electron microscope and processing the photographed particles with image analysis processing software. S and circumference L are obtained, and the circularity of each dialkoxymagnesium particle is expressed by the following formula: Circularity of each dialkoxymagnesium particle = L ² ÷ (4π × S)
This means the arithmetic average value when calculated by (1). The closer the particle shape is to a perfect circle, the closer the circularity is to 1.

The average particle size of the dialkoxymagnesium is 1 in terms of an average particle size D ₅₀ (50% particle size in the cumulative particle size distribution) when measured using a laser light scattering diffraction particle size analyzer. It is preferably ˜200 μm, more preferably 5 to 150 μm.
When dialkoxymagnesium is spherical, the average particle size is preferably 1 to 100 μm, more preferably 5 to 60 μm, and even more preferably 10 to 50 μm.

Moreover, about the particle size of dialkoxymagnesium, it is preferable that there are few fine powders and coarse powders and a narrow particle size distribution.
Specifically, the dialkoxymagnesium is preferably 20% or less, more preferably 10% or less of particles of 5 μm or less when measured using a laser light scattering diffraction particle size measuring instrument. On the other hand, when measured using a laser light scattering diffraction particle size measuring machine, the particle size of 100 μm or more is preferably 10% or less, more preferably 5% or less.
Furthermore, the particle size distribution of dialkoxymagnesium is ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is the cumulative particle size in the volume cumulative particle size distribution and 90% of the particle size, and D ₁₀ is the cumulative particle size in the volume cumulative particle size distribution of 10%. The particle size is preferably 3 or less, more preferably 2 or less.

  The spherical dialkoxymagnesium can be produced by, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-8- This is exemplified in Japanese Patent No. 73388.

  In the solid catalyst component for olefin polymerization used in the present invention, the magnesium compound is preferably in the form of a solution or a suspension at the time of reaction, and the reaction is suitably advanced by being in the form of a solution or a suspension. be able to.

When the magnesium compound is a solid, the magnesium compound can be made into a solution-like magnesium compound by dissolving in a solvent capable of solubilizing the magnesium compound, or suspended in a solvent not having the solubilizing ability of the magnesium compound. By turbidity, a magnesium compound suspension can be obtained.
When the magnesium compound is in a liquid form, it may be used as it is as a solution-like magnesium compound, or it may be further dissolved in a solvent having a solubilizing ability of the magnesium compound and used as a solution-like magnesium compound. .

Examples of the compound that can solubilize the solid magnesium compound include at least one compound selected from the group consisting of alcohols, ethers, and esters.
Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol , Alcohols having 1 to 18 carbon atoms such as ethylene glycol, halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol, trichlorohexanol, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether , Tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, diphenyl ether, etc. Examples include ethers having 2 to 20 elementary atoms, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium. Among them, alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol are preferable, and 2-ethylhexanol is particularly preferable.

On the other hand, examples of the medium having no solubilizing ability with respect to the solid magnesium compound include one or more selected from saturated hydrocarbon solvents or unsaturated hydrocarbon solvents that do not dissolve the magnesium compound.
Saturated hydrocarbon solvents or unsaturated hydrocarbon solvents are high in safety and industrial versatility, and are specifically linear or branched with a boiling point of 50 to 200 ° C. such as hexane, heptane, decane, and methylheptane. Alicyclic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as cycloaliphatic hydrocarbon compounds, cyclohexane, ethylcyclohexane and decahydronaphthalene, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene and ethylbenzene. Among them, linear aliphatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as hexane, heptane and decane, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene and ethylbenzene are preferable. .

In the solid catalyst component for olefin polymerization used in the present invention, the tetravalent titanium halogen compound used in the first step is not particularly limited, but the following general formula (V)
^{_{Ti (OR 10) r X 4}} -r (V)
(In the formula, R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom, which may be the same as or different from each other, and r represents 0 or 1-3. And a plurality of OR ^{10 s,} which may be the same or different from each other, is preferably one or more compounds selected from the group consisting of titanium halides and alkoxytitanium halide groups.

Examples of the titanium halide include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
Further, as the alkoxy titanium halide, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium Examples thereof include dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, and tri-n-butoxy titanium chloride.
As the tetravalent titanium halogen compound, titanium tetrahalide is preferable, and titanium tetrachloride is more preferable.
These titanium compounds can be used alone or in combination of two or more.

In the first step, the solid catalyst component for olefin polymerization used in the present invention has the following general formula (I):
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and when a plurality of R ¹ are present, they may be the same or different, and R ² and R ³ are 1 to 12 alkyl groups which may be the same or different, and the number j of the substituent R ¹ is 0, 1 or 2, and when j is 2, each R ¹ is the same One or more first internal electron donating compounds selected from aromatic dicarboxylic acid diesters (phthalic diesters or substituted phthalic diesters) represented by: It will be.

In the aromatic dicarboxylic acid diester represented by the general formula (I), R ¹ is a halogen atom or an alkyl group having 1 to 8 carbon atoms.

When R ¹ is a halogen atom, examples of the halogen atom include one or more atoms selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When R ¹ is an alkyl group having 1 to 8 carbon atoms, examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- Selected from butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group One or more of them.

R ¹ is preferably a methyl group, a bromine atom, or a fluorine atom, and more preferably a methyl group or a bromine atom.

In the aromatic dicarboxylic acid diester represented by the general formula (I), R ² and R ³ are alkyl groups having 1 to 12 carbon atoms, and R ² and R ³ may be the same or different from each other. Also good.

  Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n -Hexyl group, isohexyl group, 2,2-dimethylbutyl group, 2,2-dimethylpentyl group, isooctyl group, 2,2-dimethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-dodecyl group. Among them, an ethyl group, an n-butyl group, an isobutyl group, a t-butyl group, a neopentyl group, an isohexyl group, and an isooctyl group can be exemplified, and an ethyl group, an n-propyl group, an n-butyl group, an isobutyl group, and a neopentyl group. It is preferable that

In the aromatic dicarboxylic acid diester represented by the general formula (I), the number j of the substituent R ¹ is 0, 1 or 2, and when a plurality of R ¹ are present (when j is 2), each R ¹ ( Two R ¹ ) may be the same or different.
When j is 0, the compound represented by general formula (I) is a phthalic diester, and when j is 1 or 2, the compound represented by general formula (I) is a substituted phthalic diester.
When j is 1, in the aromatic dicarboxylic acid diester represented by the general formula (I), ^{one in} which R ¹ is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the benzene ring is preferable.
When j is 2, in the aromatic dicarboxylic acid diester represented by the general formula (I), those in which R ¹ is substituted with hydrogen atoms at positions 4 and 5 of the benzene ring are preferred.

  Specific examples of the aromatic dicarboxylic acid diester represented by the general formula (I) include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate , Di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, di-n-hexyl phthalate, ditexyl phthalate, methyl ethyl phthalate, n-propyl phthalate, ethyl isopropyl phthalate, phthalic acid Phthalic acid diesters such as (ethyl) n-butyl, ethyl isobutyl phthalate, (ethyl) n-pentyl phthalate, ethyl isopentyl phthalate, ethyl neopentyl phthalate, (ethyl) n-hexyl phthalate, 4-chlorophthal Diethyl acetate, di-n-propyl 4-chlorophthalate, -Diisopropyl chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-propyl 4-bromophthalate, diisopropyl 4-bromophthalate, di-n 4-bromophthalate Halogen-substituted phthalic acid diesters such as butyl and diisobutyl 4-bromophthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, diisopropyl 4-methylphthalate, di-n-butyl 4-methylphthalate, 4- And alkyl-substituted phthalic acid diesters such as diisobutyl methylphthalate.

  Among the above aromatic dicarboxylic acid diesters, diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, phthalate Di-n-hexyl acid, (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, n-butyl phthalate, ethyl isobutyl phthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate , Diisobutyl 4-methylphthalate, diisobutyl 4-bromophthalate, diisopentyl 4-bromophthalate and dineopentyl 4-bromophthalate, etc., preferably diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, phthalic acid Diisobutyl, phthalic acid (ethyl n-propyl, ethyl isopropyl phthalate, n-butyl phthalate, ethyl isobutyl phthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, diisobutyl 4-methylphthalate, diisobutyl 4-bromophthalate More preferred are diisopentyl 4-bromophthalate and dineopentyl 4-bromophthalate.

  In the solid catalyst component for olefin polymerization used in the present invention, in the first step, a kind selected from a magnesium compound, a tetravalent titanium halogen compound and an aromatic dicarboxylic acid diester represented by the general formula (I) The first internal electron donating compound is brought into contact and reacted, and then washed.

In the first step, the magnesium compound, the tetravalent titanium halogen compound, and the aromatic dicarboxylic acid diester represented by the general formula (I) are brought into contact with each other and reacted in the presence of an inert organic solvent. preferable.
The inert organic solvent is preferably an aromatic hydrocarbon compound which is liquid at normal temperature (20 ° C.) and has a boiling point of 50 to 150 ° C., is liquid at normal temperature and has a boiling point of 50 to 150 ° C. Saturated hydrocarbon compounds are more preferred.
Specific examples of the inert organic solvent include straight chain aliphatic hydrocarbon compounds such as hexane, heptane, and decane, branched aliphatic hydrocarbon compounds such as methylheptane, and alicyclic rings such as cyclohexane, methylcyclohexane, and ethylcyclohexane. 1 type or more chosen from aromatic hydrocarbon compounds, such as a formula hydrocarbon compound, toluene, xylene, and ethylbenzene, etc. are mentioned.
Among the above inert organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150 ° C. improve the activity of the resulting solid catalyst component and improve the stereoregularity of the resulting polymer. Therefore, it is preferable.

  In the solid catalyst component for olefin polymerization used in the present invention, in the first step, the magnesium compound, the tetravalent titanium halogen compound and the aromatic dicarboxylic acid diester represented by the general formula (I) are not appropriately used. Contact can be achieved by mixing in the presence of an active organic solvent.

In the first step, a magnesium compound, a tetravalent titanium halogen compound and an aromatic dicarboxylic acid diester represented by the general formula (I) are contacted and reacted.
0-130 degreeC is preferable, the temperature at the time of the said reaction has more preferable 40-130 degreeC, 30-120 degreeC is further more preferable, 80-120 degreeC is still more preferable. The reaction time is preferably 1 minute or longer, more preferably 10 minutes or longer, further preferably 30 minutes to 6 hours, more preferably 30 minutes to 5 hours, and even more preferably 1 to 4 hours.

  In the first step, prior to the above reaction, the magnesium compound, the tetravalent titanium halogen compound and the aromatic dicarboxylic acid diester represented by the general formula (I) are contacted at a temperature of room temperature or lower, and further 5 minutes to A maturing step of pre-reacting for about 4 hours may be performed.

  In the first step, when a magnesium compound, a tetravalent titanium halogen compound and an aromatic dicarboxylic acid diester represented by the general formula (I) are contacted and reacted, use of the tetravalent titanium halogen compound with respect to 1 mol of the magnesium compound The amount is preferably 0.5 to 100 mol, more preferably 1 to 50 mol, still more preferably 1 to 10 mol.

In the first step, when the magnesium compound, the tetravalent titanium halogen compound and the aromatic dicarboxylic acid diester represented by the general formula (I) are contacted and reacted, the magnesium compound is represented by the general formula (I) with respect to 1 mol of the magnesium compound. The amount of the aromatic dicarboxylic acid diester used is preferably from 0.01 to 10 mol, more preferably from 0.01 to 1 mol, and even more preferably from 0.02 to 0.6 mol. .
Moreover, when using an inert organic solvent at a 1st process, it is preferable that the usage-amount of an inert organic solvent is 0.001-500 mol with respect to 1 mol of magnesium compounds, and 0.5-100 mol More preferably, it is 1.0-20 mol.

In the first step, the contact of each component is preferably performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed.
After completion of the above reaction, the reaction product is allowed to stand after the reaction liquid is removed, and the supernatant liquid is appropriately removed to obtain a wet state (slurry state) or further dried by hot air drying or the like and then subjected to a washing treatment. Is preferred.

After completion of the above reaction, the reaction solution is allowed to stand, and the supernatant is appropriately removed, and then the resulting reaction product is washed.
The cleaning treatment is usually performed using a cleaning solution.
Examples of the cleaning liquid include those similar to the inert organic solvent used as appropriate in the first step, and are liquid at room temperature such as hexane, heptane, decane, etc., and have a straight chain having a boiling point of 50 to 150 ° C. Aliphatic hydrocarbon compounds, liquids at normal temperatures such as methylcyclohexane and ethylcyclohexane, and cyclic aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C., toluene, xylene, ethylbenzene, orthodichlorobenzene, etc. at normal temperatures One or more selected from liquid and aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C. are preferred.
By using the cleaning liquid, by-products and impurities can be easily dissolved and removed from the reaction product.

  In the solid catalyst component for olefin polymerization used in the present invention, the washing treatment in the first step is preferably performed at a temperature of 0 to 120 ° C, more preferably at a temperature of 0 to 110 ° C. More preferably, the reaction is performed at a temperature of 30 to 110 ° C, more preferably 50 to 110 ° C, and still more preferably 50 to 100 ° C.

In the solid catalyst component for olefin polymerization used in the present invention, the washing treatment is performed by adding a desired amount of washing liquid to the reaction product and stirring, and then by a filtration method (filtration method) or a decantation method. It is preferable to carry out by removing the liquid phase.
Further, as will be described later, when the number of times of washing is a plurality of times (two or more times), the reaction product can be directly subjected to the reaction in the next step without removing the lastly added washing solution. .

In the first step, the amount of the cleaning liquid used is preferably 1 to 500 mL, more preferably 3 to 200 mL, and even more preferably 5 to 100 mL per 1 g of the reaction product.
The number of washings may be multiple, and the number of washings is preferably 1-20, more preferably 2-15, and even more preferably 2-10.
Even when the number of times of cleaning is plural, it is preferable to use the amount of the cleaning liquid described above for each cleaning.
In the solid catalyst component for olefin polymerization used in the present invention, each component is contacted and reacted in the first step, and then subjected to a washing treatment, whereby unreacted raw material components and reactions remaining in the reaction product. Impurities of by-products (alkoxy titanium halide, titanium tetrachloride-carboxylic acid complex, etc.) can be removed.

  In the solid catalyst component for olefin polymerization used in the present invention, the first step includes a mode in which post-treatment is appropriately performed after the washing treatment. In the method for producing a solid catalyst component for olefin polymerization according to the present invention, after the above-mentioned post-treatment in the first step, the obtained product may be subjected to the second step described below. It is preferable to perform the second step as it is without performing post-treatment or the like.

  After completion of the reaction in the first step, the suspension after the washing treatment may be allowed to stand, and the supernatant may be removed to obtain a wet state (slurry state), or may be dried by hot air drying or the like. The second step may be applied in the state of a suspension. When the second step is applied in the state of a suspension, the drying process can be omitted and the addition of an inert organic solvent in the second step can be omitted.

[Second step]
The solid catalyst component for olefin polymerization used in the present invention is subjected to the first step, and a tetravalent titanium halogen compound and one or more second internal electron donating compounds are obtained with respect to the obtained product. Are contacted and reacted, followed by a second step of washing.

  In the solid catalyst component for olefin polymerization used in the present invention, the tetravalent titanium halogen compound used in the second step is the same as the tetravalent titanium halogen compound used in the first step. be able to.

In the solid catalyst component for olefin polymerization used in the present invention, the second internal electron donating compound used in the second step is selected from silicon-free organic compounds having two or more electron donating sites. Suitably one or more. Examples of the electron donating moiety include a hydroxyl group (—OH), a carbonyl group (> C═O), an ether bond (—OR), an amino group (—NH ₂ , —NHR, —NHRR ′), a cyano group (—CN). ), Isocyanate groups (—N═C═O), amide bonds (—C (═O) NH—, —C (═O) NR—). The carbonyl group (> C═O) includes an aldehyde group (—C (═O) H), a carboxy group (—C (═O) OH), a keto group (—C (═O) R), a carbonate group ( —O—C (═O) O—), ester bond (—C (═O) O—), urethane bond (—NH—C (═O) O—) and the like are included.
Among these, esters such as polycarboxylic acid esters and ether compounds such as diethers and ether carbonates are preferable. These internal electron donating compounds can be used alone or in combination of two or more.
More specifically, as the second internal electron donating compound, for example, (1) the same aromatic dicarboxylic acid diester as the first internal electron donating compound, (2) the fragrance represented by the general formula (I) Aromatic dicarboxylic acid diester different from the first internal electron-donating compound among the group dicarboxylic acid diester, (3) alkyl-substituted malonic acid diester, (4) cycloalkane dicarboxylic acid ester, (5) cycloalkene dicarboxylic acid diester , (6) diethers, (7) ether carboxylic acids, and (8) ether carbonates.

  Examples of polycarboxylic acid esters used in the second step include carboxylic acid diesters and substituted carboxylic acid diesters in which some of the hydrogen atoms bonded to the carbon atoms forming the molecular skeleton are substituted with other groups. it can.

Specific examples of the carboxylic acid diester include aromatic dicarboxylic acid diesters such as phthalic acid diester and isophthalic acid diester, succinic acid diester, maleic acid diester, malonic acid diester, and glutaric acid diester, Examples include cycloalkane dicarboxylic acid diesters and cycloalkene dicarboxylic acid diester alicyclic dicarboxylic acid diesters.
Further, as the substituted carboxylic acid diester, specifically, a halogen-substituted carboxylic acid diester in which a hydrogen atom is substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and a hydrogen atom has 1 to 8 carbon atoms. And alkyl-substituted carboxylic acid diesters substituted with an alkyl group, and halogenated alkyl-substituted carboxylic acid diesters in which a hydrogen atom is substituted with a halogen atom and an alkyl group having 1 to 8 carbon atoms.
Specific examples of the substituted carboxylic acid diester include a cycloalkanedicarboxylic acid diester having a substituent, in which a part of hydrogen atoms of the cycloalkyl group constituting the cycloalkanedicarboxylic acid diester is substituted with an alkyl group, substituted malon Examples include acid diesters and alkyl-substituted maleic acid diesters.

  When an aromatic dicarboxylic acid diester is used as the second internal electron donating compound, the aromatic dicarboxylic acid diester should be the same as the aromatic dicarboxylic acid diester defined by the general formula (I) described above. Can do.

  When succinic acid diester is used as the second internal electron donating compound, examples of succinic acid diester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diethyl 2,3-diisopropyl succinate, and the like. Diethyl or diethyl 2,3-diisopropyl succinate is preferred.

When maleic diester is used as the second internal electron donating compound, maleic diester includes diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, diisobutyl maleate. , Di-n-pentyl maleate, dineopentyl maleate, dihexyl maleate, dioctyl maleate, and the like. Among these, diethyl maleate, di-n-butyl maleate, and diisobutyl maleate are preferred. .
When an alkyl-substituted maleic diester is used as the second internal electron donating compound, the alkyl-substituted maleic diester includes diethyl isopropyl bromomaleate, diethyl butyl bromomaleate, diethyl isobutyl bromomaleate, diethyl diisopropylmaleate, Diethyl dibutyl maleate, diethyl diisobutyl maleate, diethyl diisopentyl maleate, diethyl isopropyl isobutyl maleate, dimethyl isopropyl isopentyl maleate, diethyl (3-chloro-n-propyl) maleate, bis (3-bromo-n -Propyl) diethyl maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate, etc., among them, dibutyl dimethyl maleate, dibutyl Chirumarein dibutyl and diisobutyl diethyl maleate are preferred.

When malonic acid diester is used as the second internal electron donating compound, malonic acid diester includes dimethyl malonate, diethyl malonate, di-n-propyl malonate, diisopropyl malonate, di-n-butyl malonate. , Diisobutyl malonate, dineopentyl malonate and the like. Among these, dimethyl malonate, diethyl malonate or diisobutyl malonate are preferred.
Further, as the second internal electron donating compound, a substituted malonic acid diester is suitable.
When a substituted malonic acid diester is used as the second internal electron donating compound, examples of the substituted malonic acid diester include alkyl-substituted malonic acid diesters, halogen-substituted malonic acid diesters, halogenated alkyl-substituted malonic acid diesters, and the like. Of these, alkyl-substituted malonic acid diesters and halogen-substituted malonic acid diesters are preferred, and alkyl-substituted malonic acid diesters are more preferred.

  The alkyl-substituted malonic acid diester is preferably a dialkyl malonic acid diester or an alkylidene malonic acid diester. More preferred are alkylidene malonic acid diesters such as dimethyl malonate and diethyl benzylidene malonate.

  When cycloalkane dicarboxylic acid diester is used as the second internal electron donating compound, cycloalkane dicarboxylic acid diester includes cyclopentane-1,2-dicarboxylic acid diester, cyclopentane-1,3-dicarboxylic acid diester, cyclohexane. -1,2-dicarboxylic acid diester, cyclohexane-1,3-dicarboxylic acid diester, cycloheptane-1,2-dicarboxylic acid diester, cycloheptane-1,2-dicarboxylic acid diester, cyclooctane-1,2-dicarboxylic acid Diester, cyclooctane-1,3-dicarboxylic acid diester, cyclononane-1,2-dicarboxylic acid diester, cyclononane-1,3-dicarboxylic acid diester, cyclodecane-1,2-dicarboxylic acid diester, norbornane- , 3-dicarboxylic acid diesters.

  In addition, as the second internal electron donating compound, a cycloalkanedicarboxylic acid diester having a substituent in which a part of hydrogen atoms of the cycloalkyl group constituting the cycloalkanedicarboxylic acid diester is substituted with an alkyl group or the like is used. In this case, the cycloalkanedicarboxylic acid diester having the substituent includes diethyl 3-methylcyclohexane-1,2-dicarboxylate, diethyl 4-methylcyclohexane-1,2-dicarboxylate, 5-methylcyclohexane-1,2 -Diethyl dicarboxylate, diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate, di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylate and the like.

  When cycloalkene dicarboxylic acid diester is used as the second internal electron donating compound, cyclopentene dicarboxylic acid diester, cyclohexene dicarboxylic acid diester, cycloheptene dicarboxylic acid diester, cyclooctene dicarboxylic acid diester, norbornene dicarboxylic acid diester, dicyclopentadiene Examples include dicarboxylic acid diester, cyclodecene dicarboxylic acid diester, biphenyl dicarboxylic acid diester, and the like. Specifically, 1-cyclohexene-1,2-dicarboxylic acid diester, 4-cyclohexene-1,2-dicarboxylic acid diester, and norbornene dicarboxylic acid. One or more selected from acid diesters are preferred.

When diethers are used as the second internal electron donating compound, the diethers are represented by the following general formula (VI)
R ¹¹ _k H _(3-k) C—O— (CR ¹² R ¹³ ) _m —O—C R ¹⁴ _n H _(3-n) (VI)
(In the general formula ^{(VI), R 11} and ^{R 14} is an organic group having a halogen atom or a C 1-20, it may be the being the same or ^{different, R 12} and ^{R 13} are hydrogen An atom, an oxygen atom, a sulfur atom, a halogen atom or an organic group having 1 to 20 carbon atoms, which may be the same as or different from each other. , A chlorine atom, a bromine atom, an iodine atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a boron atom may be contained, and there are a plurality of organic groups having 1 to 20 carbon atoms. In this case, a plurality of organic groups may be bonded to each other to form a ring, k is an integer of 0 to 3, and when k is an integer of 2 or more, a plurality of R ¹¹ may be the same as each other. May be different, m is an integer from 1 to 10 Ri, when m is an integer of 2 or more, each of R ¹² and R ¹³ there exist a plurality may be the same or different, n is an integer of 0 to 3, when n is an integer of 2 or more A plurality of R ¹⁴ may be the same as or different from each other.)
The compound represented by these can be used.
In the compound represented by the general formula (VI), when R ¹¹ or R ¹⁴ is a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom, a chlorine atom or a bromine atom. It is.

When R ¹¹ or R ¹⁴ is an organic group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, isopropyl group, isobutyl group, n-propyl group, n-butyl group, t-butyl group, hexyl Group, octyl group, cyclopentyl group, cyclohexyl group, and phenyl group. Preferred are methyl group and ethyl group.

In the compound represented by the general formula (VI), when a plurality of organic groups having 1 to 20 carbon atoms are present, the plurality of organic groups may be bonded to each other to form a ring. In this case, as the plurality of organic groups constituting the ring, (1) R ^{11 to} each other (when k is 2 or more), (2) R ^{14 to} each other (when n is 2 or more), (3) R ¹² (when m is 2 or more), (4) R ¹³ (when m is 2 or more), (5) R ¹¹ and R ¹² , (6) R ¹¹ and R ¹³ , (7) R ¹¹ and R ¹⁴ , (8) R ¹² and R ¹³ , (9) R ¹² and R ¹⁴ , (10) R ¹³ and R ¹⁴ , and (8) R ¹² and R ¹³ The combination of R ¹² and R ¹³ is preferably bonded to each other to form a fluorene ring or the like.

  Specific examples of the compound represented by the general formula (VI) include 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, and 2-isopropyl-2. Isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane or 9,9-bis (methoxymethyl) fluorene 9,9-bis (ethoxymethyl) fluorene, 9-methoxy-9-ethoxymethylfluorene, 9,9-bis (methoxymethyl) -2,7-dimethylfluorene, 9,9-bis (methoxymethyl) -2 , 6-diisopropylfluorene, 9,9-bis (methoxymethyl) -3,6-diisobutylfluorene, 9, 9-bis (methoxymethyl) -2-isobutyl-7-isopropylfluorene, 9,9-bis (methoxymethyl) -2,7-dichlorofluorene, 9,9-bis (methoxymethyl) -2-chloro-7- Examples include isopropyl fluorene, and preferably 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3- Examples include dimethoxypropane, 3,3-bis (methoxymethyl) -2,6-dimethylheptane, 9,9-bis (methoxymethyl) fluorene, and more preferably 2,2-diisobutyl-1,3-dimethoxy. Propane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 3,3-bis (methoxy Methyl) -2,6-dimethyl heptane, one or more selected from 9,9-bis (methoxymethyl) fluorene and the like. Among these, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-bis (methoxymethyl) fluorene are preferable.

In the compound represented by the general formula (VI), k is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. When k is an integer of 2 or more, a plurality of R ¹¹ may be the same as or different from each other.
In the compound represented by the general formula (VI), m is an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably an integer of 1 to 6. When m is an integer of 2 or more, a plurality of R ¹² and R ¹³ may be the same as or different from each other.
In the compound represented by the general formula (VI), n is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1. When n is an integer of 2 or more, a plurality of R ¹⁴ may be the same as or different from each other.

When an ether carbonate is used as the second internal electron donating compound, the ether carbonate is represented by the following general formula (VII)
R ¹⁵ —O—C (═O) —O—Z—OR ¹⁶ (VII)
(In the general formula (VII), R ¹⁵ and R ¹⁶ are a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, and a linear alkenyl having 3 to 20 carbon atoms. Group or branched alkenyl group, C1-C20 linear halogen-substituted alkyl group, C3-C20 branched halogen-substituted alkyl group, C2-C20 linear halogen-substituted alkenyl group, C3-C3 20 branched halogen-substituted alkenyl groups, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, halogen-substituted cycloalkyl groups having 3 to 20 carbon atoms, and halogen-substituted cycloalkenyl groups having 3 to 20 carbon atoms Groups, aromatic hydrocarbon groups having 6 to 24 carbon atoms, halogen-substituted aromatic hydrocarbon groups having 6 to 24 carbon atoms, and nitrogen atom-containing hydrocarbon groups having 2 to 24 carbon atoms whose bond ends are carbon atoms (however, And an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms in which the bond terminal is a carbon atom (excluding those in which the bond terminal is a carbonyl group), Or a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms in which the bond terminal is a carbon atom (excluding those in which the bond terminal is a C═P group), and R ¹⁵ and R ¹⁶ are the same or different. Z represents a bonding group bonded via a carbon atom or a carbon chain.), And a compound represented by

In the compound represented by the general formula (VII), when R ¹⁵ or R ¹⁶ is a linear alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, An n-pentyl group, an n-hexyl group, an n-pentyl group, an n-octyl group, an n-nonyl group, an n-decyl group and the like can be mentioned, and a linear alkyl group having 1 to 12 carbon atoms is preferable. .

When R ¹⁵ or R ¹⁶ is a branched alkyl group having 3 to 20 carbon atoms, for example, an alkyl group having a secondary carbon or a tertiary carbon such as an isopropyl group, an isobutyl group, a t-butyl group, an isopentyl group, or a neopentyl group Preferably, a C3-C12 branched alkyl group is mentioned.

When R ¹⁵ or R ¹⁶ is a linear alkenyl group having 3 to 20 carbon atoms, for example, allyl group, 3-butenyl group, 4-hexenyl group, 5-hexenyl group, 7-octenyl group, 10-dodecenyl group Preferably, a C3-C12 linear alkenyl group is mentioned.

When R ¹⁵ or R ¹⁶ is a branched alkenyl group having 3 to 20 carbon atoms, examples thereof include an isopropenyl group, an isobutenyl group, an isopentenyl group, a 2-ethyl-3-hexenyl group, and preferably 3 carbon atoms. -12 branched alkenyl groups.

When R ¹⁵ or R ¹⁶ is a linear halogen-substituted alkyl group having 1 to 20 carbon atoms, for example, a halogenated methyl group, a halogenated ethyl group, a halogenated n-propyl group, a halogenated n-butyl group, a halogen N-pentyl group, halogenated n-hexyl group, halogenated n-pentyl group, halogenated n-octyl group, halogenated nonyl group, halogenated decyl group, halogen-substituted undecyl group, halogen-substituted dodecyl group and the like. Preferably, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms is used.

When R ¹⁵ or R ¹⁶ is a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, examples thereof include a halogenated isopropyl group, a halogenated isobutyl group, a halogenated 2-ethylhexyl group, a halogenated neopentyl group, and the like. Includes a branched halogen-substituted alkyl group having 3 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, for example, a 2-halogenated vinyl group, a 3-halogenated allyl group, a 3-halogenated-2-butenyl group, 4 -Halogenated-3-butenyl group, perhalogenated-2-butenyl group, 6-halogenated-4-hexenyl group, 3-trihalogenated methyl-2-propenyl group, etc., preferably 2 carbon atoms ˜12 halogen-substituted alkenyl groups.

When R ¹⁵ or R ¹⁶ is a branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, for example, 3-trihalogenated-2-butenyl group, 2-pentahalogenated ethyl-3-hexenyl group, 6-halogenated group A -3-ethyl-4-hexenyl group, a 3-halogenated isobutenyl group, and the like are preferable, and a branched halogen-substituted alkenyl group having 3 to 12 carbon atoms is preferable.

When R ¹⁵ or R ¹⁶ is a cycloalkyl group having 3 to 20 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, tetramethylcyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group , A cyclononyl group, a cyclodecyl group, a butylcyclopentyl group, and the like, preferably a cycloalkyl group having 3 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a cycloalkenyl group having 3 to 20 carbon atoms, examples thereof include a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a norbornene group, and the like, preferably 3 carbon atoms ˜12 cycloalkenyl groups.

When R ¹⁵ or R ¹⁶ is a halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, for example, a halogen-substituted cyclopropyl group, a halogen-substituted cyclobutyl group, a halogen-substituted cyclopentyl group, a halogen-substituted trimethylcyclopentyl group, a halogen-substituted cyclohexyl group, Examples include a halogen-substituted methylcyclohexyl group, a halogen-substituted cycloheptyl group, a halogen-substituted cyclooctyl group, a halogen-substituted cyclononyl group, a halogen-substituted cyclodecyl group, and a halogen-substituted butylcyclopentyl group, preferably a halogen-substituted cyclohexane having 3 to 12 carbon atoms. An alkyl group is mentioned.

When R ¹⁵ or R ¹⁶ is a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, for example, a halogen-substituted cyclopropenyl group, a halogen-substituted cyclobutenyl group, a halogen-substituted cyclopentenyl group, a halogen-substituted trimethylcyclopentenyl group, a halogen-substituted cycloalkenyl group A hexenyl group, a halogen-substituted methylcyclohexenyl group, a halogen-substituted cycloheptenyl group, a halogen-substituted cyclooctenyl group, a halogen-substituted cyclononenyl group, a halogen-substituted cyclodecenyl group, a halogen-substituted butylcyclopentenyl group, and the like, preferably a halogen having 3 to 12 carbon atoms A substituted cycloalkenyl group may be mentioned.

When R ¹⁵ or R ¹⁶ is an aromatic hydrocarbon group having 6 to 24 carbon atoms, for example, phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, benzyl group, 1-phenylethyl group, 2-phenyl Examples include ethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group, 1,8-dimethylnaphthyl group, etc. A C6-C12 aromatic hydrocarbon group is mentioned.

When R ¹⁵ or R ¹⁶ is a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogenated phenyl group, a halogenated methylphenyl group, a trihalogenated methylphenyl group, a perhalogenated benzyl group, or a perhalogenated group. A phenyl group, a 2-phenyl-2-halogenated ethyl group, a perhalogenated naphthyl group, a 4-phenyl-2,3-dihalogenated butyl group, and the like, preferably a halogen-substituted aromatic carbon atom having 6 to 12 carbon atoms A hydrogen group is mentioned.

In the compound represented by the general formula (VII), when R ¹⁵ or R ¹⁶ is a group containing a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Preferably a fluorine atom, a chlorine atom, or a bromine atom is mentioned.

In addition, when R ¹⁵ or R ¹⁶ is a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms in which the bond terminal is a carbon atom (excluding those in which the bond terminal is a C═P group), for example, dimethyl Dialkylphosphinoalkyl groups such as phosphinomethyl group, dibutylphosphinomethyl group, dicyclohexylphosphinomethyl group, dimethylphosphinoethyl group, dibutylphosphinoethyl group, dicyclohexylphosphinoethyl group, diphenylphosphinomethyl group, ditolyl Examples include diarylphosphinoalkyl groups such as phosphinomethyl groups, phosphino group-substituted aryl groups such as dimethylphosphinophenyl groups, and diethylphosphinophenyl groups, preferably phosphorus-containing hydrocarbon groups having 2 to 12 carbon atoms. It is done.

Note that the binding end of R ¹⁵ or R ^16, in the compound represented by formula (VII), an atom or a group of the oxygen atom side ends R ¹⁵ or R ¹⁶ is attached.

R ¹⁵ includes a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, and 1 to 1 carbon atom. 12 straight-chain halogen-substituted alkyl groups, branched halogen-substituted alkyl groups having 3 to 12 carbon atoms, straight-chain halogen-substituted alkenyl groups or branched halogen-substituted alkenyl groups having 3 to 12 carbon atoms, and cycloalkyl having 3 to 12 carbon atoms Group, a C3-C12 cycloalkenyl group, a C3-C12 halogen-substituted cycloalkyl group, a C3-C12 halogen-substituted cycloalkenyl group, or a C6-C12 aromatic hydrocarbon group is preferable. ,
C1-C12 linear alkyl group, C3-C12 branched alkyl group, vinyl group, C3-C12 linear alkenyl group or branched alkenyl group, C1-C12 linear A halogen-substituted alkyl group, a branched halogen-substituted alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. More preferred,
A linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms are more preferable.

R ¹⁶ includes a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms whose bonding terminal is —CH ₂ —, a vinyl group, and a linear alkenyl group having 3 to 12 carbon atoms. A branched alkenyl group having 3 to 12 carbon atoms whose bonding end is —CH ₂ —, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, and a branching group having 3 to 12 carbon atoms whose bonding end is —CH ₂ —. halogen-substituted alkyl group, linear halogen-substituted alkenyl group having 3 to 12 carbon atoms, bond terminal -CH ₂ - in which the branch halogen substituted alkenyl group having 3 to 12 carbon atoms, bond terminal -CH ₂ - carbon is number 4-12 cycloalkyl group, coupling terminal -CH ₂ - in which cycloalkenyl group having 4 to 12 carbon atoms, bond terminal -CH ₂ - in which halogen substituted cycloalkyl group having 4 to 12 carbon atoms, bond The end is- H ₂ - a is halogen-substituted cycloalkenyl group having 4 to 12 carbon atoms or a bond terminal -CH _2, - preferably an aromatic hydrocarbon group having 7 to 12 carbon atoms is, having 1 to 12 carbon atoms linear alkyl group, coupling terminal -CH ₂ - in which branched alkyl group having 3 to 12 carbon atoms, bond terminal -CH ₂ - in which branched alkenyl group having 3 to 12 carbon atoms, is bound terminal -CH ₂ - is linear halogen-substituted alkyl group having 1 to 12 carbon atoms, bond terminal -CH ₂ - in which branched halogen substituted alkyl group having 3 to 12 carbon atoms, bond terminal -CH ₂ - of 3 to 12 carbon atoms is branched halogen substituted alkenyl group, coupling terminal -CH ₂ - in which the cycloalkyl group having 4 to 12 carbon atoms, bond terminal -CH ₂ - in which cycloalkenyl group having 4 to 12 carbon atoms, bonds end -CH ₂ -Charcoal A halogen-substituted cycloalkyl group having 4 to 12 prime atoms, a halogen-substituted cycloalkenyl group having 4 to 12 carbon atoms whose bonding end is —CH ₂ —, or an aromatic group having 7 to 12 carbon atoms whose bonding end is —CH ₂ —. more preferably a hydrocarbon group, a linear hydrocarbon group having 1 to 12 carbon atoms, bond terminal -CH ₂ - in which branched alkyl group having 3 to 12 carbon atoms or a bond terminus, are -CH ₂ - is An aromatic group hydrocarbon group having 7 to 12 carbon atoms is more preferable.

Note that the binding end of R ^16, the compound represented by formula (VII), means an oxygen atom side ends R ¹⁶ is bonded.

Examples of the combination of R ¹⁵ and R ¹⁶ include a combination of preferable groups among the groups described above, and a more preferable combination is preferable.

In the compound represented by the general formula (VII), Z is a divalent linking group that binds a carbonate group and an ether group (OR ¹⁶ group), and is a linking group that is bonded via a carbon atom or a carbon chain. Yes, there can be mentioned, for example, a bonding group in which two oxygen atoms to which Z is bonded are bonded by a carbon chain, and the carbon chain is preferably a bonding group composed of two carbon atoms. .

  Z is a linear alkylene group having 1 to 20 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, a vinylene group, a linear alkenylene group having 3 to 20 carbon atoms or a branched alkenylene group, and 1 to 20 carbon atoms. A linear halogen-substituted alkylene group, a branched halogen-substituted alkylene group having 3 to 20 carbon atoms, a linear halogen-substituted alkenylene group or branched halogen-substituted alkenylene group having 3 to 20 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, C3-C20 cycloalkenylene group, C3-C20 halogen-substituted cycloalkylene group, C3-C20 halogen-substituted cycloalkenylene group, C6-C24 aromatic hydrocarbon group, C6-C6 24 halogen-substituted aromatic hydrocarbon groups, nitrogen atom-containing hydrocarbon groups having 1 to 24 carbon atoms, oxygen atoms-containing hydrocarbon groups having 1 to 24 carbon atoms, and It is preferably a phosphorus-containing hydrocarbon group having 1 to 24 carbon atoms.

  Z is an ethylene group having 2 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, a vinylene group, a linear alkenylene group having 3 to 12 carbon atoms or a branched alkenylene group, or a linear halogen substitution having 2 to 12 carbon atoms. Alkylene group, branched halogen-substituted alkylene group having 3 to 12 carbon atoms, linear halogen-substituted alkenylene group or branched halogen-substituted alkenylene group having 3 to 12 carbon atoms, cycloalkylene group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms A cycloalkenylene group having 3 to 12 carbon atoms, a halogen-substituted cycloalkenylene group having 3 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a halogen-substituted aromatic having 6 to 12 carbon atoms Group hydrocarbon group, a C2-C12 nitrogen atom-containing hydrocarbon group, a C2-C12 oxygen atom-containing hydrocarbon group, or a C2-C1 The phosphorus-containing hydrocarbon group is particularly preferably a bidentate bonding group selected from an ethylene group having 2 carbon atoms and a branched alkylene group having 3 to 12 carbon atoms. The bonding group in (1) means that two oxygen atoms to which Z is bonded are bonded by a carbon chain, and the carbon chain is composed of two carbon atoms).

When Z is a linear alkylene group having 1 to 20 carbon atoms, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group , Undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group and the like, and a linear alkylene group having 2 to 12 carbon atoms is preferable. More preferably, an ethylene group is mentioned.
In the case of the branched alkylene group having 3 to 20 carbon atoms of Z, for example, 1-methylethylene group, 2-methyltrimethylene group, 2-methyltetramethylene group, 2-methylpentamethylene group, 3-methylhexamethylene group 4-methylheptamethylene group, 4-methyloctamethylene group, 5-methylnonamethylene group, 5-methyldecamethylene group, 6-methylundecamethylene group, 7-methyldodecamethylene group, 7-methyltridecamethylene group Groups, preferably branched alkylene groups having 3 to 12 carbon atoms, more preferably 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group.

  When Z is a linear alkenylene group having 3 to 20 carbon atoms, examples thereof include a propenylene group, a butenylene group, a hexenylene group, an octenylene group, and an octadecenylene group, and preferably a linear chain having 3 to 12 carbon atoms. Alkenylene group is mentioned.

  When Z is a branched alkenylene group having 3 to 20 carbon atoms, for example, isopropenylene group, 1-ethylethenylene group, 2-methylpropenylene group, 2,2-dimethylbutenylene group, 3-methyl-2- A butenylene group, a 3-ethyl-2-butenylene group, a 2-methyloctenylene group, a 2,4-dimethyl-2-butenylene group, and the like. Preferably, the linking part is an ethenylene group having 3 to 12 carbon atoms. A branched alkenylene group is mentioned, More preferably, an isopropenylene group and 1-ethylethenylene group are mentioned.

  When Z is a linear halogen-substituted alkylene group having 1 to 20 carbon atoms, examples thereof include a dichloromethylene group, a chloromethylene group, a dichloromethylene group, a tetrachloroethylene group, and the like, and preferably a straight chain having 3 to 12 carbon atoms. A chain halogen-substituted alkylene group is mentioned, More preferably, a chloroethylene group, a fluoroethylene group, a dichloroethylene group, a difluoroethylene group, and a tetrafluoroethylene group are mentioned.

  When Z is a branched halogen-substituted alkylene group having 1 to 20 carbon atoms, for example, 1,2-bischloromethylethylene group, 2,2-bis (chloromethyl) propylene group, 1,2-bisdichloromethylethylene group 1,2-bis (trichloromethyl) ethylene group, 2,2-dichloropropylene group, 1,1,2,2-tetrachloroethylene group, 1-trifluoromethylethylene group, 1-pentafluorophenylethylene group, etc. Preferably a branched halogen-substituted alkylene group having 3 to 12 carbon atoms, more preferably 1-chloroethylethylene group, 1-trifluoromethylethylene group, 1,2-bis (chloromethyl) ethylene group. Is mentioned.

  When Z is a linear halogen-substituted alkenylene group having 1 to 20 carbon atoms, for example, a dichloroethenylene group, a difluoroethenylene group, a 3,3-dichloropropenylene group, a 1,2-difluoropropenylene group, etc. Preferably, a C3-C12 linear halogen-substituted alkenylene group is mentioned, More preferably, a dichloro ethenylene group and a difluoro ethenylene group are mentioned.

  When Z is a branched halogen-substituted alkylene group having 1 to 20 carbon atoms, for example, 3,4-dichloro-1,2-butylene group, 2,2-dichloro-1,3-butylene group, 1,2-difluoro -1,2-propylene group and the like, preferably a branched halogen-substituted alkylene group having 3 to 12 carbon atoms, more preferably a chloromethylethenylene group, a trifluoromethylethenylene group, 3,4 -Dichloro-1,2-butenylene group.

  When Z is a cycloalkylene group having 3 to 20 carbon atoms, for example, a cyclopentylene group, a cyclohexylene group, a cyclopropylene group, a 2-methylcyclopropylene group, a cyclobutylene group, a 2,2-dimethylcyclobutylene group, 2,3-dimethylcyclopentylene group, 1,3,3-trimethylcyclohexylene group, cyclooctylene group and the like can be mentioned, preferably a cycloalkylene group having 3 to 12 carbon atoms, more preferably, A 1,2-cycloalkylene group or a hydrocarbon group-substituted-1,2-cycloalkylene group may be mentioned.

  When Z is a C3-C20 cycloalkenylene group, for example, cyclopentenylene group, 2,4-cyclopentadienylene group, cyclohexenylene group, 1,4-cyclohexadienylene group, cycloheptene group, Examples thereof include a tenylene group, a methylcyclopentenylene group, a methylcyclohexenylene group, a methylcycloheptenylene group, a dicyclodecylene group, and a tricyclodecylene group. Preferably, a C3-C12 cycloalkenylene group is used. More preferably, a 1,2-cycloalkenylene group or a hydrocarbon-substituted-1,2-cycloalkenylene group is mentioned.

  When Z is a halogen-substituted cycloalkylene group having 3 to 20 carbon atoms, for example, 3-chloro-1,2-cyclopentylene group, 3,4,5,6-tetrachloro-1,2-cyclohexylene group 3,3-dichloro-1,2-cyclopropylene group, 2-chloromethylcyclopropylene group, 3,4-dichloro-1,2-cyclobutylene group, 3,3-bis (dichloromethyl) -1,2 -Cyclobutylene group, 2,3-bis (dichloromethyl) cyclopentylene group, 1,3,3-tris (fluoromethyl) -1,2-cyclohexylene group, 3-trichloromethyl-1,2-cyclooctyl For example, a halogen-substituted cycloalkylene group having 3 to 12 carbon atoms.

  When Z is a halogen-substituted cycloalkenylene group having 3 to 20 carbon atoms, for example, 5-chloro-1,2-cyclo-4-hexenylene group, 3,3,4,4-tetrafluoro-1,2-cyclo -6-octenylene group etc. are mentioned, Preferably, a C3-C12 halogen substituted cycloalkenylene group is mentioned.

  When Z is an aromatic hydrocarbon group having 6 to 24 carbon atoms, for example, 1,2-phenylene, 3-methyl-1,2-phenylene, 3,6-dimethyl-1,2-phenylene, 1,2 -Naphthylene, 2,3-naphthylene, 5-methyl-1,2-naphthylene, 9,10-phenanthrylene, 1,2-anthracenylene and the like, preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Can be mentioned.

  When Z is a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, for example, 3-chloro-1,2-phenylene, 3-chloromethyl-1,2-phenylene, 3,6-dichloro-1, 2-phenylene, 3,6-dichloro-4,5-dimethyl-1,2-phenylene, 3-chloro-1,2-naphthylene, 3-fluoro-1,2-naphthylene, 3,6-dichloro-1, 2-phenylene, 3,6-difluoro-1,2-phenylene, 3,6-dibromo-1,2-phenylene, 1-chloro-2,3-naphthylene, 5-chloro-1,2-naphthylene, 2, Examples include 6-dichloro-9,10-phenanthrylene, 5,6-dichloro-1,2-anthracenylene, 5,6-difluoro-1,2-anthracenylene, and preferably halogen substitution having 6 to 12 carbon atoms. It includes aromatic hydrocarbon groups.

  When Z is a nitrogen atom-containing hydrocarbon group having 1 to 24 carbon atoms, for example, 1-dimethylaminoethylene group, 1,2-bisdimethylminoethylene group, 1-diethylaminoethylene group, 2-diethylamino-1,3 -Propylene group, 2-ethylamino-1,3-propylene group, 4-dimethylamino-1,2-phenylene group, 4,5-bis (dimethylamino) phenylene group, etc., preferably 2 carbon atoms The nitrogen atom containing hydrocarbon group of -12 is mentioned.

  When Z is an oxygen atom-containing hydrocarbon group having 1 to 24 carbon atoms, for example, 1-methoxyethylene group, 2,2-dimethoxy-1,3-propanylene group, 2-ethoxy-1,3-propanylene group, 2-t-butoxy-1,3-propanylene group, 2,3-dimethoxy-2,3-butylene group, 4-methoxy-1,2-phenylene group and the like are preferable, preferably having 2 to 12 carbon atoms. An oxygen atom containing hydrocarbon group is mentioned.

  When Z is a phosphorus-containing hydrocarbon group having 1 to 24 carbon atoms, for example, 1-dimethylphosphinoethylene group, 2,2-bis (dimethylphosphino) -1,3-propanylene group, 2-diethylphosphino -1,3-propanylene group, 2-t-butoxymethylphosphino-1,3-propanylene group, 2,3-bis (diphenylphosphino) -2,3-butylene group, 4-methylphosphate-1,2 -A phenylene group etc. are mentioned, Preferably, a C1-C12 phosphorus containing hydrocarbon group is mentioned.

  In addition, when Z is a cyclic group such as a cycloalkylene group, a cycloalkenylene group, a halogen-substituted cycloalkylene group, a halogen-substituted cycloalkenylene group, an aromatic hydrocarbon group or a halogen-substituted aromatic hydrocarbon group, Z is bonded. A bonding group in which two oxygen atoms are bonded by a carbon chain, and the carbon chain is composed of two carbon atoms, is an adjacent two carbon chains in a carbon chain constituting a ring, This means that the Z is a carbon chain between two oxygen atoms to which Z is bonded.

  As specific examples of the compound represented by the general formula (VII), (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate, and (2-ethoxyethyl) phenyl carbonate are particularly preferable.

  As the second internal electron donating compound, in particular, diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dimethyl diisobutyl malonate, diethyl diisobutyl malonate, benzylidene malonic acid One or more selected from dimethyl, diethyl benzylidenemalonate, isopentylisoptyl 1,3-dimethoxypropane, diisobutyl 1,3-dimethoxypropane, 9,9-dimethoxyfluorene, ethoxyethyl ethyl carbonate and methoxyethyl ethyl carbonate are preferred.

As a combination of the first internal electron donating compound and the second internal electron donating compound, any combination of (1) to (5) in Table 1 below is preferable.

  When a combination of any one of (1) to (5) above is used as a combination of the first internal electron donating compound and the second internal electron donating compound, MFR, stereoregularity, molecular weight distribution A homopolymer and a copolymer having a moderately wide width can be easily produced.

In the second step, the solid catalyst component for olefin polymerization used in the present invention is a tetravalent titanium halogen compound and one or more second internal electrons with respect to the reaction product obtained in the first step. It is obtained by bringing a donor compound into contact with and reacting.
In the second step, the tetravalent titanium halogen compound and the second internal electron donating compound are suitably mixed in the presence of the same inert organic solvent as exemplified in the first step. Can be contacted.

  The conditions for contacting and reacting each component in the second step are not particularly limited, but specific examples include the same contact and reaction conditions as in the first reaction step.

  In the second step, when the tetravalent titanium halogen compound and the second internal electron donating compound are brought into contact with and reacted with the reaction product obtained in the first step (added in the first step). ) The amount of tetravalent titanium halogen compound used per mole of magnesium compound is preferably 0.1 to 50 moles, more preferably 0.2 to 20 moles, and 0.3 to 10 moles. More preferably.

  In the second step, when the tetravalent titanium halogen compound and the second internal electron donating compound are contacted and reacted with the reaction product obtained in the first step (added in the first step) I) The molar ratio of the amount of the second internal electron-donating compound used relative to 1 mol of the magnesium compound (the molar amount of the second internal electron-donating compound / the molar amount of the magnesium compound) is 0.001 to 10. It is preferably 0.001-1, more preferably 0.002-1, even more preferably 0.002-0.6, and 0.003-0.6. More preferably it is.

  The solid catalyst component for olefin polymerization comprises the first internal electron-donating compound and the second internal electron-donating compound, wherein the molar amount of the first internal electron-donating compound is greater than that of the second internal electron-donating compound. It is preferably obtained by contacting so as to satisfy the relationship of the molar amount.

  In the second step, when the tetravalent titanium halogen compound and the second internal electron donating compound are contacted and reacted with the reaction product obtained in the first step (added in the first step) (Ii) The molar ratio of the amount of the second internal electron donating compound used relative to 1 mol of the aromatic dicarboxylic acid diester represented by the general formula (I) as the first internal electron donating compound (second internal electron donating) The molar amount of the functional compound / the molar amount of the aromatic dicarboxylic acid diester represented by the general formula (I) as the first internal electron donating compound) is preferably 0.01 to 0.9, preferably It is more preferably 01 to 0.6, and further preferably 0.02 to 0.4.

  The ratio expressed by the molar amount of the second internal electron donating compound / the molar amount of the aromatic dicarboxylic acid diester represented by the general formula (I) as the first internal electron donating compound is within the above range. , It becomes easy to suppress the complex compound consisting of the second internal electron donating compound and the tetravalent titanium halogen compound from being excessively formed, and when the olefins are polymerized using the obtained solid catalyst component, Polymerization activity and stereoregularity can be easily improved.

  Moreover, when using an inert organic solvent at a 2nd process, the usage-amount of an inert organic solvent shall be 0.001-500 mol with respect to 1 mol of magnesium compounds (added at the 1st process). Is preferable, it is more preferable that it is 0.5-100 mol, and it is further more preferable that it is 1.0-20 mol.

  In the method for producing a solid catalyst component for olefin polymerization according to the present invention, it is preferable that the magnesium compound is added to the reaction system in a required amount in the first step in consideration of the efficiency of the reaction. In the second step, it is preferable not to add a magnesium compound to the reaction system.

In the second step, the contact of each component is preferably performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed.
After completion of the above reaction, it is preferable that the reaction solution is allowed to stand, and the supernatant is appropriately removed to obtain a wet state (slurry state).

In the second step, the reaction product obtained is washed after the completion of the reaction.
The cleaning treatment is usually performed using a cleaning solution. Examples of the cleaning liquid include the same ones as exemplified in the first step.
The processing temperature, processing method, amount of cleaning liquid used, number of times of cleaning, and the like in the second cleaning step are the same as those in the above-described first step.
In the solid catalyst component for olefin polymerization used in the present invention, each component is brought into contact with and reacted in the second step, and then subjected to a washing treatment, whereby unreacted raw material components and reactions remaining in the reaction product. Impurities of by-products (alkoxy titanium halide, titanium tetrachloride-carboxylic acid complex, etc.) can be removed.

  In the solid catalyst component for olefin polymerization used in the present invention, in the second step, as a post-treatment, for example, after completion of the above washing treatment, the product obtained is further subjected to tetravalent titanium as a post-treatment. It is intended to include a form in which it is brought into contact with a halogen compound and washed. The cleaning in this post-treatment can be performed in the same manner as the above-described cleaning.

  After completion of the reaction in the second step, the suspension after the washing treatment may be allowed to stand, and the supernatant liquid may be removed to obtain a wet state (slurry state), or may be dried by hot air drying or the like.

Preferred embodiments for producing the solid catalyst component for olefin polymerization used in the present invention include the following embodiments.
In the first step, a spherical magnesium compound is suspended in an inert organic solvent to prepare a suspension, and then a tetravalent titanium halogen compound is brought into contact with the suspension to carry out a reaction treatment. Before or after the tetravalent titanium halide compound is brought into contact with the suspension, the first internal electron donating compound represented by formula (I) as the first internal electron donating compound is- After contacting at 20 to 130 ° C., the reaction product is washed with an inert organic solvent to obtain a solid reaction product (α). It is preferable to carry out a low temperature aging reaction before or after contacting the first internal electron donating compound represented by the general formula (I).
Next, in the second step, the solid reaction product (α) obtained in the first step is added to the tetravalent titanium halogen compound and the second internal electron donating property in the presence of an inert organic solvent. The compound is contacted at 20 to 130 ° C., preferably 30 to 120 ° C., more preferably 80 ° C. to 110 ° C., and after reaction treatment, it is washed with an inert organic solvent to obtain a solid reaction product (β). . The treatment of contacting, reacting and washing with the tetravalent titanium halogen compound may be repeated a plurality of times.

In addition to the first step and the second step, between the first step and the second step, or after the second step, as an additional step, an electron donating compound is not used and a tetravalent titanium halogen compound is used. You may give the reaction process by an active solvent, and may further give the reaction process by an electron-donating compound and an inert solvent.

  In the method for producing a solid catalyst component for olefin polymerization of the present invention, the contacting and reaction of each component in the first step may be performed in the presence of polysiloxane as the third component.

Polysiloxane is a polymer having a siloxane bond (—Si—O— bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10,000 cm). Stokes), more preferably 0.03 to ⁵ cm ² / s (3 to 500 centistokes), a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1, , 3-dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis (chloromethyl) tetramethyldisiloxane, and dimethylpolysiloxane and methylphenylpolysiloxane as polysiloxanes other than disiloxane are partially hydrogenated As hydrogenated polysiloxane, methyl hydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As cyclic polysiloxane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamera is used. Rucyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid group-substituted dimethylsiloxane and epoxy group-substituted dimethylsiloxane. And polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

In the solid catalyst component for olefin polymerization used in the present invention, the content of magnesium atom is preferably 10 to 70% by mass, more preferably 10 to 50% by mass, further preferably 15 to 40% by mass, and 15 to 25%. Mass% is particularly preferred.
In the solid catalyst component for olefin polymerization obtained by the production method of the present invention, the content of titanium atoms is preferably 0.5 to 8.0 mass%, preferably 0.5 to 5.0 mass%, 0.5 -3.0 mass% is more preferable.
In the solid catalyst component for olefin polymerization used in the present invention, the halogen atom content is preferably 20 to 88% by mass, more preferably 30 to 85% by mass, further preferably 40 to 80% by mass, and 45 to 75%. More preferred is mass%.
In the solid catalyst component for olefin polymerization used in the present invention, the content of the first internal electron donating compound is preferably 0.1 to 30% by mass, more preferably 0.3 to 25% by mass, and 5-20 mass% is further more preferable.
In the solid catalyst component for olefin polymerization used in the present invention, the content of the second internal electron donating compound is preferably 0.1 to 30% by mass, more preferably 0.3 to 20% by mass, and 5-10 mass% is further more preferable.
In the solid catalyst component for olefin polymerization used in the present invention, the total amount of the first internal electron donating compound and the second internal electron donating compound is preferably 1.5 to 30% by mass. More preferably, it is 0.0-25 mass%, and it is further more preferable that it is 6.0-25 mass%.

  The solid catalyst component for olefin polymerization used in the present invention has, for example, a magnesium atom content of 15 to 25% by mass, a titanium atom content of 0.5 to 3.0% by mass, and a halogen atom content of 45 to 75% by mass, the content of the first internal electron donating compound is 2 to 20% by mass, the content of the second internal electron donating compound is 0.3 to 10% by mass, the first internal electron donating When the total amount of the active compound and the second internal electron donating compound is 6.0 to 25% by mass, the performance as the solid catalyst component can be exhibited in a well-balanced manner.

In the present application document, the content of magnesium atoms in the solid catalyst component means a value measured by an EDTA titration method in which the solid catalyst component is dissolved with a hydrochloric acid solution and titrated with an EDTA solution.
In the present application documents, the content of titanium atom in the solid catalyst component means a value measured according to the method (redox titration) described in JIS 8311-1997 “Method for quantifying titanium in titanium ore”. To do.
In the present application document, the content of halogen atoms in the solid catalyst component is determined by treating the solid catalyst component with a mixed solution of sulfuric acid and pure water to obtain an aqueous solution, and then separating a predetermined amount of the halogen atom with a silver nitrate standard solution. Means the value measured by the silver nitrate titration method.
In the present application document, the content of the first internal electron donating compound, the content of the second internal electron donating compound, the first internal electron donating compound to the second internal electron donating in the solid catalyst component The total content of the functional compound means a value measured by the method described later.

  In the present invention, an olefin polymerization catalyst obtained by contacting the solid catalyst component for olefin polymerization, an organoaluminum compound represented by the following general formula (II), and an external electron donating compound is used.

The organoaluminum compound constituting the olefin polymerization catalyst is represented by the following general formula (II)
R ⁴ _p AlQ _3-p (II)
(Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other; Q is a hydrogen atom or a halogen atom; When present, they may be the same or different, and p is a real number of 0 <p ≦ 3.)
And an external electron donating compound are brought into contact with each other.

  The details of the solid catalyst component for olefin polymerization of the present invention are as described above.

In the organoaluminum compound represented by the general formula (II), R ⁴ is an alkyl group having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group. And isobutyl group.

  In the organoaluminum compound represented by the general formula (II), Q represents a hydrogen atom or a halogen atom. When Q is a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  In the organoaluminum compound represented by the general formula (II), p is a real number of 0 <p ≦ 3, preferably a real number of 1.5 ≦ p ≦ 3, and a real number of 2 ≦ p ≦ 3. It is more preferable.

  Specifically, the organoaluminum compound represented by the general formula (II) is selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, tri-n-butylaluminum, tri-n-octylaluminum, diethylaluminum bromide and diethylaluminum hydride. One or more of them can be mentioned, and triethylaluminum and triisobutylaluminum are preferable.

  In the olefin polymerization catalyst used in the present invention, examples of the external electron donating compound include organic compounds containing an oxygen atom or a nitrogen atom. Specific examples include alcohols, phenols, ethers, esters. , Ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds, especially organosilicon compounds having Si—O—C bonds or aminosilanes having Si—N—C bonds Compounds and the like.

  Among the external electron-donating compounds, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate 1,3-diethers, organosilicon compounds containing Si—O—C bonds, aminosilane compounds containing Si—N—C bonds, organosilicon compounds having Si—O—C bonds, Si—N— Particularly preferred are aminosilane compounds having a C bond.

Among the external electron donating compounds, the organosilicon compound having a Si—O—C bond includes the following general formula (III):
R ⁵ Si (OR ⁶ ) _4-q (III)
(However, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, a linear or branched alkylamino group, or a polycyclic amino group, and R ⁵ R ⁶ may be the same as or different from each other when R ² is present, and R ⁶ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, A vinyl group, an allyl group or an aralkyl group, and when a plurality of R ⁶ are present, they may be the same or different from each other, q is an integer of 0 ≦ q ≦ 3.
The organosilicon alkoxy compound represented by these is mentioned.

Among the external electron donating compounds, the aminosilane compound having a Si—N—C bond includes the following general formula (IV):
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are each a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. A group selected from an alkyl group and an aryl group, which may be the same or different from each other; R ⁷ and R ⁸ may be bonded to each other to form a ring; and the R ⁷ R ⁸ N group is When there are a plurality of them, they may be the same or different from each other, and R ⁹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or 1 carbon atom. linear or branched alkoxy group to 20, vinyloxy group, a group selected from aryloxy group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group or an aryloxy group, if R ⁹ there are a plurality, more of ^{R 9} Optionally be the same or different .s can be mentioned aminosilane compound represented by 1 to 3. integer.).

  Examples of the organosilicon compound represented by the above general formula (III) or general formula (IV) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) ) Alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl And (alkylamino) silane. Specifically, n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis (Ethylamino) methylethylsilane, bis (ethylamino) t-butylmethylsilane, bis ( Tilamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, Examples include bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and the like. Among them, n-propyltriethoxysilane, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxy Silane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane , Cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino ) One or more selected from dimethoxysilane, diethylaminotriethoxysilane and the like.

  In the olefin polymerization catalyst used in the present invention, the content ratio of the solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donating compound is arbitrarily selected within a range in which the effects of the present invention can be obtained. Although not particularly limited, the organoaluminum compound is preferably 1 to 2000 mol, and preferably 50 to 1000 mol, per 1 mol of titanium atom in the solid catalyst component for olefin polymerization. It is more preferable. Further, the external electron donating compound is preferably 0.002 to 10 mol, more preferably 0.01 to 2 mol, and 0.01 to 0.5 mol per mol of the organoaluminum compound. More preferably it is.

The olefin polymerization catalyst used in the present invention can be prepared by bringing the olefin polymerization solid catalyst component, the organoaluminum compound and the external electron donating compound into contact with each other by a known method.
The order in which the above components are brought into contact is arbitrary, but the following contact order can be exemplified.
(I) The solid catalyst component for olefin polymerization → the external electron donating compound → the organoaluminum compound (ii) the organoaluminum compound → the external electron donating compound → the solid catalyst component for olefin polymerization (iii) External electron donating compound → solid catalyst component for olefin polymerization → organo aluminum compound (iv) external electron donating compound → organoaluminum compound → solid catalyst component for olefin polymerization The contact examples (i) to ( In iv), contact example (ii) is preferred.
In the contact examples (i) to (iv), “→” means the contact order. For example, “the solid catalyst component for olefin polymerization → the organoaluminum compound → the external electron donating compound” It means that after the organoaluminum compound is added and brought into contact with the solid catalyst component for olefin polymerization, the external electron donating compound is added and brought into contact.

  The olefin polymerization catalyst used in the present invention may be a catalyst obtained by contacting the solid catalyst component for olefin polymerization, an organoaluminum compound and an external electron donating compound in the absence of olefins, The contact may be made in the presence of olefins (in the polymerization system).

  The method for producing an olefin polymer according to the present invention uses an olefin polymerization catalyst, (1) a homopolymerization reaction of propylene, and (2) a content ratio of an α-olefin having 2 or 4 to 10 carbon atoms is 5 One or more polymerization reactions selected from a copolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms performed so as to be less than or equal to mass% (a homopolymerization reaction of (1) and a copolymerization of (2) One or more polymerization reactions selected from the reaction are performed a plurality of times under different molecular weight regulator concentrations.

In the method for producing an olefin polymer of the present invention, the olefin to be polymerized is propylene alone, propylene and an α-olefin having 2 or 4 to 10 carbon atoms (an α-olefin having 2 to 10 carbon atoms). Of these, other than propylene.
The α-olefin having 2 or 4 to 10 carbon atoms is preferably an α-olefin having 2 or 4 to 8 carbon atoms, specifically, ethylene, 1-butene, 1-pentene, 4 -Methyl-1-pentene, vinylcyclohexane and the like can be mentioned.
When a copolymerization reaction between propylene and an α-olefin having 2 or 4 to 10 carbon atoms is performed, one or two or more α-olefins having 2 or 4 to 10 carbon atoms are used. In the step of polymerization, different α-olefins may be used for each step together with propylene.

When the copolymerization reaction of (2) propylene and an α-olefin having 2 or 4 to 10 carbon atoms is carried out, the content ratio of the structural unit derived from the α-olefin having 2 or 4 to 10 carbon atoms is 5 mass. The copolymerization reaction may be performed so as to be not more than%, and the copolymerization reaction may be performed so that the content ratio of the structural unit derived from the α-olefin having 2 or 4 to 10 carbon atoms is 4% by mass or less. Preferably, the copolymerization reaction is more preferably performed so that the content of the structural unit derived from the α-olefin having 2 or 4 to 10 carbon atoms is 3% by mass or less.
(2) When the copolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms is performed, the number of carbon atoms relative to the total amount of propylene used and the α-olefin having 2 or 4 to 10 carbon atoms is 2 Alternatively, the amount of the α-olefin having 4 to 10 is preferably the same or slightly excessive as the theoretical amount, and 10 to the total amount of propylene to be used and the α-olefin having 2 or 4 to 10 carbon atoms. The content is preferably at most mass%, more preferably at most 6 mass%, further preferably at most 5 mass%.
As apparent from the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms in the polymer obtained by the copolymerization reaction, the copolymer of the propylene and the α-olefin having 2 or 4 to 10 carbon atoms is used. The polymerization reaction means a so-called random copolymerization reaction.

  In the present invention, (1) propylene homopolymerization reaction and (2) propylene and the carbon number of 2 or 4 are carried out so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less. One or more polymerization reactions selected from a copolymerization reaction with 10 α-olefins are performed several times each in the concentration of different molecular weight regulators (in the presence or absence of different amounts of molecular weight regulators). Do.

  Examples of the molecular weight regulator include hydrogen, alkylsilane hydride, metal alkyl and the like, and hydrogen is preferable.

In the present invention, (1) propylene homopolymerization reaction and (2) propylene and the carbon number of 2 or 4 are carried out so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less. One or more polymerization reactions selected from a copolymerization reaction with 10 α-olefins are performed several times each in the concentration of different molecular weight regulators (in the presence or absence of different amounts of molecular weight regulators). Do.
The number of polymerization reactions is preferably 2 to 8 times, more preferably 2 to 5 times, and even more preferably 2 to 3 times.
(1) When propylene homopolymerization is performed a plurality of times, or (1) with propylene homopolymerization, (2) The proportion of α-olefin having 2 or 4 to 10 carbon atoms is 5 mass% or less. When the polymerization reaction selected from the copolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms is performed a plurality of times, the number of homopolymerization reactions of propylene is preferably 2 to 5 times, and 2 to 3 times. More preferred. Each of the above polymerization reactions may be carried out continuously using a plurality of reactors under different molecular weight regulator concentrations for each reactor.
In the present invention, from the viewpoint of producing a polymer having excellent rigidity, wide molecular weight distribution, and high stereoregularity, it is preferable to carry out propylene homopolymerization multiple times under different molecular weight regulator concentrations. In addition, when a copolymerization reaction between propylene and an α-olefin having 2 or 4 to 10 carbon atoms is performed, it is preferable to have a step of performing the homopolymerization reaction of propylene a plurality of times under different molecular weight regulator concentrations. .

In the present application documents, the number of polymerization reactions means the number of concentrations of the molecular weight regulator adjusted (controlled) in a polymerization atmosphere when the polymerization reaction is performed under a temperature condition of 50 ° C. or higher, For example, when the homopolymerization of propylene is carried out under the condition of the molecular weight regulator concentration C ₁ under the temperature condition of 50 ° C. or higher, and further carried out under the condition of the molecular weight regulator concentration C ₂ , the number of polymerization reactions is “2”. As will be described later, the present invention includes an embodiment in which a preliminary polymerization reaction is performed under a temperature condition of less than 50 ° C. prior to the polymerization reaction. In the present application document, the polymerization is performed under the temperature condition of less than 50 ° C. The number of prepolymerizations to be performed is not included in the number of polymerization reactions.

In the polymerization reaction performed a plurality of times in the present invention, the amount of the molecular weight regulator used in the first polymerization reaction is a ratio represented by the molar amount of the molecular weight regulator / the molar amount of propylene used, and is 0 to 5 × 10 ^{− 3} (mol / mol), preferably 0 to 3 × 10 ⁻³ (mol / mol), more preferably 0 to 2 × 10 ⁻³ (mol / mol), More preferably, it is 0.01-2 * 10 < ^-3 > (mol / mol).
As described above, in the present application document, the number of polymerization reactions is the number of molecular weight regulators adjusted (controlled) in a polymerization atmosphere when the polymerization reaction is performed under a temperature condition of 50 ° C. or higher. This means that even when the amount of molecular weight regulator used is 0 mol (the amount of molecular weight regulator used is 0 (mol / mol) in the ratio expressed by the molar amount of molecular weight regulator / the molar amount of propylene used). Even if it is made to react on 50 degreeC or more temperature conditions, it shall be regarded as one polymerization reaction.

In the polymerization reaction carried out a plurality of times in the present invention, the amount of the molecular weight regulator used in the second and subsequent polymerization reactions is preferably larger than that of the first time, and the molar amount of the molecular weight regulator / the molar amount of propylene used. Is preferably 1 × 10 ⁻² (mol / mol) or more, more preferably 1.5 × 10 ⁻² (mol / mol) or more, and 2 × 10 ⁻² (mol). / Mol) or more.

The molecular weight regulator is generally polymerized using a smaller amount in the first polymerization reaction than in the second and subsequent polymerization reactions to produce a high molecular weight substance, and then the amount of the molecular weight regulator used in the second and subsequent polymerization reactions is increased. It is preferable to produce a polymer having a low molecular weight.
In the present invention, when the polymerization reaction is carried out twice, the use ratio of the molecular weight regulator is expressed by the molar amount of the molecular weight regulator used in the first polymerization reaction / the molar amount of the molecular weight regulator used in the second polymerization reaction. The ratio is preferably 0 to 200 (mol / mol), more preferably 0.0005 to 100 (mol / mol), still more preferably 0.0015 to 50 (mol / mol), and 0.002 to 10 (mol). / Mol) is more preferable.
In the present invention, the polymerization time of the first polymerization reaction is adjusted while adopting the use ratio of the molecular weight regulator, and at least 5% by mass or more of the obtained polymer is produced by the first polymerization reaction. Is preferred.

In the present invention, a propylene polymer having a desired molecular weight distribution is suitably obtained by changing the use amount of the molecular weight regulator in multiple stages for each polymerization reaction and controlling the polymerization time of each stage as necessary. Can be manufactured.
The amount of polymer produced is the amount of molecular weight regulator and propylene used, the ratio between the molecular weight regulator and propylene, the polymerization temperature, the polymerization pressure, the nature of the solid catalyst component, the type of organoaluminum compound used, the organoaluminum compound Can be appropriately controlled by controlling the amount of external electron donating compound, the type of external electron donating compound, the amount of external electron donating compound used, and the like.

In the present invention, the polymerization of olefins can be carried out in the presence or absence of an organic solvent.
The olefins to be polymerized can be used in either a gas or liquid state.

  The polymerization of olefins can be carried out, for example, by introducing olefins in the presence of the above-mentioned catalyst for olefin polymerization in a reaction furnace such as an autoclave, and reacting them under heating and pressure.

In the present invention, the polymerization temperature is usually 50 to 200 ° C., preferably 50 to 100 ° C., more preferably 60 to 100 ° C., and further preferably 70 to 90 ° C. from the viewpoint of improving activity and stereoregularity. preferable.
In the present invention, the pressure during the polymerization reaction (polymerization pressure) is preferably 10 MPa or less, and more preferably 5 MPa or less.
Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in two stages or in three or more stages.

In the present invention, propylene is homopolymerized, or propylene is used so that the content of α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less and α- having 2 or 4 to 10 carbon atoms. After one or more polymerization reactions selected from copolymerization reactions with olefins are performed a plurality of times, the resulting polymer is further subjected to a subsequent reaction as propylene and an α-olefin having 2 or 4 to 10 carbon atoms. So-called propylene block copolymer may be produced.
The copolymer of propylene obtained by the propylene block copolymer and an α-olefin having 2 or 4 to 10 carbon atoms has a rubber-like property in which two or more monomer compositions are randomly polymerized. Those that do not have many derived crystal parts are preferred.
As a comonomer to be used for copolymerization with propylene, that is, an α-olefin having 2 or 4 to 10 carbon atoms (other than propylene among α-olefins having 2 to 10 carbon atoms), specifically, ethylene , 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane and the like, and ethylene and 1-butene are preferable.

When a block copolymerization reaction between the propylene and an α-olefin having 2 or 4 to 10 carbon atoms (other than propylene) is carried out, usually, in the preceding stage, propylene is added in the presence of the olefin polymerization catalyst described above. After contacting and polymerizing alone (or under the condition that α-olefin other than propylene coexists in an amount of 5% by mass or less of the total amount of monomers) alone or in the absence of a molecular weight regulator, propylene is used alone. (Or under the condition that an α-olefin other than propylene coexists in an amount of 5% by mass or less of the total amount of monomers) and polymerized by contacting at least once under a concentration of the molecular weight regulator different from the molecular weight regulator, Next, in the latter stage, propylene and an α-olefin other than propylene (ethylene, etc.) are contacted, so-called propylene block It can be carried out by preparing the polymer.
In the preceding polymerization reaction, the polymerization reaction may be performed a plurality of times while changing the amount of the molecular weight regulator, and may be terminated as it is (only by the polymerization reaction in the previous stage), but the block copolymerization reaction in the latter stage is further performed. In this case, the copolymerization reaction of the latter stage propylene and an α-olefin other than propylene (ethylene or the like) may be performed in a single stage or a plurality of times.
It is preferable that the number of polymerization reactions to be carried out alone with the above-mentioned propylene alone (or under the condition that an α-olefin other than propylene coexists with 5% by mass or less of the total amount of monomers) is 2 to 5 times. It is more preferably 4 times, even more preferably 2 to 3 times, and the number of copolymerization reactions of the latter stage propylene and the α-olefin having 2 or 4 to 10 carbon atoms is 1 to 4 times. It is preferable that it is 1 to 3 times, more preferably 1 to 2 times.
The copolymerization reaction of propylene in the latter stage and an α-olefin other than propylene (ethylene, etc.) can be used in any state of gas and liquid as the olefins. It is preferable to carry out with.

  When performing the block copolymerization reaction of the propylene with an α-olefin other than propylene having 2 or 4 to 10 carbon atoms, in the preceding stage, the homopolymerization reaction of propylene and the α-olefin having 2 or 4 to 10 carbon atoms At least one polymerization reaction selected from the copolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms carried out so that the content ratio of the polymer is 5% by mass or less. In the latter stage, the copolymerization reaction between propylene and the α-olefin having 2 or 4 to 10 carbon atoms is 20 to 80 masses in content of the α-olefin having 2 or 4 to 10 carbon atoms. % Or less is preferable.

The polymerization reaction in the preceding stage is performed so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less in the obtained polymerization, and is 0 to 4% by mass. It is preferable to carry out so that it may become 0-3 mass%.
The copolymerization reaction in the latter stage is performed so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 20 to 80% by mass or less in the obtained copolymer, and 25 to 70% by mass. It is preferable to carry out so that it becomes 30-60 mass%.

In the polymerization reaction in the preceding stage and the subsequent stage, the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms can be controlled by appropriately adjusting the amount of α-olefins used, the polymerization temperature, and the polymerization time. it can.
The polymerization temperature in the first and second stages is preferably 50 to 200 ° C, more preferably 50 to 100 ° C, further preferably 60 to 90 ° C, and the polymerization pressure is preferably 10 MPa or less, more preferably 7 MPa or less, 5 MPa or less is more preferable.
In the above copolymerization reaction, either a continuous polymerization method or a batch polymerization method can be employed. The polymerization reaction may be performed in one stage or in two or more stages.
In addition, the polymerization time (residence time in the reaction furnace) is preferably 1 minute to 5 hours in each of the polymerization stages in the preceding stage or the subsequent stage, or even in the continuous polymerization.
Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method using substantially no solvent. A bulk polymerization method or a gas phase polymerization method is suitable, and the subsequent reaction is generally a gas phase polymerization reaction for the purpose of suppressing elution of EPR from PP particles.

  In the present invention, when polymerizing olefins (hereinafter referred to as main polymerization as appropriate), some or all of the components of the olefin polymerization catalyst of the present invention are brought into contact with the olefins to be polymerized. Thus, preliminary polymerization (hereinafter, referred to as preliminary polymerization as appropriate) may be performed. However, the prepolymerization performed under the temperature condition of less than 50 ° C. as described above is not included in the main polymerization.

In the prepolymerization, the constituent components of the olefin polymerization catalyst of the present invention and the contact order of the olefins are arbitrary, but the organoaluminum compound is first put in the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere. After charging and then contacting the solid catalyst component for olefin polymerization of the present invention, one or more olefins such as propylene are preferably contacted. Alternatively, an organoaluminum compound is first charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, then contacted with an external electron donating compound, and further contacted with the solid catalyst component for olefin polymerization according to the present invention. Then, it is preferable to contact one or more olefins such as propylene.
In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

The polymerization temperature during preliminary polymerization is less than 50 ° C, preferably 0 ° C or more and less than 50 ° C, and more preferably 0 to 30 ° C. The prepolymerization time is also preferably 1 minute to 1 hour, more preferably 1 to 15 minutes.
Further, the molecular weight modifier may be used also in the prepolymerization, and the amount used is not particularly limited as long as it does not affect the amount of the first molecular weight regulator in the main polymerization.

  By performing the prepolymerization, the catalytic activity is improved, and the stereoregularity and particle properties of the resulting polymer can be further improved.

  According to the present invention, when performing homopolymerization or copolymerization of olefins, the polymerization activity of olefins and the hydrogen activity during polymerization are excellent, the MFR and rigidity are excellent, the molecular weight distribution is wide, and the stereoregularity is high. It is possible to provide a novel production method capable of producing a polymer under a high polymerization activity persistence.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, these are examples and do not limit the present invention.
In Examples and Comparative Examples shown below, the degree of circularity of dialkoxymagnesium particles and the contents of magnesium atoms, titanium atoms, halogen atoms and internal electron donating compounds in the solid catalyst component were measured by the following methods. Is.

(Circularity of dialkoxymagnesium particles)
The degree of circularity of dialkoxymagnesium particles is obtained by photographing the dialkoxymagnesium particles with a scanning electron microscope (manufactured by JEOL Ltd., JSM-7500F) at a magnification such that 500 to 1000 particles are displayed on one screen. After randomly extracting 500 or more particles from the photographed particles and measuring the area S and the perimeter L of each particle with image analysis processing software (manufactured by MOUNTECH, MacView version 4.0), The circularity of the alkoxymagnesium particles was determined as an arithmetic average value when calculated by the following formula.
Circularity of each dialkoxymagnesium particle = L ² ÷ (4π × S)

(Content of magnesium atom in the solid catalyst component)
The magnesium atom content in the solid catalyst component is determined by weighing the solid catalyst component from which the solvent component has been completely removed by heating under reduced pressure in advance, dissolving in hydrochloric acid solution, adding indicator methyl orange and saturated ammonium chloride solution, and adding ammonia. Heated after neutralization with water, filtered to a constant volume after cooling to remove the precipitate (Ti hydroxide), and a certain amount of the obtained filtrate was taken, and after heating, mixed buffer and EBT indicator And was measured by the EDTA titration method of titrating with an EDTA solution.

(Titanium atom content in the solid catalyst component)
The titanium atom content in the solid catalyst component was measured according to the method (oxidation-reduction titration) described in JIS 8311-1997 “Titanium determination method in titanium ore”.

(Halogen atom content in the solid catalyst component)
The halogen atom content in the solid catalyst component is a constant volume after weighing the solid catalyst component from which the solvent component has been completely removed by heating under reduced pressure and treating it with a mixed solution of sulfuric acid and pure water to obtain an aqueous solution. Was measured by a silver nitrate titration method in which halogen atoms were titrated with a silver nitrate standard solution using an automatic titrator (COM-1500, manufactured by Hiranuma Sangyo Co., Ltd.).

(Content of internal electron donating compound in solid catalyst component)
The contents of the first internal electron donating compound and the second internal electron donating compound contained in the solid catalyst component are as follows using gas chromatography (manufactured by Shimadzu Corporation, GC-14B). It was determined by measuring at Further, the number of moles of each component (each internal electron donating compound) was determined from a measurement result of gas chromatography using a calibration curve measured in advance at a known concentration.
<Measurement conditions>
Column: Packed column (φ2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Inc.)
Detector: FID (Frame Ionization Detector, hydrogen flame ionization detector)
Carrier gas: helium, flow rate 40 ml / min Measurement temperature: vaporization chamber 280 ° C., column 225 ° C., detector 280 ° C.

(Example 1)
<Preparation of solid catalyst component>
(1) Preparation of solid catalyst component (first step)
A 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene to form a mixed solution.
It is then formed using 20 g (175 mmol) of spherical diethoxymagnesium (circularity: 1.10), 80 ml (753 mmol) of toluene and 1.8 ml (7.8 mmol) of di-n-propyl phthalate. The suspension was added into the mixed solution. Then, it stirred at -5 degreeC for 1 hour, and heated up to 110 degreeC. During the temperature increase, 3.6 ml (15.5 mmol) of di-n-propyl phthalate was added in portions. After maintaining the temperature at 110 ° C. while stirring for 2 hours, the resulting reaction solution was allowed to stand and the supernatant was removed to obtain a slurry-like reaction product.
To the above slurry-like reaction product, 187 ml of 100 ° C. toluene was added, stirred, allowed to stand, and then washed by repeating the process of removing the supernatant four times to obtain a slurry-like solid component (I ) Was obtained.

(Second step)
To the reaction product containing the slurry-like solid component (I), 170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titanium tetrachloride were added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours with stirring. After completion of the reaction, the supernatant of toluene was removed, 180 ml of toluene and 20 ml (182 mmol) of titanium tetrachloride were added, and the temperature was raised. At 80 ° C., 0.5 ml (2.2 mmol) of di-n-propyl phthalate was added. After the addition, the temperature was raised to 110 ° C., the reaction was allowed to stir for 2 hours, the resulting reaction solution was allowed to stand, and the supernatant was removed to obtain a slurry-like reaction product.
After completion of the reaction, 187 ml of 100 ° C. toluene was added to the slurry-like reaction product obtained, stirred, allowed to stand, and then the treatment of removing the supernatant was repeated twice. After adding 150 ml of heptane, stirring, and allowing to stand, washing was performed by repeating the process of removing the supernatant 5 times to obtain about 20 g of a slurry-like solid catalyst component (A1) for olefin polymerization.
The solid catalyst component (A1) has a magnesium atom content of 16.8% by mass, a titanium atom content of 2.1% by mass, and a halogen atom content of 60.8% by mass. The total content of the acid diester was 16.7% by mass.

(2) Formation of propylene polymerization catalyst and propylene polymerization In an autoclave equipped with a stirrer with an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum and 0.13 mmol of diisoprodimethoxysilane (DIPDMS) Then, 0.0013 mmol of the solid catalyst component (A1) was charged in terms of titanium atom to prepare a catalyst for olefin polymerization.
The autoclave with a stirrer having an internal volume of 2.0 liters was further charged with 0.5 liters of hydrogen gas and 1.4 liters of liquefied propylene, preliminarily polymerized at 20 ° C. and 1.1 MPa for 5 minutes, and then heated. As the first stage polymerization reaction, the polymerization reaction was carried out at 70 ° C. and 3.0 MPa for 20 minutes. Thereafter, 12 liters of hydrogen was further injected, and the total pressure was increased to 3.6 MPa. Then, as a second stage polymerization reaction, a polymerization reaction was performed at 70 ° C. for 45 minutes to obtain a propylene polymer (polypropylene).
The polymerization conditions are shown in Table 2.

  While measuring the polymerization activity per gram of the solid catalyst component during the above polymerization reaction, the polymer p-xylene soluble fraction (XS), the polymer melt flow rate (MFR), the polymer molecular weight distribution (Mw) / Mn), the Z average molecular weight Mz, and the flexural modulus (FM) of the polymer were measured by the following methods. The results are shown in Table 3.

<Propylene polymerization activity>
The polymerization activity per 1 g of the solid catalyst component was determined by the following formula.
Polymerization activity (g-pp / g-cat) = mass of polymer (g) / mass of solid catalyst component in olefin polymerization catalyst (g)

<Xylene solubles in polymer (XS)>
A flask equipped with a stirrer was charged with 4.0 g of a polymer (polypropylene) and 200 ml of p-xylene, and the external temperature was set to be equal to or higher than the boiling point of xylene (about 150 ° C.). While maintaining the temperature of p-xylene at the boiling point (137 to 138 ° C.), the polymer was dissolved over 2 hours. Thereafter, the liquid temperature was cooled to 23 ° C. over 1 hour, and insoluble components and dissolved components were separated by filtration. The solution of the above-mentioned dissolved component is collected, p-xylene is distilled off by heating under reduced pressure, the weight of the obtained residue is obtained, and the relative ratio (mass%) to the produced polymer (polypropylene) is calculated. Xylene soluble matter (XS) was used.

<Polymer melt flowability (MFR)>
The melt flow rate (MFR) (g / 10 minutes) indicating the melt flowability of the polymer was measured according to ASTM D 1238 and JIS K 7210.

<Molecular weight distribution of polymer (Mw / Mn), Z average molecular weight Mz>
The molecular weight distribution (weight average molecular weight / number average molecular weight, Mw / Mn) of the polymer was measured using a GPC apparatus (GPC2000 manufactured by Waters) under the following conditions.
Solvent: Orthodichlorobenzene (ODCB)
Flow rate: 1 mg / min
Column: shodex UT-806M × 3, HT-803 × 1
Sample concentration: 1 mg / ml

<Flexural modulus (FM) of polymer>
In accordance with JIS K 7171, a test piece for measuring physical properties was injection-molded using the above polymer, and after conditioning for 144 hours or more in a thermostatic chamber adjusted to 23 ° C., liquid or powder exuded on the surface The sample in which no was observed was used as a test piece, and the flexural modulus (FM) (MPa) of the test piece was measured.

(Example 2 to Example 5)
<Formation of propylene polymerization catalyst and propylene polymerization>
Molar ratio of hydrogen amount to added propylene amount (hydrogen amount / propylene amount (mol / mol)) and polymerization time during prepolymerization and first stage polymerization reaction, and addition during second stage polymerization reaction The polymerization reaction was carried out in the same manner as in Example 1 except that the molar ratio of hydrogen amount to propylene amount (hydrogen amount / propylene amount (mol / mol)) and the polymerization time were changed as shown in Table 2. And evaluated in the same manner. The results are shown in Table 3.

(Examples 6 to 8)
<Formation of propylene polymerization catalyst and propylene polymerization>
As shown in Table 2, instead of dipropyldimethoxysilane (DIPDMS) as an external electron-donating compound used during polymerization, the same mole of dicyclopentyldimethoxysilane (DCPDMS), cyclohexylmethyldimethoxysilane (CMDMS), or diethylaminotrimethyl A polymerization reaction was carried out in the same manner as in Example 1 except that it was changed to ethoxysilane (DEATES), and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

Example 9
<Formation of propylene polymerization catalyst and propylene polymerization>
As shown in Table 2, the polymerization reaction was performed in the same manner as in Example 5 except that no hydrogen was added at the time of the first-stage polymerization reaction, and evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 1)
<Formation of propylene polymerization catalyst and propylene polymerization>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of diisopropyldimethoxysilane (DIPDMS) and the solid catalyst component obtained in Example 1 above ( A catalyst for olefin polymerization was prepared by charging 0.0013 mmol of A1) as a titanium atom.
The autoclave with a stirrer having an internal volume of 2.0 liters was further charged with 4.0 liters of hydrogen gas and 1.4 liters of liquefied propylene, preliminarily polymerized at 20 ° C. and 1.1 MPa for 5 minutes, and then heated. The polymerization reaction was carried out at 70 ° C. and 3.0 MPa for 60 minutes to obtain a propylene polymer (polypropylene), which was evaluated in the same manner as in Example 1. The polymerization conditions are shown in Table 2 and the results are shown in Table 3.

(Example 10)
In the first step of Example 1, 2.7 ml (11 mmol) of n-butyl phthalate was used instead of 1.8 ml of di-n-propyl phthalate, and in the second step of Example 1. A solid catalyst component for olefin polymerization (as in Example 1) except that 3.3 ml (mmol) of dimethyl diisobutylmalonate was used instead of 0.5 ml (2.2 mmol) of di-n-propyl phthalate. A2) About 20 g was obtained.
The solid catalyst component (A2) has a magnesium atom content of 17.1% by mass, a titanium atom content of 2.5% by mass, and a halogen atom content of 61.5% by mass. The total content of acid diesters was 10.3% by mass, and dimethyl isobutylmalonate was 4.8% by weight.
<Formation of propylene polymerization catalyst and propylene polymerization>
In an autoclave equipped with a stirrer with an internal volume of 2.0 liters that is completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of diisoprodimethoxysilane (DIPDMS) and the above solid catalyst component (A2) are converted into titanium atoms. Was added at 0.0013 mmol to prepare a catalyst for olefin polymerization.
The autoclave with a stirrer having an internal volume of 2.0 liters was further charged with 0.5 liters of hydrogen gas and 1.4 liters of liquefied propylene, preliminarily polymerized at 20 ° C. and 1.1 MPa for 5 minutes, and then heated. As the first stage polymerization reaction, the polymerization reaction was carried out at 70 ° C. and 3.0 MPa for 20 minutes. Thereafter, 12 liters of hydrogen was injected, the total pressure was increased to 3.6 MPa, and then the polymerization reaction was carried out at 70 ° C. for 45 minutes as the second stage polymerization reaction, whereby the desired propylene polymer (polypropylene) And evaluated in the same manner as in Example 1. The polymerization conditions are shown in Table 2 and the results are shown in Table 3.

(Comparative Example 2)
<Formation of propylene polymerization catalyst and propylene polymerization>
Propylene polymerization was carried out in the same manner as in Comparative Example 1 except that the solid catalyst component (A2) obtained in Example 10 was used. The polymerization conditions are shown in Table 2 and the results are shown in Table 3.

(Comparative Example 3)
<Preparation of solid catalyst component>
(1) Preparation of solid catalyst component (first step)
A 500 ml round bottom flask fully substituted with nitrogen gas and equipped with a stirrer was charged with 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene to form a mixed solution.
The suspension was then formed using 20 g (175 mmol) of spherical diethoxymagnesium (circularity: 1.10), 80 ml (753 mmol) of toluene and 2.7 ml (11 mmol) of di-n-butyl phthalate. The turbid solution was added into the mixed solution. Then, it stirred at -5 degreeC for 1 hour, and heated up to 110 degreeC. After maintaining the temperature at 110 ° C. for 2 hours with stirring, the reaction solution obtained was allowed to stand and the supernatant was removed to obtain a slurry-like reaction product containing the solid component (I). .
(Second step)
To the reaction product containing the slurry-like solid component (I), 170 ml (1600 mmol) of toluene and 30 ml (273 mmol) of titanium tetrachloride were added, the temperature was raised to 110 ° C., and the mixture was reacted for 2 hours with stirring. After completion of the reaction, the toluene supernatant was removed, 180 ml of toluene and 20 ml of titanium tetrachloride (182 mmol) were further added, the temperature was raised to 110 ° C., the mixture was allowed to react with stirring for 2 hours, and the resulting reaction solution was allowed to stand. By removing the supernatant, a slurry-like reaction product was obtained.
After completion of the reaction, 187 ml of 100 ° C. toluene was added to the slurry-like reaction product obtained, stirred, allowed to stand, and then the treatment of removing the supernatant was repeated twice. After adding 150 ml of heptane, stirring, and allowing to stand, washing was performed by repeating the process of removing the supernatant liquid 5 times to obtain about 20 g of a slurry-like solid catalyst component (A3) for olefin polymerization.
The solid catalyst component (A3) has a magnesium atom content of 16.9% by mass, a titanium atom content of 2.7% by mass, and a halogen atom content of 62.5% by mass. The total content of the acid diester was 11.2% by mass.

<Formation of polymerization catalyst and propylene polymerization>
Except that the solid catalyst component (A3) obtained in Comparative Example 3 was used, the polymerization catalyst was formed and propylene was polymerized in the same manner as in Example 1 to evaluate the polymerization activity. The polymer was evaluated.
The polymerization conditions are shown in Table 2 and the results are shown in Table 3.

(Example 11)
<Formation of polymerization catalyst and ethylene-propylene block copolymer>
(1) Propylene polymerization (first stage polymerization reaction)
Except for using the solid catalyst component (A2) obtained in Example 10 above, after forming the polymerization catalyst and propylene polymerization in the same manner as in Example 1, the autoclave internal pressure was returned to normal pressure, and polymer particles were obtained. The amount of (polypropylene) produced was weighed together with the autoclave to evaluate the polymerization activity (propylene polymerization activity), and a part (about 20 g) of the obtained polymer particles was extracted and obtained in the same manner as in Example 1. The obtained propylene polymer was evaluated.
(2) Ethylene-propylene block copolymerization (second stage polymerization reaction)
Next, ethylene-propylene and hydrogen are mixed so that the quantitative ratio (molar ratio) represented by ethylene (mol) / propylene (mol) / hydrogen (mol) is 1.0 / 1.0 / 0.043. After being put in an autoclave with a stirrer, the temperature is raised to 70 ° C., and ethylene, propylene and hydrogen are further converted into a ratio represented by ethylene (liter / minute) / propylene (liter / minute) / hydrogen (liter / minute). An ethylene-propylene copolymer was obtained by reacting under the conditions of 1.2 MPa, 70 ° C., and 1 hour while introducing it at a ratio of 2/2 / 0.086.
In the obtained ethylene-propylene copolymer, the flexural modulus (FM) was measured by the same method as described above, and the ethylene-propylene block copolymerization activity (ICP activity) (kg-ICP) was measured by the following method. / (G-cat · time)), the block ratio (% by mass) of the obtained copolymer, the ethylene-propylene copolymer (EPR) content (% by mass), the ethylene-propylene copolymer ( EPR) was measured for ethylene content (mass%) and Izod impact strength.
The polymerization conditions are shown in Table 4 and the results are shown in Tables 5 and 6.

<Ethylene-propylene block copolymerization activity (ICP activity) (g-ICP / (g-cat · time))>
The copolymerization activity (ICP activity) at the time of forming the ethylene-propylene block copolymer was calculated by the following formula.
Ethylene-propylene block copolymerization activity (g-ICP / (g-cat · time)) = ((I (g) -G (g)) / (mass of solid catalyst component contained in olefin polymerization catalyst (g ) X 1.0 (hours))
Here, I is the autoclave mass (g) after completion of the copolymerization reaction, and G is the autoclave mass (g) after removal of the unreacted monomer after completion of the homo PP polymerization.

<Block ratio (mass%)>
The block ratio of the obtained copolymer was calculated by the following formula.
Block ratio (mass%) = {(I (g) −G (g)) / (I (g) −F (g))} × 100
Here, I is autoclave mass (g) after completion of copolymerization reaction, G is autoclave mass (g) after removal of unreacted monomers after completion of homo PP polymerization, and F is autoclave mass (g).

<Izod impact strength>
IRGANOX 1010 (manufactured by BASF) 0.10% by weight, IRGAFOS 168 (manufactured by BASF) 0.10% by weight, and calcium stearate 0.08% by weight are blended with the obtained ethylene-propylene copolymer. By kneading and granulating with a single screw extruder, a pellet-like ethylene-propylene copolymer was obtained.
Next, the pellet-shaped copolymer was introduced into an injection molding machine maintained at a mold temperature of 60 ° C. and a cylinder temperature of 230 ° C., and a test piece for measuring physical properties was injection molded by injection molding.
About the test piece after shaping | molding, after performing condition adjustment for 144 hours or more in the thermostatic chamber adjusted to 23 degreeC, IZOD test machine (Corporation | KK Toyo Seiki Seisakusho, Izod impact tester model number A-12804405) is used. According to JIS K7110 “Testing method for Izod impact strength”, the Izod impact strength of the test pieces at 23 ° C. and −30 ° C. was measured.
Test piece shape: ISO 180 / 4A, thickness 3.2 mm, width 12.7 mm, length 63.5 mm
Notch shape: Type A notch (notch radius 0.25 mm), formed with a notched die Temperature conditions: 23 ° C and -30 ° C
Impact speed: 3.5m / s
Nominal pendulum energy: 5.5J at 23 ° C measurement, 2.75J at -30 ° C measurement

(Comparative Example 4)
(1) Propylene polymerization (first stage polymerization reaction)
Except for using the solid catalyst component (A2) obtained in Comparative Example 1 above, in the same manner as in Example 11, formation of a polymerization catalyst, propylene polymerization, evaluation of polymerization activity (propylene polymerization activity) and obtained propylene The polymer was evaluated.
(2) Ethylene-propylene block copolymerization (second stage polymerization reaction)
The polypropylene obtained in (1) was subjected to ethylene-propylene block copolymerization in the same manner as in Example 11 (2), and in the same manner as in Example 11, ICP activity was obtained. The rate (mass%), the ethylene-propylene copolymer content (mass%), the ethylene content ratio (mass%) in the ethylene-propylene copolymer, and the Izod impact strength were measured.
The polymerization conditions are shown in Table 4 and the results are shown in Tables 5 and 6.

From Table 2 to Table 6, in Examples 1 to 11, when performing homopolymerization or copolymerization of olefins, the polymerization activity of olefins and the hydrogen activity during polymerization are excellent, and the MFR and rigidity are excellent. It can be seen that a polymer having a wide molecular weight distribution and high stereoregularity can be produced under a high polymerization activity persistence.
On the other hand, from Tables 2 to 6, it can be seen that Comparative Examples 1 to 4 are inferior in molecular weight distribution of the obtained polymer.

  According to the present invention, when performing homopolymerization or copolymerization of olefins, the polymerization activity of olefins and the hydrogen activity during polymerization are excellent, the MFR and rigidity are excellent, the molecular weight distribution is wide, and the stereoregularity is high. It is possible to provide a novel production method capable of producing a polymer under a high polymerization activity persistence.

Claims (7)

A method for producing an olefin polymer comprising:
Magnesium compound, tetravalent titanium halogen compound, and the following general formula (I)
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a halogen atom, and when a plurality of R ¹ are present, they may be the same as or different from each other, and R ² and R ³ may have 1 to 1 carbon atoms. 12 alkyl groups, which may be the same or different, and the number j of substituents R ¹ is 0, 1 or 2, and when j is 2, each R ¹ is the same And the first internal electron donating compound selected from the aromatic dicarboxylic acid diesters represented by the following formula: For the resulting product,
A solid catalyst component for olefin polymerization obtained by subjecting a tetravalent titanium halogen compound and one or more second internal electron donating compounds to contact, reacting, and then performing a second step of washing;
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(Wherein R ⁴ is an alkyl group having 1 to 6 carbon atoms, and when a plurality of R ⁴ are present, they may be the same as or different from each other; Q is a hydrogen atom or a halogen atom; When present, they may be the same or different, and p is a real number of 0 <p ≦ 3.)
An organoaluminum compound represented by:
Using an olefin polymerization catalyst obtained by contacting an external electron donating compound,
A homopolymerization reaction of propylene and a copolymerization reaction of propylene with an α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less. A method for producing an olefin polymer, wherein one or more polymerization reactions selected from the above are performed a plurality of times under different molecular weight regulator concentrations.   The method for producing an olefin polymer according to claim 1, wherein the homopolymerization reaction of propylene is performed a plurality of times under different molecular weight regulator concentrations. In the polymerization reaction performed a plurality of times,
The amount of the molecular weight regulator used in the first polymerization reaction is 0 to 5 × 10 ⁻³ (mol / mol) in a ratio represented by the molar amount of the molecular weight regulator / the molar amount of propylene used.
The amount of the molecular weight regulator used in the second polymerization reaction is 1 × 10 ⁻² (mol / mol) or more in a ratio represented by the molar amount of the molecular weight regulator / the molar amount of propylene used. The manufacturing method of the olefin polymer of Claim 1 or Claim 2.   The method for producing an olefin polymer according to claim 1 or 2, wherein the molecular weight regulator is hydrogen. The external electron donating compound is represented by the following general formula (III);
R ⁵ _q Si (OR ⁶ ) _4-q (III)
(However, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group or an aralkyl group, a linear or branched alkylamino group, or a polycyclic amino group, and R ⁵ R ⁶ may be the same as or different from each other when R ² is present, and R ⁶ represents a linear or branched alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, A vinyl group, an allyl group or an aralkyl group, and when a plurality of R ⁶ are present, they may be the same or different from each other, q is an integer of 0 ≦ q ≦ 3.
An organosilicon alkoxy compound represented by the following general formula (IV):
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are each a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or a cyclohexane having 3 to 20 carbon atoms. A group selected from an alkyl group and an aryl group, which may be the same or different from each other; R ⁷ and R ⁸ may be bonded to each other to form a ring; and the R ⁷ R ⁸ N group is When there are a plurality of them, they may be the same or different from each other, and R ⁹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, or 1 carbon atom. linear or branched alkoxy group to 20, vinyloxy group, a group selected from aryloxy group, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group or an aryloxy group, if R ⁹ there are a plurality, more of ^{R 9} Optionally be the same or different .s is an integer from 1 to 3.)
The manufacturing method of the olefin polymer of Claim 1 or Claim 2 which is 1 or more types chosen from the aminosilane compound represented by these. The solid catalyst component for polymerizing olefins comprises the first internal electron donating compound and the second internal electron donating compound,
3. The olefin according to claim 1, wherein the olefin is obtained by contact so as to satisfy a relationship of a molar amount of the first internal electron-donating compound> a molar amount of the second internal electron-donating compound. A method for producing a similar polymer. A homopolymerization reaction of propylene and a copolymerization reaction of propylene with an α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms is 5% by mass or less. After performing one or more polymerization reactions selected from the above several times under different molecular weight regulator concentrations,
The content ratio of the α-olefin having 2 or 4 to 10 carbon atoms in the copolymerization reaction of propylene and the α-olefin having 2 or 4 to 10 carbon atoms with respect to the obtained polymer is 20 to 80% by mass or less. The manufacturing method of the olefin polymer of Claim 1 or Claim 2 performed so that it may become.