JP6810653B2 - Method for producing olefin polymer - Google Patents

Description

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

Conventionally, olefins such as propylene have been polymerized using a catalyst for olefin polymerization, and the obtained propylene-based polymer is melted and then molded by various molding machines, stretching machines and the like. It is used for various purposes such as containers and films, as well as molded products such as automobile parts and home appliance parts.

As a constituent component of a catalyst for olefin polymerization, a solid catalyst component containing magnesium, titanium, an electron donating compound and a halogen atom as essential components is known, and the above solid catalyst component, an organoaluminum compound and an organosilicon compound are used. Many catalysts for olefin polymerization have been proposed.

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

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

In recent years, in large household appliances and automobile parts, especially products such as bumpers, olefin polymers having high MFR and stereoregularity, as well as thin walls and high physical strength, that is, excellent rigidity have been used. It has come to be required. On the other hand, in order to maintain uneven flow during molding and homogeneity of the film or sheet, it is necessary to appropriately control the molecular weight distribution.

Under such circumstances, the applicant has previously stated in Patent Document 1 (Japanese Unexamined Patent Publication No. 2004-107462) that an internal electron donating compound composed of a magnesium compound, a tetravalent titanium halogen compound, malonic acid diesters, and the like. We have proposed a catalyst for olefin polymerization consisting of a solid catalyst component obtained by contacting an internal electron donating compound made of phthalic acid diesters, an organoaluminum compound and an organosilicon compound, and polymerizing the olefins using the polymerization catalyst. Proposing a method.
Alternatively, an olefin polymerization catalyst composed of a solid catalyst component obtained from an internal electron donating compound composed of a magnesium compound, a tetravalent titanium halogen compound and a phthalic acid diester, an organoaluminum compound and an organosilicon compound is used. It has been proposed to improve the activity, improve the stereoregularity, and widen the molecular weight distribution by using the compound (see Patent Document 2 (Japanese Unexamined Patent Publication No. 2006-169283)).

Japanese Unexamined Patent Publication No. 2004-107462 Japanese Unexamined Patent Publication No. 2006-169283

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

However, as a result of further studies by the present inventors, in order to simultaneously contact and react two or more different types of 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 addition. Therefore, a complex of a surplus internal electron donating compound and a tetravalent titanium halogen compound is easily formed, and when used as a constituent component of a catalyst for olefin polymerization, the polymerization activity during polymerization and the obtained olefins It was found that the stereoregularity of the polymer was likely to decrease.

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

By the way, when producing a large-sized molded product 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 kinds of α-olefins such as propylene and ethylene May be required.
In this case, for example, when a homopolymerization reaction is first carried out using propylene and then a copolymerization reaction is carried out using propylene and ethylene to produce a block copolymer, the proportion of the copolymerization portion is increased. Since the rigidity of the polymer is lowered, it is necessary to form polypropylene having higher rigidity during the homopolymerization in the previous stage.

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

Under such circumstances, the present invention is excellent in polymerization activity of olefins and hydrogen resistance activity at the time of polymerization, excellent in MFR and rigidity, wide molecular weight distribution, and three-dimensional when carrying out homopolymerization or copolymerization of 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 persistence.

As a result of diligent studies by the present inventors in order to solve the above technical problems, it is a method for producing an olefin polymer, which is a magnesium compound, a tetravalent titanium halogen compound, and a specific aromatic dicarboxylic acid. The first internal electron donating compound composed of the diester is contacted, reacted, and then washed, and the obtained product is subjected to a first step of carrying out a tetravalent titanium halogen compound and one or more of the first. A solid catalyst component for olefin polymerization obtained by subjecting the second internal electron donating compound to a contact, reacting, and then performing a second step of washing, a specific organic aluminum compound, and an external electron donating compound. Using a catalyst for olefin polymerization, which is obtained by contacting propylene, a homopolymerization reaction of propylene is carried out so that the content ratio of α-olefin having 2 or 4 to 10 carbon atoms is 5% by weight or less. Alternatively, the above object is achieved by producing an olefin polymer by carrying out one or more polymerization reactions selected from the copolymerization reactions with 4 to 10 α-olefins a plurality of times under different molecular weight modifier concentrations. We have found that we can obtain it, and have completed the present invention 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 or a halogen atom having 1 to 8 carbon atoms, and when a plurality of R ^1s are present, they may be the same or different from each other, and R ² and R ³ have 1 to 8 carbon atoms. It is an alkyl group of 12, which may be the same or different, and when the number j of the substituent R ¹ is 0, 1 or 2, and j is 2, each R ¹ is the same. The first step of contacting with one or more first internal electron donating compounds selected from the aromatic dicarboxylic acid diesters represented by), reacting them, and then washing them is performed. For the resulting product
A solid catalyst component for olefin polymerization obtained by contacting a tetravalent titanium halogen compound with one or more second internal electron donating compounds, reacting them, and then performing a second step of washing.
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(In the formula, 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 or different from each other, Q is a hydrogen atom or a halogen atom, and Q is a plurality. If they exist, they may be the same or different from each other, and p is a real number of 0 <p≤3.)
Organoaluminium compound represented by
Using a catalyst for olefin polymerization formed by contacting an external electron donating compound,
A homopolymerization reaction of propylene and a copolymerization reaction of propylene and 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. There multiple rows of one or more of the polymerization reaction, phase in different molecular weight modifier concentration under selected from,
In the polymerization reaction performed a plurality of times,
The amount of the molecular weight adjusting agent used in the first polymerization reaction is 0 to 5 × 10 ^-3 (mol / mol) in a ratio expressed by the molar amount of the molecular weight adjusting agent / the molar amount of propylene used .
The amount of the molecular weight modifier used in the second polymerization reaction is 1 × ^10-2 (mol / mol) or more in a ratio expressed by the molar amount of the molecular weight modifier / the molar amount of propylene used. A method for producing an olefin polymer, which is characterized by the above.
(2) The second internal electron donating compound is one or more selected from alkyl-substituted malonic acid diesters, cycloalkanedicarboxylic acid esters, cycloalkene dicarboxylic acid diesters, diethers, ethercarboxylic acids and ether carbonates. The method for producing an olefin polymer according to (1),
( 3 ) The method for producing an olefin polymer according to (1) or (2) above, wherein the homopolymerization reaction of propylene is carried out a plurality of times under different molecular weight modifier concentrations.
(4) A homopolymerization reaction of propylene and an α-olefin having 2 or 4 to 10 carbon atoms are carried out so that the content ratio of the α-olefin is 5% by mass or less. After performing one or more polymerization reactions selected from the copolymerization reactions multiple times under different molecular weight modifier concentrations,
The obtained polymer is copolymerized with propylene and an α-olefin having 2 or 4 to 10 carbon atoms to obtain a propylene block copolymer.
The method for producing an olefin polymer according to (1) or (2) above,
( 5 ) The method for producing an olefin polymer according to any one of (1) to (4) above, wherein the molecular weight modifier is hydrogen.
( 6 ) The external electron donating compound is the following general formula (III);
R ⁵ _q Si (OR ⁶ ) _4-q (III)
(Wherein, 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, a polycyclic amino group, R ⁵ When a plurality of carbon groups are present, they may be the same or different from each other. R ⁶ is an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, and the like. a vinyl group, an allyl group or an aralkyl group, an optionally .q even being the same or different if R ⁶ there are multiple integers of 0 ≦ q ≦ 3.)
Organosilicon alkoxy compound represented by and the following general formula (IV);
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, vinyl groups, allyl groups, aralkyl groups, and cyclos having 3 to 20 carbon atoms. It is a group selected from an alkyl group and an aryl group, and may be the same or different from each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring, and the R ⁷ R ⁸ N group is formed. When there are a plurality of them, they may be the same or different from each other. R ⁹ is a linear alkyl group 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, and 1 carbon group. 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 R ⁹ may be the same or different. S is an integer from 1 to 3.)
The method for producing an olefin polymer according to any one of (1) to (5) above, which is one or more selected from the aminosilane compounds represented by.
( 7 ) The solid catalyst component for olefin polymerization comprises the first internal electron donating compound and the second internal electron donating compound.
Any of the above (1) to (6) obtained by contacting the compounds so as to satisfy the relationship of the molar amount of the first internal electron donating compound> the molar amount of the second internal electron donating compound. The method for producing an olefin polymer according to the above,
( 8 ) Copolymerization of propylene and co-polymerization of propylene having 2 or 4 to 10 carbon atoms and α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of 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 polymerization reactions multiple times under different molecular weight modifier concentrations,
A copolymerization reaction of propylene with α-olefin having 2 or 4 to 10 carbon atoms with respect to the obtained polymer results in a content ratio of α-olefin having 2 or 4 to 10 carbon atoms of 20 to 80% by mass or less. The method for producing an olefin polymer according to the above (1) or (2), as described above.
Is to provide.

According to the present invention, when homopolymerization or copolymerization of olefins is carried out, the polymerization activity of the olefins and the activity against hydrogen at the time of 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 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 or a halogen atom having 1 to 8 carbon atoms, and when a plurality of R ^1s are present, they may be the same or different from each other, and R ² and R ³ have 1 to 8 carbon atoms. It is an alkyl group of 12, which may be the same or different, and when the number j of the substituent R ¹ is 0, 1 or 2, and j is 2, each R ¹ is the same. The first step of contacting with one or more first internal electron donating compounds selected from the aromatic dicarboxylic acid diesters represented by), reacting them, and then washing them is performed. For the resulting product
A solid catalyst component for olefin polymerization obtained by contacting a tetravalent titanium halogen compound with one or more second internal electron donating compounds, reacting them, and then performing a second step of washing.
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(In the formula, 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 or different from each other, Q is a hydrogen atom or a halogen atom, and Q is a plurality. If they exist, they may be the same or different from each other, and p is a real number of 0 <p≤3.)
Organoaluminium compound represented by
Using a catalyst for olefin polymerization formed by contacting with an external electron donating compound,
Polypolymerization reaction of propylene and copolymerization reaction of propylene and α-olefin having 2 or 4 to 10 carbon atoms so that the content ratio of α-olefin having 2 or 4 to 10 carbon atoms is 5% by weight or less. It is characterized in that one or more polymerization reactions selected from the above are carried out a plurality of times under different molecular weight modifier 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 or a halogen atom having 1 to 8 carbon atoms, and 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 substituents R ¹ is 0, 1 or 2, when j is 2, selected from an aromatic dicarboxylic acid diester which each R ¹ is represented by may be the same or different.) After contacting and reacting with one or more of the first internal electron donating compounds, the first step of washing is performed, and the obtained product is subjected to the first step.
It is obtained by subjecting a tetravalent titanium halogen compound to one or more second internal electron donating compounds, reacting them, and then performing 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, dihalogenated magnesium, alkoxymagnesium halide 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.

Among the above magnesium compounds, dialkoxymagnesium may be obtained by reacting metallic magnesium with alcohol in the presence of halogen, halogen-containing metal compound or the like.

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

When a spherical dialkoxymagnesium is used, a polymer powder having a better particle shape (more spherical) and a narrow particle size distribution can be obtained, and the operability of handling the polymer powder produced during the polymerization operation is improved. It can be improved and the occurrence of clogging and the like caused by the fine powder contained in the produced polymer powder can be suppressed.

The spherical dialkoxymagnesium described above does not necessarily have to be a true spherical shape, and an elliptical shape or a potato-shaped one can also be used. Specifically, the circularity of the particles is preferably 3 or less, more preferably 1-2, and even more preferably 1-1.5.
In the documents of the present application, the circularity of the dialkoxymagnesium particles is defined by photographing 500 or more dialkoxymagnesium particles with a scanning electron microscope and processing the photographed particles with image analysis processing software to obtain the area of each particle. Obtain S and the peripheral length L, and calculate the circularity of each dialkoxymagnesium particle by the following formula. Circularity of each dialkoxymagnesium particle = L ² ÷ (4π × S)
It means the arithmetic mean value when calculated by, and the closer the shape of the particle is to a perfect circle, the closer the circularity is to 1.

The average particle size of the dialkoxymagnesium is 1 at the average particle size D ₅₀ (50% of the integrated particle size in the volume integrated particle size distribution) when measured using a laser light scattering diffraction method particle size counter. It is preferably ~ 200 μm, more preferably 5 to 150 μm.
When the 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.

The particle size of dialkoxymagnesium is preferably one with a small amount of fine powder and coarse powder and a narrow particle size distribution.
Specifically, the dialkoxymagnesium preferably contains 20% or less of particles having a size of 5 μm or less, and more preferably 10% or less, when measured using a laser light scattering diffraction method particle size measuring machine. On the other hand, when measured using a laser light scattering diffraction method particle size measuring machine, the content of particles having a size of 100 μm or more is preferably 10% or less, and more preferably 5% or less.
Further, the particle size distribution of dialkoxymagnesium is ln (D ₉₀ / D ₁₀ ) (where D ₉₀ is 90% of the integrated particle size in the volume integrated particle size distribution and D ₁₀ is 10% of the integrated particle size in the volume integrated particle size distribution. The particle size is preferably 3 or less, and more preferably 2 or less.

Examples of the method for producing spherical dialkoxymagnesium include JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-. It is exemplified in Japanese Patent Application Laid-Open 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 suspension at the time of reaction, and the reaction is preferably promoted by being in the form of a solution or suspension. be able to.

When the magnesium compound is a solid, it can be made into a solution magnesium compound by dissolving it in a solvent having a solubilizing ability of the magnesium compound, or it is suspended in a solvent having no solubilizing ability of the magnesium compound. By making it turbid, it can be made into a magnesium compound suspension.
When the magnesium compound is in a liquid state, it may be used as it is as a solution magnesium compound, or it may be further dissolved in a solvent having a solubilizing ability of the magnesium compound and used as a solution magnesium compound. ..

Examples of the compound capable of solubilizing 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, isopropyl benzyl alcohol. , Alcohols with 1 to 18 carbon atoms such as ethylene glycol, halogen-containing alcohols with 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol, methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether , Tetrahydrofuran, ethylbenzyl ether, dibutyl ether, anisole, diphenyl ether and other ethers with 2 to 20 carbon atoms, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, Examples thereof include metal acid esters such as tetrabutoxyzylzyl and tetraethoxyzaldehyde. 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 and unsaturated hydrocarbon solvents that do not dissolve the magnesium compounds.
Since saturated hydrocarbon solvents or unsaturated hydrocarbon solvents are highly safe and industrially versatile, specifically, linear or branched chains having a boiling point of 50 to 200 ° C. such as hexane, heptane, decane, and methyl heptane. Examples thereof include alicyclic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as aliphatic 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. Of these, 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 or different from each other, and r is 0 or 1-3. It is preferable that the compound is one or more of the compounds selected from the titanium halide or alkoxy titanium halide group represented by (they may be the same or different from each other when a plurality of OR ^10s are present).

Examples of the titanium halide include titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide.
Examples of the alkoxytitanium halide include methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, and di-n-butoxytitanium. Examples thereof include dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, tri-n-butoxytitanium chloride and the like.
As the tetravalent titanium halogen compound, titanium tetrahalide is preferable, and titanium tetrachloride is more preferable.
These titanium compounds may be used alone or in combination of two or more.

The solid catalyst component for olefin polymerization used in the present invention has the following general formula (I) in the first step.
(R ¹ ) _j C ₆ H _4-j (COOR ² ) (COOR ³ ) (I)
(In the formula, R ¹ represents an alkyl group or a halogen atom having 1 to 8 carbon atoms, and when a plurality of R ^1s are present, they may be the same or different from each other, and R ² and R ³ have carbon atoms. C1-12 alkyl groups may be the same or different and also, the number j of the substituents R ¹ is 0, 1 or 2, when j is 2, each R ¹ is the same It may be present or different.) Using one or more first internal electron donating compounds selected from aromatic dicarboxylic acid diesters (phthalic acid diesters or phthalic acid diesters having substituents). 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, the alkyl group having 1 to 8 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and t-. Select 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. There are more than one type.

As R ¹ , a methyl group, a bromine atom and a fluorine atom are preferable, and a methyl group and a bromine atom are more preferable.

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 as or different from each other. May be good.

The alkyl groups 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 and 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, It is an n-dodecyl group. Among these, ethyl group, n-butyl group, isobutyl group, t-butyl group, neopentyl group, isohexyl group and isooctyl group can be mentioned, and ethyl group, n-propyl group, n-butyl group, isobutyl group and neopentyl group can be mentioned. Is preferable.

In the aromatic dicarboxylic acid diester represented by the general formula (I), the number j of the substituents ^{R 1} is 0, 1 or 2, (when j is 2) ^{when R 1} there are a plurality, each ^R 1 ( two R ¹⁾ may or may not be the same.
When j is 0, the compound represented by the general formula (I) is a phthalic acid diester, and when j is 1 or 2, the compound represented by the general formula (I) is a substituted phthalic acid diester.
When j is 1, in the aromatic dicarboxylic acid diester represented by the general formula (I), it is preferable that R ¹ is substituted with a hydrogen atom at the 3-position, 4-position or 5-position of the benzene ring.
When j is 2, in the aromatic dicarboxylic acid diester represented by the general formula (I), R ¹ is preferably replaced with a hydrogen atom at the 4- and 5-position positions of the benzene ring.

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, and diisobutyl phthalate. , Di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, di-n-hexyl phthalate, ditexyl phthalate, methyl ethyl phthalate, (ethyl) n-propyl phthalate, ethyl isopropyl phthalate, phthalate Phthalic acid diesters such as (ethyl) n-butyl, ethylisobutyl phthalate, (ethyl) n-pentyl phthalate, ethylisopentyl phthalate, ethylneopentyl phthalate, n-hexyl phthalate, 4-chlorophthalate Diethyl acid, di-n-propyl 4-chlorophthalate, diisopropyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-propyl 4-bromophthalate , Halogen-substituted phthalates such as diisopropyl 4-bromophthalate, di-n-butyl 4-bromophthalate, diisobutyl 4-bromophthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, 4-methylphthalic acid Examples thereof include alkyl-substituted phthalic acid diesters such as diisopropyl, di-n-butyl 4-methylphthalate and diisobutyl 4-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, n-propyl phthalate, ethyl isopropyl phthalate, n-butyl phthalate, ethyl isobutyl phthalate, diethyl 4-methyl phthalate, di-n-propyl 4-methyl phthalate , 4-Methylphthalate diisobutyl, 4-bromophthalate diisobutyl, 4-bromophthalate diisopentyl, 4-bromophthalate dineopentyl, etc. are preferred, and diethyl phthalate, di-n-propyl phthalate, di-n-butyl phthalate, phthalic acid, etc. Diisobutyl, n-propyl phthalate, ethylisopropyl phthalate, n-butyl phthalate, ethylisobutyl phthalate, diethyl 4-methylphthalate, di-n-propyl 4-methylphthalate, 4-methylphthalic acid More preferred are diisobutyl, diisobutyl 4-bromophthalate, diisopentyl 4-bromophthalate and dineopentyl 4-bromophthalate.

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

In the first step, the treatment of contacting and reacting the magnesium compound, the tetravalent titanium halogen compound and the aromatic dicarboxylic acid diester represented by the general formula (I) may be carried out in the presence of an inert organic solvent. preferable.
The inert organic solvent is preferably a liquid at room temperature (20 ° C.) and a boiling point of 50 to 150 ° C., and is an aromatic hydrocarbon compound or an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. at room temperature. Saturated hydrocarbon compounds are more preferred.
Specific examples of the inert organic solvent include linear aliphatic hydrocarbon compounds such as hexane, heptane and decane, branched aliphatic hydrocarbon compounds such as methylheptan, and alicyclic compounds such as cyclohexane, methylcyclohexane and ethylcyclohexane. Formula One or more selected from hydrocarbon compounds, aromatic hydrocarbon compounds such as toluene, xylene, ethylbenzene and the like can be mentioned.
Among the above-mentioned inert organic solvents, the aromatic hydrocarbon compound which is liquid at room temperature and has a boiling point of 50 to 150 ° C. improves the activity of the obtained solid catalyst component and improves the stereoregularity of the obtained polymer. It is suitable because it can be made to grow.

In the solid catalyst component for olefin polymerization used in the present invention, the magnesium compound, the tetravalent titanium halogen compound and the aromatic dicarboxylic acid diester represented by the general formula (I) are appropriately inappropriate in the first step. It can be contacted by mixing in the presence of an active organic solvent.

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.
The temperature at the time of the reaction is preferably 0 to 130 ° C., more preferably 40 to 130 ° C., even more preferably 30 to 120 ° C., and even more preferably 80 to 120 ° C. The reaction time is preferably 1 minute or longer, more preferably 10 minutes or longer, further preferably 30 minutes to 6 hours, further 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 brought into contact with each other at a temperature below room temperature for another 5 minutes to 5 minutes. A aging step of pre-reacting for about 4 hours may be performed.

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 tetravalent titanium halogen compound is used with respect to 1 mol of the magnesium compound. The amount is preferably 0.5 to 100 mol, more preferably 1 to 50 mol, and even more preferably 1 to 10 mol.

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, it 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 0.01 to 10 mol, more preferably 0.01 to 1 mol, still more preferably 0.02 to 0.6 mol. ..
When the Inactive Organic Solvent is used in the first step, the amount of the Inactive Organic Solvent used is preferably 0.001 to 500 mol, preferably 0.5 to 100 mol, based on 1 mol of the magnesium compound. Is more preferable, and 1.0 to 20 mol is further preferable.

In the first step, the contact of each component is preferably carried out in a container equipped with a stirrer while stirring in an inert gas atmosphere and in a state where water and the like are removed.
After completion of the above reaction, the reaction product is washed by allowing the reaction solution to stand still, appropriately removing the supernatant liquid to make it wet (slurry), or further drying it by hot air drying or the like. Is preferable.

After completion of the above reaction, the reaction solution is allowed to stand, the supernatant solution is appropriately removed, and the obtained reaction product is washed.
The above cleaning treatment is usually performed using a cleaning liquid.
Examples of the cleaning liquid include the same as the above-mentioned inert organic solvent appropriately used in the first step, which is a liquid at room temperature such as hexane, heptane, and decan, and has a linear boiling point of 50 to 150 ° C. Liquid at room temperature such as aliphatic hydrocarbon compounds, methylcyclohexane and ethylcyclohexane, and at room temperature such as cyclic aliphatic hydrocarbon compounds having a boiling point of 50 to 150 ° C., toluene, xylene, ethylbenzene, orthodichlorobenzene and the like. It is preferably one or more selected from liquid and aromatic hydrocarbon compounds having a boiling point of 50 to 150 ° C.
By using the above cleaning solution, 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 cleaning 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. , 30 to 110 ° C., more preferably 50 to 110 ° C., and even more preferably 50 to 100 ° C.

In the solid catalyst component for olefin polymerization used in the present invention, the cleaning treatment is carried out by adding a desired amount of cleaning liquid to the reaction product, stirring the mixture, and then using a filtration method (filtration method) or a decantation method. It is preferably carried out by removing the liquid phase.
Further, as described later, when the number of washings is a plurality of times (twice or more), the washing liquid added last to the reaction product can be directly used for the reaction in the next step without being removed. ..

In the first step, the amount of the washing 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 a plurality of times, and the number of washings is preferably 1 to 20 times, more preferably 2 to 15 times, still more preferably 2 to 10 times.
Even when the number of washings is a plurality of times, it is preferable to use the above-mentioned amount of the washing liquid for each washing.
In the solid catalyst component for olefin polymerization used in the present invention, unreacted raw material components and reactions remaining in the reaction product are formed by contacting and reacting each component in the first step and then performing a washing treatment. It is possible to remove impurities of by-products (alkoxytitanium halide, titanium tetrachloride-carboxylic acid complex, etc.).

In the solid catalyst component for olefin polymerization used in the present invention, the first step includes a form in which a post-treatment is appropriately performed after the washing treatment. In the method for producing a solid catalyst component for olefin polymerization of the present invention, the above post-treatment may be performed in the first step, and then the second step described below may be applied to the obtained product. It is preferable to carry out the second step as it is without performing post-treatment or the like.

After the reaction in the first step is completed, the suspension after the washing treatment may be allowed to stand as appropriate to remove the supernatant liquid to make it wet (slurry), or further to dry it by hot air drying or the like. , The suspension may be subjected to the second step as it is. When the suspension is subjected to the second step as it is, the drying treatment can be omitted and the addition of the 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 above-mentioned first step, and a tetravalent titanium halogen compound and one or more second internal electron donating compounds are applied to the obtained product. It is obtained by performing a second step of cleaning after contacting and reacting with.

In the solid catalyst component for olefin polymerization used in the present invention, examples of the tetravalent titanium halogen compound used in the second step include those similar to 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. It is appropriate that there is more than one kind. Examples of electron donating sites are hydroxyl groups (-OH), carbonyl groups (> C = O), ether bonds (-OR), amino groups (-NH ₂ , -NHR, -NHRR'), cyano groups (-CN). ), Isocyanate group (-N = C = O), amide bond (-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), and a carbonate group (-C (= O) R). -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 may 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). Among the group dicarboxylic acid diesters, an aromatic dicarboxylic acid diester different from the first internal electron donating compound, (3) alkyl-substituted malonic acid diester, (4) cycloalkane dicarboxylic acid ester, and (5) cycloalkene dicarboxylic acid diester. , (6) Diethers, (7) Ethercarboxylic acids, and (8) Ether carbonates.

Examples of the polycarboxylic acid esters used in the second step include carboxylic acid diesters and substituted carboxylic acid diesters in which a part of hydrogen atoms bonded to carbon atoms forming a molecular skeleton are replaced 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 aliphatic dicarboxylic acid diesters such as glutaric acid diester. Examples thereof include a cycloalkanedicarboxylic acid diester and an alicyclic dicarboxylic acid diester of a cycloalkenedicarboxylic acid diester.
Specific examples of the substituted carboxylic acid diester include 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, and an iodine atom, and a hydrogen atom having 1 to 8 carbon atoms. Examples thereof include an alkyl-substituted carboxylic acid diester substituted with an alkyl group of the above, a halogenated alkyl-substituted carboxylic acid diester 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 cycloalkane dicarboxylic acid diester having a substituent and a substituted malon in which a part of the hydrogen atom of the cycloalkyl group constituting the cycloalkane dicarboxylic acid diester is substituted with an alkyl group or the like. Examples thereof 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 may be the same as the aromatic dicarboxylic acid diester defined by the general formula (I) described above. Can be done.

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

When maleic acid diester is used as the second internal electron donating compound, the maleic acid diesters include diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-n-butyl maleate, and diisobutyl maleate. , Di-n-pentyl maleate, dineopentyl maleate, dihexyl maleate, dioctyl maleate and the like can be exemplified, and among these, diethyl maleate, di-n-butyl maleate, and diisobutyl maleate are preferable. ..
When an alkyl-substituted maleic acid diester is used as the second internal electron donating compound, the alkyl-substituted maleic acid diesters include diethyl isopropylbromomaleate, diethylbutylbromomaleate, diethylisobutylbromomaleate, diethyl diisopropylmaleate, Dibutyl maleate diethyl, diisobutyl maleate diethyl, diisopentyl maleate diethyl, isopropylisobutyl maleate diethyl, isopropylisopentyl maleate dimethyl, (3-chloro-n-propyl) maleate diethyl, bis (3-bromo-n) -Propyl) diethyl maleate, dibutyl dimethyl maleate, dibutyl diethyl maleate and the like can be exemplified, and among these, dibutyl dimethyl maleate, dibutyl diethyl maleate and diethyl diisobutyl maleate are preferable.

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

As the alkyl-substituted malonic acid diester, dialkylmalonic acid diester or alkylidenemalonic acid diester is preferable, and dialkylmalonic acid diesters such as ethylcyclopentylmalonic acid dimethyl, ethylcyclopentylmalonic acid diethyl, diisobutylmalonic acid dimethyl, and diisobutylmalonate diethyl, and benzylidene are used. Alkylidene malonic acid diesters such as dimethyl malonate and diethyl benziliden malonate are more preferred.

When a cycloalcandicarboxylic acid diester is used as the second internal electron donating compound, the cycloalcandicarboxylic acid diester includes cyclopentane-1,2-dicarboxylic acid diester, cyclopentane-1,3-dicarboxylic acid diester, and 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, cyclononan-1,3-dicarboxylic acid diester, cyclodecane-1,2-dicarboxylic acid diester, norbornan-1,3-dicarboxylic acid Examples include acid diesters.

Further, as the second internal electron donating compound, a cycloalkanedicarboxylic acid diester having a substituent in which a part of the hydrogen atom of the cycloalkyl group constituting the cycloalkanedicarboxylic acid diester is substituted with an alkyl group or the like is used. When the cycloalkane dicarboxylic acid diester having the substituent is used, 3-methylcyclohexane-1,2-dicarboxylic acid diethyl, 4-methylcyclohexane-1,2-dicarboxylic acid diethyl, 5-methylcyclohexane-1,2 Examples thereof include diethyl dicarboxylic acid, diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid, and di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylic acid.

When a cycloalkene dicarboxylic acid diester is used as the second internal electron donating compound, cyclopentene dicarboxylic acid diester, cyclohexene dicarboxylic acid diester, cyclohexene dicarboxylic acid diester, cyclooctene dicarboxylic acid diester, norbornene dicarboxylic acid diester, dicyclopentadiene. Examples thereof include a dicarboxylic acid diester, a cyclodecene dicarboxylic acid diester, a biphenyldicarboxylic acid diester, and the like, and specific examples thereof include 1-cyclohexene-1,2-dicarboxylic acid diester, 4-cyclohexene-1,2-dicarboxylic acid diester, and norbornene dicarboxylic acid. One or more selected from the acid diester is preferable.

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) CO- (CR ¹² R ¹³ ) _m- O-CR ¹⁴ _n H _(3-n) (VI)
(In general formula (VI), R ¹¹ and R ¹⁴ are halogen atoms or organic groups having 1 to 20 carbon atoms, which may be the same or different from each other, and R ¹² and R ¹³ are hydrogen. Atoms, oxygen atoms, sulfur atoms, halogen atoms or organic groups having 1 to 20 carbon atoms, which may be the same or different from each other. Organic groups having 1 to 20 carbon atoms are oxygen atoms and fluorine atoms. , Chlorine atom, bromine atom, iodine atom, nitrogen atom, sulfur atom, phosphorus atom, and boron atom may contain at least one atom, and there are a plurality of organic groups having 1 to 20 carbon atoms. case, a plurality of organic groups may be bonded together to form a ring, k is an integer of 0 to 3, when k is an integer of 2 or more, R ¹¹ to plural present also identical to one another They may be different, m is an integer of 1 to 10, and when m is an integer of 2 or more, a plurality of R ¹² and R ¹³ may be the same or different, and n is 0 to 3. When n is an integer of 2 or more, the plurality of R ^14s existing may be the same or different from each other.)
A compound represented by is used.
In the compound represented by the general formula (VI), when R ¹¹ or R ¹⁴ is a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be mentioned, and a fluorine atom, a chlorine atom or a bromine atom is preferable. Is.

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

When a plurality of organic groups having 1 to 20 carbon atoms are present in the compound represented by the general formula (VI), the plurality of organic groups may be bonded to each other to form a ring. In this case, the plurality of organic groups constituting the ring, ⁽¹⁾ (when k is 2 or more) ^{R 11} with each other, ⁽²⁾ (when n is 2 or more) ^{R 14} each other, (3) R ^{12 to} each other (when m is 2 or more), (4) R ^{13 to} each other (when m is 2 or more), (5) R ¹¹ and R ¹² , (6) R ¹¹ and R ¹³ , (7) R ^{The combinations of 11} and R ¹⁴ , (8) R ¹² and R ¹³ , (9) R ¹² and R ¹⁴ , and (10) R ¹³ and R ¹⁴ can be mentioned, of which (8) R ¹² and R ¹³ Is preferable, and it is more preferable that R ¹² and R ¹³ are 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-isopropylfluorene and the like, preferably 2,2-diisobutyl-1,3-dimethoxypropane, 2- Isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 3,3-bis (methoxymethyl) -2,6-dimethylheptane, 9,9-bis Examples thereof include (methoxymethyl) fluorene, and more preferably 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 3,3-bis (methoxymethyl). ) -2,6-Dimethylheptane, 9,9-bis (methoxymethyl) fluorene, one or more selected. Among the above, 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. If k is an integer of 2 or more, R ¹¹ may be the same to each other there exist a plurality, it may be different.
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 existing may be the same as each other or may be 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 ^14s existing may be the same as each other or may be different from each other.

When ether carbonates are used as the second internal electron donating compound, the ether carbonates are represented by the following general formula (VII).
R ^15- OC (= 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, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, branched halogen-substituted alkyl group having 3 to 20 carbon atoms, linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, 3 to 20 carbon atoms. 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, halogen-substituted cycloalkenyl groups having 3 to 20 carbon atoms Group, aromatic hydrocarbon group having 6 to 24 carbon atoms, halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms having a carbon atom at the bond end (however, (Excluding those having a C = N group at the bond end), an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms having a carbon atom at the bond end (excluding those having a carbonyl group at the bond end), or a bond It shows a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms with a carbon atom at the end (excluding those having a C = P group at the bond end), and R ¹⁵ and R ¹⁶ are the same but different. Also, Z may indicate a compound represented by a carbon atom or a bonding group bonded via a carbon chain.).

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, Examples thereof include n-pentyl group, n-hexyl group, n-pentyl group, n-octyl group, n-nonyl group, n-decyl group and the like, 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, 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 may be used. Examples thereof include branched alkyl groups having 3 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a linear alkenyl group having 3 to 20 carbon atoms, for example, an allyl group, a 3-butenyl group, a 4-hexenyl group, a 5-hexenyl group, a 7-octenyl group, a 10-dodecenyl group. Etc., preferably a linear alkenyl group having 3 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a branched alkenyl group having 3 to 20 carbon atoms, for example, an isopropenyl group, an isobutenyl group, an isopentenyl group, a 2-ethyl-3-hexenyl group and the like can be mentioned, preferably having 3 carbon atoms. Examples include ~ 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 methyl halide group, an ethyl halide group, an n-propyl halogenated group, an n-butyl halogenated group, or a halogen. Examples thereof include n-pentyl halide group, n-hexyl halogenated group, n-pentyl halogenated group, n-octyl halide group, nonyl halogenated group, decyl halide 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 can be mentioned.

When R ¹⁵ or R ¹⁶ is a branched halogen-substituted alkyl group having 3 to 20 carbon atoms, examples thereof include an isopropyl halide group, an isobutyl halide group, a 2-ethylhexyl halogenated group, and a neopentyl halogenated group, which are preferable. Examples include branched halogenated alkyl groups 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, 2-vinyl halide group, 3-allyl halide group, 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 and the like can be mentioned, preferably having 2 carbon atoms. Examples include ~ 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. Examples thereof include a -3-ethyl-4-hexenyl group and a 3-halogenated isobutenyl group, and preferably a branched halogen-substituted alkenyl group having 3 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a cycloalkyl group having 3 to 20 carbon atoms, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a tetramethylcyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group. , Cyclononyl group, cyclodecyl group, butylcyclopentyl group and the like, and 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, for example, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a norbornene group, etc. can be mentioned, preferably having 3 carbon atoms. Included are ~ 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 thereof 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, a halogen-substituted butylcyclopentyl group, and the like, preferably a halogen-substituted cyclo having 3 to 12 carbon atoms. Alkyl groups can be 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 cyclo Examples thereof include 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. Substituted cycloalkenyl groups can 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. Ethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, trill group, xsilyl group, naphthyl group, 1,8-dimethylnaphthyl group and the like are preferable. Examples include aromatic hydrocarbon groups having 6 to 12 carbon atoms.

When R ¹⁵ or R ¹⁶ is a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, it is a phenyl halide group, a methylphenyl halide group, a methylphenyl trihalogenated group, a benzyl perhalogenated group, or a perhalogenated group. Examples thereof include a phenyl group, an ethyl 2-phenyl-2-halogenated group, a naphthyl perhalogenated group, a butyl 4-phenyl-2,3-dihalogenated group and the like, preferably halogen-substituted aromatic carbide having 6 to 12 carbon atoms. A hydrogen group can be 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 or an iodine atom. Preferred are fluorine atom, chlorine atom or bromine atom.

Further, when R ¹⁵ or R ¹⁶ is a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms whose bond end is a carbon atom (excluding those whose bond end 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, ditril Examples thereof include a diarylphosphinoalkyl group such as a phosphinomethyl group, a phosphino group-substituted aryl group such as a dimethylphosphinophenyl group and a diethylphosphinophenyl group, and preferably a phosphorus-containing hydrocarbon group having 2 to 12 carbon atoms. Be 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.

Examples of R ¹⁵ include 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 a branched alkenyl group having 3 to 12 carbon atoms, and 1 to 1 carbon atoms. Twelve linear halogen-substituted alkyl groups, branched halogen-substituted alkyl groups having 3 to 12 carbon atoms, linear halogen-substituted alkyl groups or branched halogen-substituted alkyl groups having 3 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms A group, a cycloalkenyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, a halogen-substituted cycloalkylalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms is preferable. ,
Linear alkyl group with 1 to 12 carbon atoms, branched alkyl group with 3 to 12 carbon atoms, vinyl group, linear alkenyl group or branched alkenyl group with 3 to 12 carbon atoms, linear chain with 1 to 12 carbon atoms 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
Linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and aromatic hydrocarbon groups having 6 to 12 carbon atoms are more preferable.

Examples of R ¹⁶ include a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms having a bond end of −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 having a bond end of −CH ₂ −, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, and a branched alkenyl group having 3 to 12 carbon atoms having a bond terminal of −CH ₂ −. Halogen-substituted alkyl group, linear halogen-substituted alkenyl group having 3 to 12 carbon atoms, branched halogen-substituted alkenyl group having 3 to 12 carbon atoms having a bond end of −CH ₂ −, carbon having a bonding end of −CH ₂ − 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 end -CH ₂ - and is halogen-substituted cycloalkenyl group having 4 to 12 carbon atoms or a bond terminus, are -CH ₂ - is preferably an aromatic hydrocarbon group having 7 to 12 carbon atoms is, having 1 to 12 carbon atoms linear alkyl groups, bonded terminally -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, bonds end -CH ₂ - can be straight chain 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 - carbon atoms is 3 12 branch 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 A halogen-substituted cycloalkyl group having 4 to 12 carbon atoms having −CH ₂ −, a halogen-substituted cycloalkenyl group having 4 to 12 carbon atoms having a bond end of −CH ₂ −, or a carbon having a bond terminal of −CH ₂ −. An aromatic group having a number of 7 to 12 is more preferable, a linear hydrocarbon group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms having a bond end of −CH ₂ −, or a bonded terminal. An aromatic group hydrocarbon group having 7 to 12 carbon atoms in which is −CH ₂ − 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 preferable combination of the above-mentioned groups, and a more preferable combination of the groups is preferable.

In the compound represented by the general formula (VII), Z is a divalent bonding group that bonds a carbonate group and an ether group (OR ¹⁶ groups), and is a bonding group that is bonded via a carbon atom or a carbon chain. For example, a bonding group that bonds two oxygen atoms to which Z is bonded with a carbon chain can be mentioned, 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 having 1 to 20 carbon atoms. Linear halogen-substituted alkylene group, branched halogen-substituted alkylene group having 3 to 20 carbon atoms, linear halogen-substituted alkenylene group having 3 to 20 carbon atoms or branched halogen-substituted alkenylene group, cycloalkylene group having 3 to 20 carbon atoms, Cycloalkenylene group having 3 to 20 carbon atoms, halogen-substituted cycloalkylene group having 3 to 20 carbon atoms, halogen-substituted cycloalkenylene group having 3 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 24 carbon atoms, 6 to 20 carbon atoms It is a halogen-substituted aromatic hydrocarbon group of 24, a nitrogen atom-containing hydrocarbon group having 1 to 24 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 24 carbon atoms, or a phosphorus-containing hydrocarbon group having 1 to 24 carbon atoms. Is preferable.

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, and a linear halogen substitution having 2 to 12 carbon atoms. An alkylene group, a branched halogen-substituted alkylene group having 3 to 12 carbon atoms, a linear halogen-substituted alkenylene group having 3 to 12 carbon atoms or a branched halogen-substituted alkenylene group, a cycloalkylene group having 3 to 12 carbon atoms, and 3 to 12 carbon atoms. Cycloalkenylene group, halogen-substituted cycloalkylene group having 3 to 12 carbon atoms, halogen-substituted cycloalkenylene group having 3 to 12 carbon atoms, aromatic hydrocarbon group having 6 to 12 carbon atoms, halogen-substituted aromatic group having 6 to 12 carbon atoms. Group hydrocarbon groups, nitrogen atom-containing hydrocarbon groups having 2 to 12 carbon atoms, oxygen atom-containing hydrocarbon groups having 2 to 12 carbon atoms, or phosphorus-containing hydrocarbon groups having 2 to 12 carbon atoms are particularly preferable groups. , It is more preferable that it is a bidentate binding group selected from an ethylene group having 2 carbon atoms and a branched alkylene group having 3 to 12 carbon atoms (note that the bidentate binding group is two groups to which Z is bonded. It means that the oxygen atoms 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, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, or a 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 used.
When it is a 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 Examples thereof include a group, preferably a branched alkylene group having 3 to 12 carbon atoms, and more preferably a 1-methylethylene group, a 2-methylethylene group, and a 1-ethylethylene group.

When Z is a linear alkenylene group having 3 to 20 carbon atoms, for example, a propenylene group, a butenylene group, a hexenylene group, an octenylene group, an octadecenylene group and the like can be mentioned, and a linear chain having 3 to 12 carbon atoms is preferable. An alkenylene group can be mentioned.

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

When Z is a linear halogen-substituted alkylene group having 1 to 20 carbon atoms, for example, a dichloromethylene group, a chloromethylene group, a dichloromethylene group, a tetrachloroethylene group and the like can be mentioned, and a direct group having 3 to 12 carbon atoms is preferable. Examples thereof include a chain halogen-substituted alkylene group, and more preferably, a chloroethylene group, a fluoroethylene group, a dichloroethylene group, a difluoroethylene group and a tetrafluoroethylene group.

When Z is a branched halogen-substituted alkylene group having 1 to 20 carbon atoms, for example, a 1,2-bischloromethylethylene group, a 2,2-bis (chloromethyl) propylene group, and a 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 and the like. A branched halogen-substituted alkylene group having 3 to 12 carbon atoms is preferable, and a 1-chloroethylethylene group, a 1-trifluoromethylethylene group, and a 1,2-bis (chloromethyl) ethylene group are more preferable. Can be 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. These include, preferably, a linear halogen-substituted alkenylene group having 3 to 12 carbon atoms, and more preferably, a dichloroethenylene group and a difluoroethenylene group.

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. Examples thereof include -1,2-propylene group, preferably a branched halogen-substituted alkylene group having 3 to 12 carbon atoms, and more preferably a chloromethylethenylene group, a trifluoromethylethenylene group, 3,4. -Dichloro-1,2-butenylene group can be mentioned.

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, Examples thereof include a 2,3-dimethylcyclopentylene group, a 1,3,3-trimethylcyclohexylene group and a cyclooctylene group, preferably a cycloalkylene group having 3 to 12 carbon atoms, and more preferably. Examples thereof include a 1,2-cycloalkylene group or a hydrocarbon group-substituted-1,2-cycloalkylene group.

When Z is a cycloalkenylene group having 3 to 20 carbon atoms, for example, a cyclopentenylene group, a 2,4-cyclopentadienylene group, a cyclohexenylene group, a 1,4-cyclohexadienylene group, a cyclohep Examples thereof include a tenylene group, a methylcyclopentenylene group, a methylcyclohexenylene group, a methylcycloheptenylene group, a dicyclodecylene group, a tricyclodecylene group, and the like, preferably a cycloalkenylene group having 3 to 12 carbon atoms. More preferably, 1,2-cycloalkenylene group or hydrocarbon group-substituted-1,2-cycloalkenylene group can be mentioned.

When Z is a halogen-substituted cycloalkylene group having 3 to 20 carbon atoms, for example, a 3-chloro-1,2-cyclopentylene group and a 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-cycloocty Examples thereof include a len group, and preferably, a halogen-substituted cycloalkylene group having 3 to 12 carbon atoms can be mentioned.

When Z is a halogen-substituted cycloalkenylene group having 3 to 20 carbon atoms, for example, 5-chloro-1,2-cyclo-4-hexenylene group, 3,3,4,5-tetrafluoro-1,2-cyclo Examples thereof include a -6-octenylene group, and preferably a halogen-substituted cycloalkenylene group having 3 to 12 carbon atoms.

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. Examples thereof include −naphthylene, 2,3-naphthylene, 5-methyl-1,2-naphthylene, 9,10-phenylene, 1,2-anthrasenylene 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 thereof include 6-dichloro-9,10-phenylene, 5,6-dichloro-1,2-anthrasenylene, 5,6-difluoro-1,2-anthrasenylene and the like, preferably a halogen-substituted fragrance having 6 to 12 carbon atoms. Group hydrocarbon groups can be mentioned.

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 Examples thereof include a −propylene group, a 2-ethylamino-1,3-propylene group, a 4-dimethylamino-1,2-phenylene group, a 4,5-bis (dimethylamino) phenylene group, and the like, preferably having 2 carbon atoms. Examples include ~ 12 nitrogen atom-containing hydrocarbon groups.

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-propanol group, 2-ethoxy-1,3-propanilen group, Examples thereof include a 2-t-butoxy-1,3-propanol group, a 2,3-dimethoxy-2,3-butylene group, a 4-methoxy-1,2-phenylene group, and the like, preferably having 2 to 12 carbon atoms. Oxygen atom-containing hydrocarbon groups can be 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-propanol 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 and the like can be mentioned, and a phosphorus-containing hydrocarbon group having 1 to 12 carbon atoms is preferable.

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. The two oxygen atoms are bonded by a carbon chain, and the bonding group in which the carbon chain is composed of two carbon atoms is a group in which two adjacent carbon chains in the cyclic carbon chain are formed. It means that it is a carbon chain between two oxygen atoms to which the 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.

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

As the 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 consisting of any of the above (1) to (5) is used as the combination of the first internal electron donating compound and the second internal electron donating compound, MFR, stereoregularity, and molecular weight distribution are used. It is possible to easily produce a homopolymer or a copolymer having a moderately wide range.

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 in the second step. It is obtained by contacting and reacting a donor compound.
In the second step, the tetravalent titanium halogen compound and the second internal electron donating compound are preferably mixed in the presence of an inert organic solvent similar to that exemplified in the first step, as appropriate. Can be contacted with.

The conditions for contacting and reacting each component in the second step are not particularly limited, and specific examples thereof 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 were contacted and reacted with the reaction product obtained in the first step (added in the first step). The amount of the tetravalent titanium halogen compound used per 1 mol of the magnesium compound is preferably 0.1 to 50 mol, more preferably 0.2 to 20 mol, and 0.3 to 10 mol. Is even more preferable.

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). The molar ratio of the amount of the second internal electron donating compound used to 1 mol of the magnesium compound (molar amount of the second internal electron donating compound / molar amount of the magnesium compound) is 0.001 to 10. It is preferably 0.001 to 1, more preferably 0.002 to 1, more preferably 0.002 to 0.6, and 0.003 to 0.6. It is more preferable to have.

The solid catalyst component for olefin polymerization is the above-mentioned first internal electron donating compound and second internal electron donating compound, and the molar amount of the first internal electron donating compound> the second internal electron donating compound. It is preferably obtained by contacting the compounds so as to satisfy the relationship of molar amounts.

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). The molar ratio of the amount of the second internal electron donating compound used to 1 mol of the aromatic dicarboxylic acid diester represented by the general formula (I), which is the first internal electron donating compound (second internal electron donating). The molar amount of the sex compound / the molar amount of the aromatic dicarboxylic acid diester represented by the general formula (I), which is the first internal electron donating compound), is preferably 0.01 to 0.9. It is more preferably 01 to 0.6, and even more preferably 0.02 to 0.4.

The ratio represented 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) which is the first internal electron donating compound is within the above range. , It becomes easy to suppress the excessive formation of a complex compound composed of a second internal electron donating compound and a tetravalent titanium halogen compound, and when the olefins are polymerized using the obtained solid catalyst component, The polymerization activity and stereoregularity can be easily improved.

When the Inactive Organic Solvent is used in the second step, the amount of the Inactive Organic Solvent used is 0.001 to 500 mol per 1 mol of the magnesium compound (added in the first step). Is more preferable, 0.5 to 100 mol is more preferable, and 1.0 to 20 mol is further preferable.

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

In the second step, the contact of each component is preferably carried out while stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where water and the like are removed.
After the above reaction is completed, it is preferable that the reaction solution is allowed to stand, the supernatant liquid is appropriately removed to form a wet state (slurry form), and the reaction solution is further dried by hot air drying or the like before washing.

In the second step, after the above reaction is completed, the obtained reactant is washed.
The above cleaning treatment is usually performed using a cleaning liquid. Examples of the cleaning liquid include those similar to those exemplified in the first step.
The treatment temperature, treatment method, amount of cleaning liquid used, number of cleanings, etc. in the second cleaning step are the same as those in the cleaning treatment in the first step described above.
In the solid catalyst component for olefin polymerization used in the present invention, unreacted raw material components and reactions remaining in the reaction product are formed by contacting and reacting each component in the second step and then performing a washing treatment. It is possible to remove impurities of by-products (alkoxytitanium halide, titanium tetrachloride-carboxylic acid complex, etc.).

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

After the reaction in the second step is completed, the suspension after the washing treatment may be allowed to stand as appropriate to remove the supernatant liquid to make it wet (slurry), or further to dry it 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 the tetravalent titanium halogen compound is brought into contact with the suspension to carry out a reaction treatment. Before or after contacting the tetravalent titanium halogen compound with the suspension, the first internally electron-donating compound represented by the general formula (I), which is the first internally electron-donating compound, is subjected to-. After contacting at 20 to 130 ° C., washing with an inert organic solvent is performed 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 subjected to a tetravalent titanium halogen compound and a second internal electron donating property in the presence of an inert organic solvent. The compounds are contacted at 20 to 130 ° C., preferably 30 to 120 ° C., more preferably 80 ° C. to 110 ° C., subjected to a reaction treatment, and then washed with an inert organic solvent to obtain a solid reaction product (β). .. The process of contacting and reacting with the tetravalent titanium halogen compound and washing 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 addition step, the tetravalent titanium halogen compound is not used as an addition step. A reaction step with an active solvent may be carried out, or a reaction step with an electron-donating compound and an inert solvent may be further carried out.

In the method for producing a solid catalyst component for olefin polymerization of the present invention, the contact and reaction of each component in the first step may be carried out 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} 10000 cm). Stokes), more preferably 0.03 to ⁵ cm ² / s (3 to 500 cm Stokes), liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

The chain polysiloxane includes hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, hexaphenyldisiloxane 1,3-divinyltetramethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, and 1 as disiloxane. , 3-Dibromotetramethyldisiloxane, chloromethylpentamethyldisiloxane, 1,3-bis (chloromethyl) tetramethyldisiloxane, and dimethylpolysiloxane and methylphenylpolysiloxane as polysiloxanes other than disiloxane are partially hydrogenated. As the modified polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used, and as the cyclic polysiloxane, hexamethylcyclodisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6 -Trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and examples of the modified polysiloxane include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Will be done. 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 atoms 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% by mass, preferably 0.5 to 5.0% by mass, and 0.5. ~ 3.0% by mass is more preferable.
In the solid catalyst component for olefin polymerization used in the present invention, the content of halogen atoms 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% by mass. Mass% is more preferred.
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 0. 5 to 20% by mass is 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 0. 5 to 10% by mass is 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. It is more preferably 0 to 25% by mass, and further preferably 6.0 to 25% by 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. 45-75% by mass, content of first internal electron donating compound is 2 to 20% by mass, content of second internal electron donating compound is 0.3 to 10% by mass, first internal electron donating When the total amount of the sex compound and the second internal electron donating compound is 6.0 to 25% by mass, the performance as a solid catalyst component can be exhibited in a well-balanced manner.

In the present application documents, the content of magnesium atom in the solid catalyst component means a value measured by an EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.
In the present application documents, the content of titanium atoms in the solid catalyst component means a value measured according to the method (oxidation-reduction titration) described in JIS 8311-1997 "Titanium quantification method in titanium ore". To do.
In the present application documents, 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, then fractionating a predetermined amount and using a silver nitrate standard solution to obtain halogen atoms. It shall mean the value measured by the silver nitrate titration method for titrating.
In the present application documents, 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 compound in the solid catalyst component. The total content of the sex compound shall mean the 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 compounds constituting the catalyst for olefin polymerization are described in the following general formula (II).
R ⁴ _p AlQ _3-p (II)
(In the formula, 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 or different from each other, Q is a hydrogen atom or a halogen atom, and Q is a plurality. If they exist, they may be the same or different from each other, and p is a real number of 0 <p≤3.)
It is characterized in that it is formed by contacting an organoaluminum compound represented by (1) and an external electron donating compound.

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, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , Isobutyl group and the like.

In the organic aluminum compound represented by the general formula (II), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be mentioned.

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 is a real number of 2 ≦ p ≦ 3. Is more preferable.

The organic aluminum compound represented by the general formula (II) is specifically selected from triethylaluminum, diethylaluminum chloride, triisobutylaluminum, trin-butylaluminum, trin-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, and specific examples thereof include alcohols, phenols, ethers and esters. Kinds, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organic silicon compounds, especially organic silicon compounds with Si—OC bonds or aminosilanes with Si—NC bonds. Examples include compounds.

Among the above external electron donating compounds, esters such as ethyl benzoate, ethyl p-methoxy benzoate, ethyl p-ethoxy benzoate, methyl p-toluic acid, ethyl p-toluic acid, methyl anisate, ethyl anisate and the like. , 1,3-Diethers, organic silicon compounds containing Si—OC bonds, aminosilane compounds containing Si—NC bonds are preferred, and organic silicon compounds having Si—OC bonds, Si—N— Aminosilane compounds having a C bond are particularly preferable.

Among the external electron donating compounds, the organosilicon compound having a Si—OC bond is described in the following general formula (III).
R ⁵ Si (OR ⁶ ) _4-q (III)
(Wherein, 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, a polycyclic amino group, R ⁵ When a plurality of carbon groups are present, they may be the same or different from each other. R ⁶ is an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, and the like. a vinyl group, an allyl group or an aralkyl group, an optionally .q even being the same or different if R ⁶ there are multiple integers of 0 ≦ q ≦ 3.)
Examples thereof include an organosilicon alkoxy compound represented by.

Among the external electron donating compounds, the aminosilane compound having a Si—NC bond is described in the following general formula (IV).
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, vinyl groups, allyl groups, aralkyl groups, and cyclos having 3 to 20 carbon atoms. It is a group selected from an alkyl group and an aryl group, and may be the same or different from each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring, and the R ⁷ R ⁸ N group is formed. When there are a plurality of them, they may be the same or different from each other. R ⁹ is a linear alkyl group 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, and 1 carbon group. 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 R ⁹ may be the same or different. S is an integer of 1 to 3).

Examples of the organic silicon compound represented by the general formula (III) or the general formula (IV) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, and (alkylamino). ) Alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (Alkylamino) silane and the like can be mentioned. 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 (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotri Examples thereof include ethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and among others, n-propyltriethoxysilane. , Phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetra Methoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotriethoxysilane One or more selected from the above can be mentioned.

In the olefin polymerization catalyst used in the present invention, the content ratios of the olefin polymerization solid catalyst component, the organoaluminum compound and the external electron donating compound are arbitrarily selected within the range in which the effect of the present invention can be obtained. The amount of the organoaluminum compound is preferably 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atoms in the solid catalyst component for olefin polymerization, although it is not particularly limited. Is more preferable. The amount of 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 1 mol of the organoaluminum compound. It is more preferable to have.

The catalyst for olefin polymerization used in the present invention can be produced by contacting the solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donating compound by a known method.
The order in which each of the above components is brought into contact is arbitrary, but for example, the following contact order can be exemplified.
(I) Solid catalyst component for olefin polymerization → External electron donating compound → Organoaluminium compound (ii) Organoaluminium compound → External electron donating compound → Solid catalyst component for olefin polymerization (iii) External electron donating compound → Solid catalyst component for olefin polymerization → Organic aluminum compound (iv) External electron donating compound → Organic aluminum compound → Solid catalyst component for olefin polymerization The contact examples (i) to ( In iv), contact example (ii) is preferable.
In the above contact examples (i) to (iv), "→" means the contact order, and for example, "the solid catalyst component for olefin polymerization-> the organoaluminum compound-> the external electron donating compound" This means that the organoaluminum compound is added to the solid catalyst component for olefin polymerization and brought into contact with the organic aluminum compound, and then the external electron donating compound is added and brought into contact with the compound.

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

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

In the method for producing an olefin polymer of the present invention, the olefins to be polymerized are propylene alone or propylene and an α-olefin having 2 or 4 to 10 carbon atoms (an α-olefin having 2 to 10 carbon atoms). Of which, 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, and specifically, ethylene, 1-butene, 1-pentene, 4 -Methyl-1-pentene, vinylcyclohexane and the like can be mentioned.
When performing a copolymerization reaction between propylene and an α-olefin having 2 or 4 to 10 carbon atoms, one or more kinds of α-olefins having 2 or 4 to 10 carbon atoms are used, and multiple times (many times). In the stepwise polymerization, different step-by-step α-olefins may be used along with propylene.

(2) When the copolymerization reaction of propylene with 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 carried out so that the content ratio of the constituent unit derived from the α-olefin having 2 or 4 to 10 carbon atoms is 4% by mass or less. It is more preferable that the copolymerization reaction is carried out so that the content ratio 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 α-olefin having 2 or 4 to 10 carbon atoms is carried out, the number of carbon atoms is 2 with respect to the total amount of propylene used and α-olefin having 2 or 4 to 10 carbon atoms. Alternatively, the amount of 4 to 10 α-olefins used is preferably the same as or slightly in excess of the theoretical amount, and is 10 with respect to the total amount of propylene and α-olefins having 2 or 4 to 10 carbon atoms used. It is preferably 1% by mass or less, more preferably 6% by mass or less, and further preferably 5% by mass or less.
As is clear 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 copolymerization of the propylene and the α-olefin having 2 or 4 to 10 carbon atoms The polymerization reaction means a so-called random copolymerization reaction.

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

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

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

In the documents of the present application, the number of times of the polymerization reaction means the number of concentrations of the molecular weight adjusting agent adjusted (controlled) in the polymerization atmosphere when the polymerization reaction is carried out under the temperature condition of 50 ° C. or higher. For example, when homopolymerization of propylene is carried out under the condition of molecular weight modifier concentration C ₁ under the temperature condition of 50 ° C. or higher, and then further carried out under the condition of the molecular weight modifier concentration C ₂ , the number of polymerization reactions is increased. It becomes "2". As will be described later, the present invention also includes an embodiment in which a prepolymerization reaction is carried out under a temperature condition of less than 50 ° C. prior to the polymerization reaction, but in the present application documents, polymerization is carried out under the temperature condition of less than 50 ° C. The number of prepolymerizations to be carried out shall not be included in the number of polymerization reactions.

In the polymerization reaction carried out a plurality of times in the present invention, the amount of the molecular weight adjusting agent used in the first polymerization reaction is 0 to 5 × 10 ^{− in} a ratio expressed by the molar amount of the molecular weight adjusting agent / the molar amount of propylene used. ³ is preferably (mol / mol), more preferably from ^{0~3 × 10 -3 (mol / mol} ), more preferably from ^{0~2 × 10 -3 (mol / mol} ), It is more preferably 0.01 to 2 × 10 ^-3 (mol / mol).
As described above, in the present application documents, the number of polymerization reactions is the number of concentrations of the molecular weight modifier adjusted (controlled) in a polymerization atmosphere when the polymerization reaction is carried out under a temperature condition of 50 ° C. or higher. This means that even if the amount of the molecular weight adjusting agent used is 0 mol (the amount of the molecular weight adjusting agent used is 0 (mol / mol) in the ratio expressed by the molar amount of the molecular weight adjusting agent / the molar amount of propylene used). However, if the reaction is carried out under a temperature condition of 50 ° C. or higher, it shall be regarded as a single polymerization reaction.

In the polymerization reaction carried out a plurality of times in the present invention, the amount of the molecular weight adjusting agent 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 adjusting agent / the molar amount of propylene used. in a ratio represented, is preferably ^{1 × 10 -2 (mol / mol} ) or more, more preferably ^{1.5 × 10 -2 (mol / mol} ) or more, 2 × ¹⁰ -2 (mol / Mol) or more is more preferable.

The molecular weight modifier is generally polymerized in the first polymerization reaction using a smaller amount than in the second and subsequent polymerization reactions to produce a high molecular weight polymer, and then the amount of the molecular weight modifier used is increased in the second and subsequent polymerization reactions. It is preferable to produce a polymer on the low molecular weight side.
When the polymerization reaction is carried out twice in the present invention, the ratio of the molecular weight adjusting agent used is expressed by the molar amount of the molecular weight adjusting agent used in the first polymerization reaction / the molar amount of the molecular weight adjusting agent used in the second polymerization reaction. The ratio is preferably 0 to 200 (mol / mol), more preferably 0.0005 to 100 (mol / mol), further 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 ratio of the above molecular weight adjusting agent used, and at least 5% by mass or more of the total obtained polymer is produced by the first polymerization reaction. Is preferable.

In the present invention, a propylene polymer having a desired molecular weight distribution is preferably used by changing the amount of the molecular weight modifier used 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 adjuster and propylene used, the ratio of molecular weight adjuster and propylene, polymerization temperature, polymerization pressure, properties of solid catalyst component, type of organic aluminum compound used, and organic aluminum compound. It can be appropriately controlled by controlling the amount of the external electron donating compound, the type of the external electron donating compound, the amount of the 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.
Further, the olefins to be polymerized can be used in either a gas state or a liquid state.

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

In the present invention, the polymerization temperature is usually 50 to 200 ° C., but is 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, more preferably 5 MPa or less.
Further, either a continuous polymerization method or a batch type polymerization method is possible. Further, the polymerization reaction may be carried out in two stages or in three or more stages.

In the present invention, the copolymerization reaction of propylene or α-olefin having 2 or 4 to 10 carbon atoms is carried out so that the content ratio of 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 copolymerization reaction with olefins a plurality of times, the obtained polymer is further subjected to a subsequent reaction with propylene and α-olefin having 2 or 4 to 10 carbon atoms. May be carried out to produce so-called propylene block copolymerization.
The copolymer of propylene obtained by the above-mentioned propylene block copolymerization and an α-olefin having 2 or 4 to 10 carbon atoms has a rubber-like property in which two or more kinds of monomer compositions are randomly polymerized, and is made into propylene. It is preferable that there are not many derived crystal sites.
As a comonomer to be copolymerized with propylene, that is, an α-olefin having 2 or 4 to 10 carbon atoms (an α-olefin having 2 to 10 carbon atoms other than propylene), specifically, ethylene. , 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, vinylcyclohexane and the like can be mentioned, and ethylene and 1-butene are preferable.

When the block copolymerization reaction between the propylene and an α-olefin (other than propylene) having 2 or 4 to 10 carbon atoms is carried out, propylene is usually used in the previous step in the presence of the above-mentioned olefin polymerization catalyst. After contacting and polymerizing alone (or, if necessary, in the presence of α-olefin other than propylene in an amount of 5% by mass or less of the total amount of the monomer) in the presence or absence of a molecular weight modifier, propylene is further added alone. (Or, if necessary, under the condition that α-olefin other than propylene coexists in an amount of 5% by mass or less of the total amount of the monomer), the polymerization is carried out by contacting and polymerizing at least once under the concentration of the molecular weight adjusting agent different from the above molecular weight adjusting agent. Next, it can be carried out by contacting propylene with an α-olefin (ethylene or the like) other than propylene in the subsequent stage to produce a so-called propylene block copolymer.
In the polymerization reaction in the first stage, the polymerization reaction may be carried out a plurality of times while changing the amount of the molecular weight modifier and terminated as it is (only by the polymerization reaction in the first stage), but the block copolymerization reaction in the second stage is further carried out. In this case, the copolymerization reaction between propylene in the subsequent stage and α-olefin (ethylene or the like) other than propylene may be carried out in a single stage or a plurality of times.
The number of polymerization reactions to be carried out with propylene alone in the previous stage (or under the condition that α-olefins other than propylene coexist in an amount of 5% by mass or less of the total amount of monomers, if necessary) is preferably 2 to 5 times. It is more preferably 4 times, further preferably 2 to 3 times, and the number of copolymerization reactions between the propylene in the subsequent stage and the α-olefin having 2 or 4 to 10 carbon atoms is 1 to 4 times. It is preferably 1 to 3 times, more preferably 1 to 2 times.
The copolymerization reaction of propylene and α-olefin (ethylene, etc.) other than propylene in the latter stage can be used in either a gas or liquid state as the olefins, but the entire polymerization system in the latter stage is under vapor phase conditions. It is preferable to carry out with.

When the block copolymerization reaction of the above propylene with an α-olefin other than propylene having 2 or 4 to 10 carbon atoms is carried out, the homopolymerization reaction of propylene and the α-olefin having 2 or 4 to 10 carbon atoms are carried out in the previous stage. One or more polymerization reactions selected from the copolymerization reaction of propylene and α-olefin having 2 or 4 to 10 carbon atoms, which are carried out so that the content ratio of propylene is 5% by mass or less, are carried out under different molecular weight modifier concentrations. After performing the copolymerization reaction between propylene and α-olefin having 2 or 4 to 10 carbon atoms in the latter stage, the content ratio of α-olefin having 2 or 4 to 10 carbon atoms is 20 to 80 mass. It is preferable to carry out so as to be% or less.

The polymerization reaction in the first step is 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 and is 0 to 4% by mass in the obtained polymerization. It is preferable, and it is more preferable that the content is 0 to 3% by mass.
The copolymerization reaction in the latter stage is carried out so that the content ratio of the α-olefin having 2 or 4 to 10 carbon atoms in the obtained copolymer is 20 to 80% by mass or less, and 25 to 70% by mass. It is preferable to carry out so as to be, and it is more preferable to carry out so as to be 30 to 60% by mass.

In the polymerization reaction in the first stage and the second stage, the content ratio of 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 both the first stage and the second stage is preferably 50 to 200 ° C., more preferably 50 ° C. to 100 ° C., further preferably 60 ° C. 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 type polymerization method can be adopted, and the polymerization reaction may be carried out in one stage or in two or more stages.
Further, the polymerization time (residence time in the reaction furnace) is preferably 1 minute to 5 hours at each polymerization step of each polymerization step of the first stage or the second stage, or even during 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 vapor phase polymerization method using substantially no solvent. , Bulk polymerization method or gas phase polymerization method is preferable, and the reaction in the latter stage is generally preferable to be a gas phase polymerization reaction for the purpose of suppressing elution of EPR from PP particles.

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

When performing the prepolymerization, the constituent components of the catalyst for olefin polymerization of the present invention and the contact order of the olefins are arbitrary, but the organic aluminum compound is first placed in the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere. It is preferable that the solid catalyst component for olefin polymerization of the present invention is contacted after charging, and then one or more olefins such as propylene are contacted. Alternatively, the organoaluminum compound is first charged into the prepolymerization system set to the inert gas atmosphere or the olefin gas atmosphere, then the external electron donating compound is contacted, and then the solid catalyst component for olefin polymerization of the present invention is contacted. After that, it is preferable to contact one or more olefins such as propylene.
At the time of prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

The polymerization temperature at the time of prepolymerization is less than 50 ° C., preferably 0 ° C. or higher and lower than 50 ° C., and more preferably 0 to 30 ° C. The polymerization time at the time of prepolymerization is also preferably 1 minute to 1 hour, more preferably 1 to 15 minutes.
Further, the above molecular weight adjusting agent 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 molecular weight adjusting agent in the first polymerization.

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

According to the present invention, when homopolymerization or copolymerization of olefins is carried out, the polymerization activity of the olefins and the activity against hydrogen at the time of 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 high polymerization activity persistence.

Next, the present invention will be described in more detail with reference to examples, but these are examples and do not limit the present invention.
In the examples and comparative examples shown below, the circularity of the 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. It is a thing.

(Circularity of dialkoxymagnesium particles)
The circularity of the dialkoxymagnesium particles is such that the dialkoxymagnesium particles are photographed with a scanning electron microscope (JSM-7500F, manufactured by Nippon Denshi Co., Ltd.) at a magnification such that 500 to 1000 particles are displayed on one screen. , 500 or more particles were randomly selected from the photographed particles, and after measuring the area S and peripheral length L of each particle with image analysis processing software (McView version 4.0, manufactured by MOUNTECH Co., Ltd.), each particle The circularity of the alkoxymagnesium particles was calculated as an arithmetic average value calculated by the following formula.
Circularity of each dialkoxymagnesium particle = L ² ÷ (4π × S)

(Content of magnesium atom in solid catalyst component)
The content of magnesium atom 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 it in a hydrochloric acid solution, adding the indicator methyl orange and saturated ammonium chloride solution, and ammonia. Neutralize with water and heat, cool to a constant volume, filter to remove precipitate (Ti hydroxide), take a certain amount of the obtained filtrate, heat and then buffer solution and EBT mixture indicator. Was added and measured by the EDTA titration method of titrating with an EDTA solution.

(Titanium atom content in 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 Quantification Method in Titanium Ore".

(Halogen atom content in solid catalyst component)
The halogen atom content in the solid catalyst component is a constant volume after weighing the solid catalyst component in which the solvent component has been completely removed by heating under reduced pressure in advance 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 determined by using gas chromatography (manufactured by Shimadzu Corporation, GC-14B) under the following conditions. It was obtained by measuring at. In addition, the number of moles of each component (each internal electron donating compound) was determined from the measurement results of gas chromatography using a calibration curve measured in advance at a known concentration.
<Measurement conditions>
Column: Packed column (φ2.6 × 2.1m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Co., Ltd.)
Detector: FID (Flame 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, or vaporization chamber 265 ° C, column 180 ° C, detector 265 ° C

(Example 1)
<Preparation of solid catalyst components>
(1) Preparation of solid catalyst component (first step)
A mixed solution was formed by charging 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene into a round-bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
It was then formed with 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. Suspension was added to the mixed solution. Then, the mixture was stirred at −5 ° C. for 1 hour and heated to 110 ° C. During the temperature rise, 3.6 ml (15.5 mmol) of di-n-propyl phthalate was added in portions. After the reaction was carried out while maintaining the temperature at 110 ° C. and stirring for 2 hours, the obtained reaction solution was allowed to stand and the supernatant solution was removed to obtain a slurry-like reaction product.
To the above slurry-like reaction product, 187 ml of toluene at 100 ° C. was added, stirred, allowed to stand, and then washed by repeating the process of removing the supernatant liquid four times to obtain a slurry-like solid component (I). ) Was obtained.

(Second step)
Toluene 170 ml (1600 mmol) and titanium tetrachloride 30 ml (273 mmol) were added to the reaction product containing the slurry-like solid component (I), the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the supernatant of toluene is removed, 180 ml of toluene and 20 ml (182 mmol) of titanium tetrachloride are added to raise the temperature, and 0.5 ml (2.2 mmol) of di-n-propyl phthalate is added at 80 ° C. After the addition, the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. The obtained reaction solution was allowed to stand and the supernatant solution was removed to obtain a slurry-like reaction product.
After completion of the reaction, 187 ml of toluene at 100 ° C. was added to the obtained slurry-like reaction product, the mixture was stirred and allowed to stand, and then the process of removing the supernatant was repeated twice, and n- at 60 ° C. After adding 150 ml of heptane, stirring and allowing to stand, the process of removing the supernatant was repeated 5 times for washing to obtain about 20 g of a slurry-like solid catalyst component for olefin polymerization (A1).
The content of magnesium atoms in the solid catalyst component (A1) is 16.8% by mass, the content of titanium atoms is 2.1% by mass, the content of halogen atoms is 60.8% by mass, and phthal. The total content of the acid diester was 16.7% by mass.

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

In addition to measuring the polymerization activity per 1 g of the solid catalyst component during the above polymerization reaction, the ratio of the p-xylene-soluble component of the polymer (XS), the melt flow rate of the polymer (MFR), and the molecular weight distribution of the polymer (Mw). / Mn), Z average molecular weight Mz, and bending elasticity (FM) of the polymer were measured by the following methods. The results are shown in Table 3.

<Propene 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-soluble component (XS) of polymer>
By charging 4.0 g of the polymer (polypropylene) and 200 ml of p-xylene into a flask equipped with a stirrer and setting the external temperature to the boiling point of xylene or higher (about 150 ° C.), the inside of the flask is charged. The polymer was dissolved over 2 hours while maintaining the temperature of p-xylene below the boiling point (137-138 ° C.). After that, the liquid temperature was cooled to 23 ° C. over 1 hour, and the insoluble component and the dissolved component were filtered and separated. A solution of the above-mentioned dissolved components was collected, p-xylene was distilled off by heating under reduced pressure drying, the weight of the obtained residue was determined, and the relative ratio (mass%) to the produced polymer (polypropylene) was calculated. It was designated as xylene-soluble component (XS).

<Melting flow property (MFR) of polymer>
The melt flow rate (MFR) (g / 10 minutes), which indicates the melt flow property 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 of polymer (FM)>
According to JIS K 7171, a test piece for measuring physical properties was injection-molded using the above polymer, and the state was adjusted for 144 hours or more in a thermostatic chamber adjusted to 23 ° C., and then liquid or powder exuded on the surface. The flexural modulus (FM) (MPa) of the test piece was measured using the test piece in which was not observed.

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

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

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

(Comparative Example 1)
<Formation of catalyst for propylene polymerization and propylene polymerization>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of diisopropyldimethoxysilane (DIPDMS) and the solid catalyst components obtained in Example 1 above (the solid catalyst components obtained in Example 1 above). A catalyst for olefin polymerization was prepared by charging 0.0013 mmol of A1) as a titanium atom.
Further, 4.0 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged into the above-mentioned autoclave with a stirrer having an internal volume of 2.0 liters, and the temperature was raised after prepolymerization at 20 ° C. and 1.1 MPa for 5 minutes. , 70 ° C., 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. Solid catalyst component for olefin polymerization (Similar to 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 content of magnesium atoms in the solid catalyst component (A2) is 17.1% by mass, the content of titanium atoms is 2.5% by mass, the content of halogen atoms is 61.5% by mass, and phthal. The total content of the acid diester was 10.3% by mass, and dimethyl isobutylmalonate was 4.8% by mass.
<Formation of catalyst for propylene polymerization and propylene polymerization>
In an autoclave with an internal volume of 2.0 liters completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of diisoprodimethoxysilane (DIPDMS) and the above solid catalyst component (A2) were converted into titanium atoms. To prepare a catalyst for olefin polymerization, 0.0013 mmol was charged.
Further, 0.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged into the above-mentioned autoclave with an internal volume of 2.0 liters, prepolymerized at 20 ° C. and 1.1 MPa for 5 minutes, and then the temperature was raised. As the first-stage polymerization reaction, a polymerization reaction was carried out at 70 ° C. and 3.0 MPa for 20 minutes. Then, 12 liters of hydrogen was press-fitted, the total pressure was increased to 3.6 MPa, and then a polymerization reaction was carried out at 70 ° C. for 45 minutes as a second-stage polymerization reaction to obtain the desired propylene polymer (polypropylene). 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.

(Comparative Example 2)
<Formation of catalyst for propylene polymerization 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, and the evaluation was carried out in the same manner. The polymerization conditions are shown in Table 2 and the results are shown in Table 3.

(Comparative Example 3)
<Preparation of solid catalyst components>
(1) Preparation of solid catalyst component (first step)
A mixed solution was formed by charging 40 ml (364 mmol) of titanium tetrachloride and 60 ml (565 mmol) of toluene into a round-bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
A suspension formed with 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 liquid was added to the mixed solution. Then, the mixture was stirred at −5 ° C. for 1 hour and heated to 110 ° C. The reaction product was maintained at 110 ° C. and reacted with stirring for 2 hours, and then the obtained reaction solution was allowed to stand and the supernatant solution was removed to obtain a slurry-like reaction product containing the solid component (I). ..
(Second step)
Toluene 170 ml (1600 mmol) and titanium tetrachloride 30 ml (273 mmol) were added to the reaction product containing the slurry-like solid component (I), the temperature was raised to 110 ° C., and the reaction was carried out with stirring for 2 hours. 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, the temperature was raised to 110 ° C., the reaction was carried out with stirring for 2 hours, and the obtained 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 toluene at 100 ° C. was added to the obtained slurry-like reaction product, the mixture was stirred and allowed to stand, and then the process of removing the supernatant was repeated twice, and n- at 60 ° C. After adding 150 ml of heptane, stirring and allowing to stand, the process of removing the supernatant was repeated 5 times for washing to obtain about 20 g of a slurry-like solid catalyst component for olefin polymerization (A3).
The content of magnesium atoms in the solid catalyst component (A3) is 16.9% by mass, the content of titanium atoms is 2.7% by mass, the content of halogen atoms is 62.5% by mass, and phthal. The total content of the acid diester was 11.2% by mass.

<Formation of polymerization catalyst and propylene polymerization>
A polymerization catalyst was formed and propylene polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component (A3) obtained in Comparative Example 3 was used, and the polymerization activity was evaluated and obtained. 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 copolymerization>
(1) Propylene polymerization (first-stage polymerization reaction)
After forming a polymerization catalyst and performing propylene polymerization in the same manner as in Example 1 except that the solid catalyst component (A2) obtained in Example 10 was used, the internal pressure of the autoclave was returned to normal pressure, and the polymer particles. 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 propylene polymer obtained was evaluated.
(2) Ethylene-propylene block copolymerization (second-stage polymerization reaction)
Next, ethylene-propylene and hydrogen are mixed so that the amount ratio (molar ratio) represented by ethylene (mol) / propylene (mol) / hydrogen (mol) is 1.0 / 1.0 / 0.043. After being placed in an autoclave with a stirrer, the temperature is raised to 70 ° C., and the ratio of ethylene, propylene and hydrogen is expressed as ethylene (liter / min) / propylene (liter / min) / hydrogen (liter / min). An ethylene-propylene copolymer was obtained by reacting under the conditions of 1.2 MPa, 70 ° C., and 1 hour while introducing the mixture at a ratio of 2/2 / 0.086.
In the obtained ethylene-propylene copolymer, the bending elasticity (FM) was measured by the same method as described above, and the ethylene-propylene block copolymer activity (ICP activity) (kg-ICP) was measured by the following method. / (G-cat · time)), and the block ratio (mass%) of the obtained copolymer, ethylene-propylene copolymer (EPR) content (mass%), ethylene-propylene copolymer (% by mass) The ethylene content (% by mass) in EPR) and the impact strength of izod were measured.
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 catalyst for olefin polymerization (g) ) X 1.0 (hours))
Here, I is the autoclave mass (g) after the completion of the copolymerization reaction, and G is the autoclave mass (g) after the unreacted monomer is removed after the completion of the homo-PP polymerization.

<Block rate (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))} x 100
Here, I is the autoclave mass (g) after the completion of the copolymerization reaction, G is the autoclave mass (g) after the unreacted monomer is removed after the completion of the homo-PP polymerization, and F is the 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 were blended with the obtained ethylene-propylene copolymer. A pellet-shaped ethylene-propylene copolymer was obtained by kneading and granulating with a single-screw extruder.
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.
After molding the test piece, the state was adjusted for 144 hours or more in a thermostatic chamber adjusted to 23 ° C., and then an IZOd impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Izod impact tester model number A-1218044405) was used. , JIS K7110 “Izod impact strength test method” was used to measure the Izod impact strength of the test piece at 23 ° C and −30 ° C.
Specimen 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 notched mold Temperature conditions: 23 ° C and -30 ° C
Impact speed: 3.5m / s
Nominal pendulum energy: 5.5J when measuring at 23 ° C, 2.75J when measuring at -30 ° C

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

From Tables 2 to 6, in Examples 1 to 11, when homopolymerization or copolymerization of olefins is carried out, the polymerization activity of the olefins and the hydrogen resistance activity at the time of 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 high polymerization activity persistence.
On the other hand, from Tables 2 to 6, it can be seen that Comparative Examples 1 to 4 are particularly inferior in the molecular weight distribution of the obtained polymer.

According to the present invention, when homopolymerization or copolymerization of olefins is carried out, the polymerization activity of the olefins and the activity against hydrogen at the time of 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 high polymerization activity persistence.

Claims (8)

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 or a halogen atom having 1 to 8 carbon atoms, and when a plurality of R ^1s are present, they may be the same or different from each other, and R ² and R ³ have 1 to 8 carbon atoms. It is an alkyl group of 12, which may be the same or different, and when the number j of the substituent R ¹ is 0, 1 or 2, and j is 2, each R ¹ is the same. The first step of contacting with one or more first internal electron donating compounds selected from the aromatic dicarboxylic acid diesters represented by), reacting them, and then washing them is performed. For the resulting product
A solid catalyst component for olefin polymerization obtained by contacting a tetravalent titanium halogen compound with one or more second internal electron donating compounds, reacting them, and then performing a second step of washing.
The following general formula (II)
R ⁴ _p AlQ _3-p (II)
(In the formula, 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 or different from each other, Q is a hydrogen atom or a halogen atom, and Q is a plurality. If they exist, they may be the same or different from each other, and p is a real number of 0 <p≤3.)
Organoaluminium compound represented by
Using a catalyst for olefin polymerization formed by contacting with an external electron donating compound,
A homopolymerization reaction of propylene and a copolymerization reaction of propylene and 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. There multiple rows of one or more of the polymerization reaction, phase in different molecular weight modifier concentration under selected from,
In the polymerization reaction performed a plurality of times,
The amount of the molecular weight adjusting agent used in the first polymerization reaction is 0 to 5 × 10 ^-3 (mol / mol) in a ratio expressed by the molar amount of the molecular weight adjusting agent / the molar amount of propylene used .
The amount of the molecular weight modifier used in the second polymerization reaction is 1 × ^10-2 (mol / mol) or more in a ratio expressed by the molar amount of the molecular weight modifier / the molar amount of propylene used. A method for producing an olefin polymer, which is characterized by the above. Claim 1 in which the second internal electron donating compound is one or more selected from alkyl-substituted malonic acid diesters, cycloalkanedicarboxylic acid esters, cycloalkene dicarboxylic acid diesters, diethers, ethercarboxylic acids and ether carbonates. The method for producing an olefin polymer according to the above. The method for producing an olefin polymer according to claim 1 or 2 , wherein the homopolymerization reaction of propylene is carried out a plurality of times under different molecular weight modifier concentrations. A homopolymerization reaction of propylene and a copolymerization reaction of propylene and 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 multiple times under different molecular weight modifier concentrations,
The obtained polymer is copolymerized with propylene and an α-olefin having 2 or 4 to 10 carbon atoms to obtain a propylene block copolymer.
The method for producing an olefin polymer according to claim 1 or 2. The method for producing an olefin polymer according to any one of claims 1 to 4, wherein the molecular weight modifier is hydrogen. The external electron donating compound is the following general formula (III);
R ⁵ _q Si (OR ⁶ ) _4-q (III)
(Wherein, 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, a polycyclic amino group, R ⁵ When a plurality of carbon groups are present, they may be the same or different from each other. R ⁶ is an alkyl group having a linear or branched chain having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, and the like. a vinyl group, an allyl group or an aralkyl group, an optionally .q even being the same or different if R ⁶ there are multiple integers of 0 ≦ q ≦ 3.)
Organosilicon alkoxy compound represented by and the following general formula (IV);
(R ⁷ R ⁸ N) _s SiR ⁹ _4-s (IV)
(However, R ⁷ and R ⁸ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, vinyl groups, allyl groups, aralkyl groups, and cyclos having 3 to 20 carbon atoms. It is a group selected from an alkyl group and an aryl group, and may be the same or different from each other, or R ⁷ and R ⁸ may be bonded to each other to form a ring, and the R ⁷ R ⁸ N group is formed. When there are a plurality of them, they may be the same or different from each other. R ⁹ is a linear alkyl group 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, and 1 carbon group. 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 R ⁹ may be the same or different. S is an integer from 1 to 3.)
The method for producing an olefin polymer according to any one of claims 1 to 5 , which is one or more selected from the aminosilane compounds represented by. The solid catalyst component for olefin polymerization comprises the first internal electron donating compound and the second internal electron donating compound.
Any of claims 1 to 6, which are obtained by contacting the compounds so as to satisfy the relationship of the molar amount of the first internal electron donating compound> the molar amount of the second internal electron donating compound. The method for producing an olefin polymer according to the above. A homopolymerization reaction of propylene and a copolymerization reaction of propylene and 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 multiple times under different molecular weight modifier concentrations,
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 copolymerization reaction between propylene and the α-olefin having 2 or 4 to 10 carbon atoms with respect to the obtained polymer. The method for producing an olefin polymer according to claim 1 or 2, wherein the method is carried out so as to be.