JP2010248469A - Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerization catalyst component and an olefin polymerization catalyst which can perform stereoregularity controlling in a relatively simple method, which has excellent hydrogen response, and which has polyfunctional aromatic compound-free. <P>SOLUTION: The olefin polymerization catalyst comprises (I) a solid titanium catalyst component containing titanium, magnesium, halogen, ester compound (B) specified by formula (1), and a diether compound (C) specified by formula (3); (II) an organic metallic compound; and (III) an electron donor as required. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a solid titanium catalyst component preferably used for olefin polymerization, particularly α-olefin polymerization. The present invention also relates to an olefin polymerization catalyst containing the solid titanium catalyst component. Furthermore, the present invention relates to an olefin polymerization method using the olefin polymerization catalyst.

Conventionally, as a catalyst used to produce an olefin polymer such as ethylene, α-olefin homopolymer or ethylene / α-olefin copolymer, a titanium compound supported on an active magnesium halide is included. Catalysts are known. (Hereinafter, polymerization may mean copolymerization such as random copolymerization and block copolymerization in addition to homopolymerization.)
Such olefin polymerization catalysts include Ziegler-Natta catalysts, catalysts containing titanium tetrachloride and titanium trichloride, solid titanium catalyst components composed of magnesium, titanium, halogen and electron donors and organometallics. Catalysts composed of compounds are widely known.

  The latter catalyst exhibits high activity for polymerization of α-olefins such as propylene and 1-butene in addition to ethylene. In addition, the α-olefin polymer obtained may have high stereoregularity.

  Among these catalysts, in particular, a solid titanium catalyst component on which an electron donor selected from carboxylic acid esters, typically phthalate esters, is supported, an aluminum-alkyl compound as a co-catalyst component, and at least Japanese Patent Application Laid-Open No. 58-83006 (patent document) expresses excellent polymerization activity and stereospecificity when a silicon compound having one Si-OR (wherein R is a hydrocarbon group) is used. Reference 1), Japanese Patent Application Laid-Open No. 56-811 (Patent Document 2), and the like.

  On the other hand, the use of polyfunctional aromatic compounds such as phthalic acid esters has recently been restricted due to health and safety issues. On the other hand, most reports including the above-mentioned patent documents show examples in which it is preferable to use a polyfunctional aromatic compound (eg, phthalate ester) as an electron donor. Patent Document 3 discloses a catalyst for making an aromatic ester free by applying a simple production method reported in Patent Document 1 or Patent Document 2. This catalyst system not only does not use an aromatic ester, but also has excellent hydrogen responsiveness, and is attractive in that it can produce a high-flow polypropylene that could not be achieved by limiting the pressure during polymerization. However, the control range of stereoregularity is narrow, and for example, there is a difficulty that the low stereoregularity required for film applications and the high stereoregularity required for automobile injection molded articles such as bumpers and instrument panels cannot be freely controlled.

JP 58-83006 A JP-A-56-811 Japanese Patent Laid-Open No. 06-336503

In view of the above background, there has been a long-awaited appearance of a catalyst for olefin polymerization that can control stereoregularity by a relatively simple production method, has excellent hydrogen responsiveness, and is free of polyfunctional aromatic compounds.

  Accordingly, an object of the present invention is to provide a catalyst component for polymerization that is capable of controlling stereoregularity by a relatively simple production method, has excellent hydrogen responsiveness, and is free of polyfunctional aromatic compounds, and a catalyst for olefin polymerization that includes the component. Is to make it possible.

  The present inventors have studied to solve the above problems. As a result, the catalyst for olefin polymerization containing solid titanium catalyst component (I) containing ester compound (B) having a specific structure with titanium, magnesium, halogen and a diether compound (C) having a specific structure However, it has been found that the catalyst has an excellent balance between stereoregularity controllability and hydrogen responsiveness than before, has a broad molecular weight distribution, and has a very balanced catalyst performance. As the titanium catalyst component (I), a magnesium compound (A) having no liquid reducing ability (hereinafter sometimes simply referred to as “liquid magnesium compound (A)”) is used as an ester compound (B). ), A diether compound (C) having a specific structure, and a liquid titanium compound (D) in contact with each other in a specific order. Fin polymerization catalyst is found that an excellent balance of controllability and hydrogen response of stereoregularity than conventional, and have completed the present invention.

That is, the present invention
Solid titanium catalyst component (I) containing titanium, magnesium, halogen and an ester compound (B) specified by the following formula (1) and a diether compound (C) specified by the following formula (3).

(In the formula (1), R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ ;
Single bonds in the skeleton (except for C ^a -C ^a bonds) may be replaced with double bonds,
A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms,
A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a plurality of Rs may be bonded to each other to form a ring, and a double bond is present in the ring skeleton formed by bonding of R to each other. Or a heteroatom may be contained. )
(In the formula (3), m is an integer of 1 to 10, preferably an integer of 3 to 10, and R ¹¹ , R ¹² and R ^{31 to} R ³⁶ are each independently a hydrogen atom, carbon, hydrogen, This is a substituent having at least one element selected from oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon.)
The solid titanium catalyst component (I) comprises a liquid magnesium compound (A), an ester compound (B) specified by the following formula (1), a diether compound (C) specified by the following formula (3), Obtained by contact with the liquid titanium compound (D) (provided that the ester compound (B) is obtained prior to the liquid titanium compound (D) or simultaneously with the liquid titanium compound (D) and the liquid magnesium compound (A). Contact).

  The solid titanium catalyst component (I) of the present invention preferably has a cyclic ester structure in which the ester compound (B) is specified by the following formula (2).

(In Formula (2), n is an integer of 5-10,
R ² and R ³ are each independently COOR ¹ or R ′, at least one of R ² and R ³ is COOR ¹ ,
A single bond in the cyclic skeleton (excluding ^a C ^a -C ^a bond and a C ^a -C ^b bond when R ³ is a hydrogen atom) may be replaced with a double bond,
A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms,
A is

Or it is a hetero atom.

A plurality of R ′ are independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A plurality of R ′ may be bonded to each other to form a ring, and in the ring skeleton formed by R ′ being bonded to each other, A double bond or a hetero atom may be contained. )
The solid titanium catalyst component (I) of the present invention preferably has n = 6 in the above formula (2). Furthermore, in the above formula (2), it is preferable that R ² is COOR ¹ and R ³ is R ′.

  Furthermore, as a contact order of each component in the present invention, the liquid magnesium compound (A) and the ester compound (B) specified by the above formula (1) are contacted before the liquid titanium compound (D). Then, the ester compound (B1) specified by the formula (1), which may be the same as or different from the ester compound (B), is contacted with the diether compound (C) specified by the formula (3). (However, the liquid titanium compound (D) may be contacted in multiple steps).

  The solid titanium catalyst component (I) of the present invention preferably has a cyclic ester structure in which the ester compound (B) and the ester compound (B1) are specified by the above formula (2).

The solid titanium catalyst component (I) of the present invention preferably has n = 6 in the above formula (2). Furthermore, in the above formula (2), it is preferable that R ² is COOR ¹ and R ³ is R ′.

In the present invention, R ^{1 of the} ester compound (B) is each independently a monovalent hydrocarbon group having 2 to 3 carbon atoms, and R ^{1 of the} ester compound (B1) is each independently a carbon atom. A monovalent hydrocarbon group having a number of 1 to 20 is particularly preferable.

The olefin polymerization catalyst of the present invention comprises the above solid titanium catalyst component (I),
It is characterized by containing an organometallic compound (II) and, if necessary, an electron donor (III).

  The olefin polymerization method of the present invention is characterized in that olefin polymerization is carried out in the presence of the olefin polymerization catalyst.

  Using the solid titanium catalyst component (I), the olefin polymerization catalyst, and the olefin polymerization method of the present invention, for example, production of an impact copolymer that requires high stereoregularity and high flow, which has been difficult to achieve at the same time. The effect that can be made easy can be expected. Further, since it does not contain any polyfunctional aromatic compound, it is possible to provide a catalyst that can cope with the above-mentioned safety and health regulations.

  The solid titanium catalyst component (I) according to the present invention comprises titanium, magnesium, halogen and an ester compound (B) specified by the following formula (1) and a diether compound (C) specified by the following formula (3). It is characterized by including.

Further, the solid titanium catalyst component (I) according to the present invention comprises a liquid magnesium compound (A), an ester compound (B) specified by the following formula (1), and a diether compound specified by the following formula (3). (C) and a liquid titanium compound (D) are contacted (however, the ester compound (B) is a liquid magnesium compound (A) prior to the liquid titanium compound (D) or simultaneously with the liquid titanium compound (D)). Or the liquid magnesium compound (A) and the ester compound (B) specified by the following formula (1) are contacted before the liquid titanium compound (D), The ester compound (B1) specified by the following formula (1), which may be the same as or different from the ester compound (B), is brought into contact with the diether compound (C) specified by the following formula (3) (however, , Liquid titanium compound (D) may be contacted a plurality of times) obtained by including titanium, magnesium, a halogen.

  Hereinafter, each component of this application is demonstrated in detail.

[Magnesium compound]
As the magnesium compound used for the preparation of the solid titanium catalyst component (I) according to the present invention, specifically,
Magnesium halides such as magnesium chloride and magnesium bromide;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, 2-ethylhexoxy magnesium;
Aryloxymagnesium such as phenoxymagnesium;
Known magnesium compounds such as magnesium carboxylates such as magnesium stearate can be mentioned.

  These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Among these, a magnesium compound containing a halogen is preferable, and a magnesium halide, particularly magnesium chloride is preferably used. In addition, alkoxymagnesium such as ethoxymagnesium is also preferably used. The magnesium compound may be derived from other substances, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with titanium halide, silicon halide, halogenated alcohol or the like. Good.

  Next, the magnesium compound (A) which does not have a reducing ability in a liquid state, which is a preferred embodiment as the magnesium compound used in the present invention, will be described in detail.

[Magnesium compound having no reducing ability in liquid state (A)]
Examples of the liquid magnesium compound (A) used for the preparation of the solid titanium catalyst component (I) according to the present invention include, for example, JP-A-58-83006 and JP-A-56-811 (Patent Documents 1 and 2). The liquid magnesium compound described in (1) can be mentioned.

For the preparation of the liquid magnesium compound (A), magnesium halides such as magnesium chloride and magnesium bromide;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride, and aryloxy magnesium halides;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, 2-ethylhexoxy magnesium;
Aryloxymagnesium such as phenoxymagnesium;
Magnesium carboxylates such as magnesium stearate;
Well-known magnesium compounds such as can be used.

These magnesium compounds may be used alone or in combination of two or more. These magnesium compounds may be complex compounds with other metals, double compounds, or mixtures with other metal compounds.

  Among these, magnesium halide, particularly magnesium chloride is preferably used, and alkoxymagnesium such as ethoxymagnesium is also preferably used. The magnesium compound may be derived from another substance, for example, obtained by contacting an organic magnesium compound such as a Grignard reagent with a halogenated titanium, a halogenated silicon, a halogenated alcohol, or the like. Good.

  For the preparation of the liquid magnesium compound (A), it is preferable to use the electron donor (a). The electron donor (a) is preferably a known compound that does not have a reducing ability in the range of room temperature to about 300 ° C., for example, can solubilize the solid magnesium compound in an inert solvent such as a liquid hydrocarbon. For example, it is preferable to use alcohol, aldehyde, amine, carboxylic acid, and a mixture thereof.

Specific examples of alcohols having solubilization ability with respect to the magnesium compound include methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, and n-octanol. Aliphatic alcohols such as 2-ethylhexanol, decanol, dodecanol;
Cycloaliphatic alcohols such as cyclohexanol and methylcyclohexanol;
Aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol;
an aliphatic alcohol containing an alkoxy group such as n-butyl cellosolve;
And so on.

  Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.

  Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.

  Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid.

  Among the electron donors (a), alcohols are preferable, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like are particularly preferable examples.

  The amount of the magnesium compound and electron donor (a) used in preparing the liquid magnesium compound (A) varies depending on the type, contact conditions, etc., but the magnesium compound is a unit of the electron donor (a). It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 5 mol / liter per volume. As an inert medium used when preparing a liquid magnesium compound (A), well-known hydrocarbon compounds, such as a heptane, an octane, and a decane, are mentioned as a preferable example.

  The composition ratio of magnesium and electron donor (a) in the obtained liquid magnesium compound (A) varies depending on the type of compound used, and thus cannot be specified unconditionally. However, the electron donor ( a) is preferably in the range of 2.0 mol or more, more preferably 2.2 mol or more, further preferably 2.4 mol or more, particularly preferably 2.6 mol or more and 5 mol or less.

[Ester compound (B)]
The ester compound (B) used for the preparation of the solid titanium catalyst component (I) according to the present invention has a plurality of carboxylic acid ester groups and is represented by the following formula (1). In the following formula, C ^a
Represents a carbon atom.

In formula (1), R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ .

All the bonds between carbon atoms in the skeleton are preferably single bonds, but any single bond in the skeleton may be replaced by a double bond, but for the C ^a -C ^a bond, It is preferably a single bond.

A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 2 to 3 carbon atoms. . The hydrocarbon group includes methyl, ethyl, n-propyl, i-propyl, n-butyl, isobutyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl. Group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group and the like, preferably methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, isobutyl group, neopentyl group 2-ethylhexyl group, and particularly preferred are ethyl group, n-propyl group and i-propyl group.

  A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a group.

  Among these, R other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, i Aliphatic hydrocarbon groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, octyl group , An alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

R may be bonded to each other to form a ring, and a ring skeleton formed by bonding R to each other may contain a double bond or a heteroatom. When the ring skeleton contains two or more C ^a bonded with COOR ¹ , the number of carbon atoms forming the ring skeleton is 5 to 10.

R ² and R ³ which are not COOR ¹ are preferably a hydrogen atom or a hydrocarbon group.
Among these, a hydrogen atom, secondary alkyl such as i-propyl group, sec-butyl group, 2-pentyl group, 3-pentyl group or cycloalkyl group such as cyclohexyl group, cyclopentyl group and cyclohexylmethyl group. Of these, at least one of R ² and R ³ which are not COOR ¹ bonded to C ^a is preferably a hydrogen atom.

Examples of the ester compound (B) represented by the formula (1) are as follows:
Diethyl 2,3-bis (2-ethylbutyl) succinate,
Diethyl 2,3-dibenzylsuccinate,
Diethyl 2,3-diisopropylsuccinate,
Diisobutyl 2,3-diisopropylsuccinate,
Diethyl 2,3-bis (cyclohexylmethyl) succinate,
Diethyl 2,3-diisobutyl succinate,
Diethyl 2,3-dineopentyl succinate,
Diethyl 2,3-dicyclopentyl succinate,
A mixture in the pure or optionally racemic form of the (S, R) (S, R) form of diethyl 2,3-dicyclohexylsuccinate.

Other examples are
sec-diethyl butyl succinate,
Diethyl texyl succinate,
Diethyl cyclopropyl succinate,
Diethyl norbornyl succinate,
(10-) diethyl perhydronaphthyl succinate,
Diethyl trimethylsilylsuccinate,
Diethyl methoxysuccinate,
diethyl p-methoxyphenylsuccinate,
diethyl p-chlorophenylsuccinate,
Diethyl phenylsuccinate,
Diethyl cyclohexylsuccinate,
Diethyl benzylsuccinate,
(Cyclohexylmethyl) diethyl succinate,
diethyl t-butylsuccinate,
Diethyl isobutyl succinate,
Diethyl isopropyl succinate,
It is diethyl neopentyl succinate.

Diethyl 2,2-dimethylsuccinate,
Diethyl 2-ethyl-2-methylsuccinate,
Diethyl 2-benzyl-2-isopropylsuccinate,
2- (cyclohexylmethyl) -2-isobutyl succinate diethyl,
2-cyclopentyl-2-n-propyl diethyl succinate,
Diethyl 2,2-diisobutyl succinate,
Diethyl 2-cyclohexyl-2-ethylsuccinate,
Diethyl 2-isopropyl-2-methylsuccinate,
Diethyl 2,2-diisopropylsuccinate,
Diethyl 2-isobutyl-2-ethylsuccinate,
Diethyl 2- (1,1,1-trifluoro-2-propyl) -2-methylsuccinate,
2-isopentyl-2-isobutyl succinate diethyl,
2-phenyl-2-n-butyl succinate diethyl,
Diisobutyl 2,2-dimethylsuccinate,
Diisobutyl 2-ethyl-2-methylsuccinate,
Diisobutyl 2-benzyl-2-isopropylsuccinate,
2- (cyclohexylmethyl) -2-isobutyl succinate diisobutyl,
2-cyclopentyl-2-n-propyl diisobutyl succinate cyclobutane-1,2-dicarboxylate,
It is ethyl 3-methylcyclobutane-1,2-dicarboxylate.

As a suitable example of the compound in which R groups are bonded to each other to form a cyclic structure in the above formula (1), a compound represented by the following formula (2) is exemplified. In the following formulae, C ^a and C ^b represent carbon atoms.

  In Formula (2), n is an integer of 5 to 10, preferably an integer of 5 to 8, more preferably an integer of 5 to 7.

R ² and R ³ are each independently COOR ¹ or R ′, and at least one of R ² and R ³ is COOR ¹ . Preferably R ² is COOR ¹ and R ³ is R ′.

Between the carbon atoms bond in the cyclic skeleton are preferably all is a single bond, either a single bond in the cyclic skeleton may be replaced with double bonds, C ^a -C ^a bond When C ³ and R ³ are hydrogen atoms, the C ^a -C ^b bond is preferably a single bond.

A plurality of R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably a carbon number, similarly to R ¹ of the compound of the above formula (1). 2 to 3 hydrocarbon groups. Examples of suitable R ¹ are methyl, ethyl, n-propyl, i-propyl,
An n-butyl group, an isobutyl group, a neopentyl group, and a 2-ethylhexyl group are preferable, and an ethyl group, an n-propyl group, and an i-propyl group are particularly preferable.

  When the number of carbon atoms is outside this range, the obtained solid titanium catalyst component may not have a large particle size, or may be difficult to collect by filtration or decantation in a fine powder state.

  A is

Or it is a hetero atom.
A is

The ring formed by C ^a , C ^b and A is preferably a cyclic carbon structure, and the cyclic structure is particularly preferably a saturated alicyclic structure composed only of carbon.

  A plurality of R ′ are independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. An atom or group.

  Among these, R ′ other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms, and examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, Aliphatic hydrocarbons such as i-propyl group, n-butyl group, i-butyl group, sec-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, octyl group Group, alicyclic hydrocarbon group, and aromatic hydrocarbon group.

R ′ may be bonded to each other to form a ring, and the ring skeleton formed by bonding R ′ to each other may contain a double bond or a heteroatom. When two or more C ^a bonded with COOR ¹ are contained in the skeleton, the number of carbon atoms forming the skeleton of the ring is 5 to 10.

  Examples of such a ring skeleton include a norbornane skeleton and a tetracyclododecacene skeleton.

  A plurality of R ′ may be a carbonyl structure-containing group such as a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group or an acetyl group.

  R ′ is preferably a hydrogen atom or a hydrocarbon group.

As the ester compound (B) represented by the formula (2),
Diethyl cyclohexane-1,2-dicarboxylate,
Di-n-propyl cyclohexane-1,2-dicarboxylate,
Diisopropylcyclohexane-1,2-dicarboxylate,
Cyclohexane-1,3-dicarboxylate diethyl,
Cyclohexane-1,3-dicarboxylate di-n-propyl cyclohexane-1,3-dicarboxylate diisopropyl,
Diethyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,3-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclohexane-1,3-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Diethyl 5-methylcyclohexane-1,3-dicarboxylate,
Di-n-propyl 5-methylcyclohexane-1,3-dicarboxylate,
Diisopropyl 5-methylcyclohexane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylate diisopropyl,
Diethyl 3-hexylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-hexylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-dihexylcyclohexane-1,2-dicarboxylate,
3-hexyl 6-pentylcyclohexane-1,2-dicarboxylate diethyl,
Diethyl cyclopentane-1,2-dicarboxylate,
Di-n-propyl cyclopentane-1,2-dicarboxylate,
Diisopropyl cyclopentane-1,2-dicarboxylate,
Diethyl cyclopentane-1,3-dicarboxylate,
Di-n-propyl cyclopentane-1,3-dicarboxylate,
Diethyl 3-methylcyclopentane-1,2-dicarboxylate,
Di-n-propyl 3-methylcyclopentane-1,2-dicarboxylate,
Diisopropyl 3-methylcyclopentane-1,2-dicarboxylate,
4-methylcyclopentane-1,3-dicarboxylate diethyl,
4-methylcyclopentane-1,3-dicarboxylic acid di-n-propyl;
4-methylcyclopentane-1,3-dicarboxylate diisopropyl,
4-methylcyclopentane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclopentane-1,2-dicarboxylate,
4-methylcyclopentane-1,2-dicarboxylate diisopropyl,
Diethyl 5-methylcyclopentane-1,3-dicarboxylate,
Di-n-propyl 5-methylcyclopentane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
3,4-dimethylcyclopentane-1,2-dicarboxylate diisopropyl,
Diethyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-propyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisopropyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3-hexylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dihexylcyclopentane-1,2-dicarboxylate,
Diethyl cycloheptane-1,2-dicarboxylate,
Di-n-propyl cycloheptane-1,2-dicarboxylate,
Diisopropyl cycloheptane-1,2-dicarboxylate,
Diethyl cycloheptane-1,3-dicarboxylate,
Di-n-propyl cycloheptane-1,3-dicarboxylate,
Diethyl 3-methylcycloheptane-1,2-dicarboxylate,
Di-n-propyl 3-methylcycloheptane-1,2-dicarboxylate,
Diisopropyl 3-methylcycloheptane-1,2-dicarboxylate,
4-methylcycloheptane-1,3-dicarboxylate diethyl,
4-methylcycloheptane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcycloheptane-1,2-dicarboxylate,
4-methylcycloheptane-1,2-dicarboxylate diisopropyl,
Diethyl 5-methylcycloheptane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
3,4-dimethylcycloheptane-1,2-dicarboxylate diisopropyl,
Diethyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-propyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisopropyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3-hexylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dihexylcycloheptane-1,2-dicarboxylate,
Diethyl cyclooctane-1,2-dicarboxylate,
Diethyl 3-methylcyclooctane-1,2-dicarboxylate,
Diethyl cyclodecane-1,2-dicarboxylate,
Diethyl 3-methylcyclodecane-1,2-dicarboxylate,
Diethyl cyclooxypentane-3,4-dicarboxylate,
Examples include ethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate.

  Further, as a compound having two R ′ bonded to each other to form a ring and having a hetero atom in the cyclic structure, compounds having the following structural formulas can be exemplified.

Moreover, the dicarboxylic acid ester of the cyclic diol compound corresponding to these can also be mentioned as a suitable compound. As such a compound, in particular,
Cyclohexyl-1,2-diacetate,
Cyclohexyl-1,2-dibutanate,
Cyclohexyl-1,2-dipentanate,
Cyclohexyl-1,2-dihexanate,
Cyclohexyl-1,2-dibenzoate,
Cyclohexyl-1,2-ditoluate,
3,6-dimethylcyclohexyl-1,2-diacetate,
3,6-dimethylcyclohexyl-1,2-dibutanate,
3,6-dimethylcyclohexyl-1,2-pentanate,
3,6-dimethylcyclohexyl-1,2-dihexanate,
3-methyl-6-propylcyclohexyl-1,2-diol acetate,
3-methyl-6-propylcyclohexyl-1,2-dibutanate,
3,6-dimethylcyclohexyl-1,2-dibenzoate,
3,6-dimethylcyclohexyl-1,2-ditoluate,
3-methyl-6-propylcyclohexyl-1,2-dibenzoate,
3-methyl-6-propylcyclohexyl-1,2-ditoluate,
Etc. can be mentioned as a preferable example. Among these, dibutanate and dipentanate compounds are particularly preferably used.

  The compound having the diester structure has isomers such as cis and trans, and any structure often has an effect meeting the object of the present invention.

  Of the above-mentioned compounds, particularly preferred are cyclohexanedicarboxylic acid esters in which n = 6 in formula (2). The reason is not only the catalyst performance, but also that these compounds can be produced relatively inexpensively using the Diels Alder reaction.

  These compounds may be used alone or in combination of two or more compounds. Moreover, you may use in combination with the electron donor (E) which is mentioned later unless the objective of this invention is impaired.

  These ester compounds (B) may be formed in the process of preparing the solid titanium catalyst component (I). For example, it can be formed in the process of contacting with the liquid magnesium compound (A). More specifically, when contacting with the liquid magnesium compound (A), the ester is provided by providing a step in which the carboxylic anhydride corresponding to the above compound and the carboxylic acid halide and the corresponding alcohol substantially contact each other. The compound (B) can also be contained in the solid titanium catalyst component.

[Ester compound (B1)]
The ester compound (B1) used for the preparation of the solid titanium catalyst component (I) according to the present invention is the same compound as the ester compound (B) represented by the above formula (1).

However, in the above formula (1), a plurality of R ^{1 s} independently have 1 to 1 carbon atoms.
20, preferably 1 to 10, more preferably 2 to 8, still more preferably 4 to 8, and particularly preferably 4 to 6 monovalent hydrocarbon group. As this hydrocarbon group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, and the like are mentioned. Among them, an n-butyl group, an isobutyl group, a hexyl group, and an octyl group are preferable, and n-butyl is more preferable because it is easy to produce an olefin polymer having a wide molecular weight distribution. Group and isobutyl group are particularly preferred.

  In the formula (1), a plurality of Rs are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, or a halogen-containing group. And an atom or group selected from silicon-containing groups, but at least one R is not a hydrogen atom.

  R other than a hydrogen atom is preferably an aliphatic hydrocarbon group, specifically a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group. Is preferred.

  Examples of such ester compound (B1) include the same compounds as the ester compound (B).

  Among the compounds represented by the above formula (1) used as the ester compound (B1), a preferred example of a compound in which R groups are bonded to form a cyclic structure is represented by the above formula (2). And the same compounds as those mentioned above.

However, in the above formula (2), a plurality of R ^{1 s} have ¹ to 20, preferably 1 to 10, more preferably 2 to 8, carbon atoms, like R ¹ of the compound of the above formula (1). More preferably, it is a monovalent hydrocarbon group of 4 to 8, particularly preferably 4 to 6. Examples of the hydrocarbon group include ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, Hexadecyl group, octadecyl group, eicosyl group and the like are mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group is more preferable because it is easy to produce an olefin polymer having a wide molecular weight distribution. Group and isobutyl group are particularly preferred.

  As such an ester compound (B1), a cyclic ester compound (B1-a) or a cyclic ester compound (B1-b) having a structure as shown below can be suitably used.

[Cyclic ester compound (B1-a)]
The cyclic ester compound (B1-a) has a plurality of carboxylic acid ester groups and is represented by the following formula (2a).

In the formula (2a), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.

R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ .

Between the carbon atoms bond in the cyclic skeleton are preferably all is a single bond, in the cyclic skeleton, any C ^a -C ^a bond and R ³ is other than C ^a -C ^b bond in the case where R These single bonds are
It may be replaced with a double bond.

A plurality of R ^{1 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8 and particularly preferably 4 to 6 carbon atoms. It is a hydrogen group. As this hydrocarbon group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, Hexadecyl group, octadecyl group, eicosyl group and the like can be mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group are more preferable. It is particularly preferable because it can be manufactured.

  A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a group, but at least one R is not a hydrogen atom.

  Among these, R other than a hydrogen atom is preferably a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso group. Aliphatic hydrocarbon groups such as -propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, vinyl group, phenyl group, octyl group , An alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group is preferable, and specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group are preferable.

R may be bonded to each other to form a ring, and a ring skeleton formed by bonding of R to each other may contain a double bond, and in the ring skeleton, When two or more C ^a bonded with COOR ¹ are contained, the number of carbon atoms constituting the ring skeleton is 5 to 10.

  Examples of such a ring skeleton include a norbornane skeleton and a tetracyclododecene skeleton.

  A plurality of Rs may be a carbonyl structure-containing group such as a carboxylic acid ester group, an alkoxy group, a siloxy group, an aldehyde group or an acetyl group, and these substituents include one or more hydrocarbon groups. It is preferable that

As such a cyclic ester compound (B1-a), diethyl 3-methylcyclohexane-1,2-dicarboxylate described in International Publication No. 2006/077945 pamphlet,
Di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclohexane-1,2-dicarboxylate,
Dihexyl 3-methylcyclohexane-1,2-dicarboxylate,
3-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,3-dicarboxylate diethyl,
4-methylcyclohexane-1,3-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisobutyl,
4-methylcyclohexane-1,2-dicarboxylic acid dihexyl,
4-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl,
Didecyl 4-methylcyclohexane-1,2-dicarboxylate,
Diethyl 5-methylcyclohexane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclohexane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
3,4-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl,
Diheptyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcyclohexane-1,2-dicarboxylate 3,2-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
3,6-dimethylcyclohexane-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisopropyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Di-n-butyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
3,6-diphenylcyclohexane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Didecyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl-6-ethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-ethylcyclohexane-1,2-dicarboxylic acid dihexyl;
3-methyl-6-ethylcyclohexane-1,2-dicarboxylic acid diheptyl,
Dioctyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Dimethyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate, didecyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diethyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid diisopropyl, 3-methyl-6-n-propyl Cyclohexane-1,2-dicarboxylate di-n-butyl,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-n-propylcyclohexane-1,2-dicarboxylate dihexyl;
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Didecyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Diethyl 3-hexylcyclohexane-1,2-dicarboxylate,
3-hexylcyclohexane-1,2-dicarboxylate diisobutyl,
Diethyl 3,6-dihexylcyclohexane-1,2-dicarboxylate,
3-hexyl-6-pentylcyclohexane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methylcyclopentane-1,2-dicarboxylate,
3-methylcyclopentane-1,2-dicarboxylic acid diheptyl;
Didecyl 3-methylcyclopentane-1,2-dicarboxylate,
4-methylcyclopentane-1,3-dicarboxylate diethyl,
4-methylcyclopentane-1,3-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylate diethyl,
4-methylcyclopentane-1,2-dicarboxylate diisobutyl,
4-methylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcyclopentane-1,2-dicarboxylate,
Diethyl 5-methylcyclopentane-1,3-dicarboxylate,
Diisobutyl 5-methylcyclopentane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
3,4-dimethylcyclopentane-1,2-dicarboxylic acid diheptyl,
Didecyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diheptyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Didecyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diethyl 3-hexylcyclopentane-1,2-dicarboxylate,
Diethyl 3,5-dihexylcyclopentane-1,2-dicarboxylate,
3-hexyl-5-pentylcyclopentane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylic acid diisopropyl, 3-methyl-5-n -Di-n-butyl propylcyclopentane-1,2-dicarboxylate,
3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate diisobutyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate dihexyl;
Dimethyl of 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Didecyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate,
Diethyl 3-methylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methylcycloheptane-1,2-dicarboxylate,
3-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 3-methylcycloheptane-1,2-dicarboxylate,
4-methylcycloheptane-1,3-dicarboxylate diethyl,
4-methylcycloheptane-1,3-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylate diethyl,
4-methylcycloheptane-1,2-dicarboxylate diisobutyl,
4-methylcycloheptane-1,2-dicarboxylic acid diheptyl,
Didecyl 4-methylcycloheptane-1,2-dicarboxylate,
Diethyl 5-methylcycloheptane-1,3-dicarboxylate,
Diisobutyl 5-methylcycloheptane-1,3-dicarboxylate,
Diethyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,4-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diheptyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Didecyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diethyl 3-hexylcycloheptane-1,2-dicarboxylate,
Diethyl 3,7-dihexylcycloheptane-1,2-dicarboxylate,
3-hexyl-7-pentylcycloheptane-1,2-dicarboxylate diisobutyl,
Diethyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid di-n-propyl, 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid diisopropyl, 3-methyl-7-n -Di-n-butyl propylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
3-methyl-7-n-propylcycloheptane-1,2-dicarboxylic acid dihexyl;
Dioctyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Didecyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate,
Diethyl 3-methylcyclooctane-1,2-dicarboxylate,
Diethyl 3-methylcyclodecane-1,2-dicarboxylate,
Diisobutyl 3-vinylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Diethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate,
Norbornane-2,3-dicarboxylate diisobutyl,
Tetracyclododecane-2,3-dicarboxylate diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,6-dimethyl-4-cyclohexene-1,2-dicarboxylic acid dihexyl;
Diheptyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Dioctyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Di-2-ethylhexyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Didecyl 3,6-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diethyl 3,6-dihexyl-4-cyclohexene-1,2-dicarboxylate,
Examples include 3-hexyl-6-pentyl-4-cyclohexene-1,2-dicarboxylate diisobutyl.

Moreover, the dicarboxylic acid ester of the cyclic diol compound corresponding to these can also be mentioned as a suitable compound. As such a compound, in particular,
3,6-dimethylcyclohexyl-1,2-diacetate,
3,6-dimethylcyclohexyl-1,2-dibutanate,
3-methyl-6-propylcyclohexyl-1,2-diol acetate,
3-methyl-6-propylcyclohexyl-1,2-dibutanate,
3,6-dimethylcyclohexyl-1,2-dibenzoate,
3,6-dimethylcyclohexyl-1,2-ditoluate,
3-methyl-6-propylcyclohexyl-1,2-dibenzoate,
3-methyl-6-propylcyclohexyl-1,2-ditoluate,
Etc. can be mentioned as a preferable example.

The compound having the diester structure as described above includes a plurality of COOR ¹ in the formula (2a).
Although isomers such as cis and trans derived from a group exist, any structure has an effect meeting the object of the present invention, but a higher trans content is preferable. The higher the trans content, the higher the activity and the stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution.

  As said ester compound (B1), the compound represented by following formula (2-1)-(2-6) is preferable.

[R ¹ and R in the above formulas (2-1) to (2-6) are the same as described above.

In the above formulas (2-1) to (2-3), the single bond in the cyclic skeleton (except for the C ^a -C ^a bond and the C ^a -C ^b bond) is replaced with a double bond. Also good.

In the above formulas (2-4) to (2-6), the single bond (excluding the C ^a -C ^a bond) in the cyclic skeleton may be replaced with a double bond.

Moreover, in said formula (2-3) and (2-6), n is an integer of 7-10. ]
As the cyclic ester compound (B1-a), a compound represented by the following formula (2b) is particularly preferable.

[In the formula (2b), n, R ¹ and R are the same as described above (that is, as defined in the formula (2a)), and a single bond (provided that a C ^a -C ^a bond and a C ^a excluding -C ^b bond.) may be replaced with a double bond. ]
Specific examples of the compound represented by the above formula (2b) include diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-hexyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-octyl, 3,6-diethylcyclohexane -1,2-dicarboxylate diisobutyl,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-dimethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-5-ethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate, di-n-octyl 3-methyl-5-n-propylcyclopentane-1,2-dicarboxylate, 3,5- Diisobutyl diethylcyclopentane-1,2-dicarboxylate,
Di-n-hexyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Di-n-octyl 3,5-diethylcyclopentane-1,2-dicarboxylate,
Diisobutyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-dimethylcycloheptane-1,2-dicarboxylate,
Diisobutyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-7-ethylcycloheptane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate, di-n-octyl 3-methyl-7-n-propylcycloheptane-1,2-dicarboxylate, 3,7- Diethylcycloheptane-1,2-dicarboxylate diisobutyl,
Di-n-hexyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Di-n-octyl 3,7-diethylcycloheptane-1,2-dicarboxylate,
Etc.

Among the above compounds,
Diisobutyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3,6-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-hexyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-ethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-hexyl, 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate di-n-octyl, 3,6-diethylcyclohexane -1,2-dicarboxylate diisobutyl,
Di-n-hexyl 3,6-diethylcyclohexane-1,2-dicarboxylate,
More preferred is di-n-octyl 3,6-diethylcyclohexane-1,2-dicarboxylate. These compounds can be produced using the Diels Alder reaction. However, since the polyene compound as a raw material is relatively expensive, the production cost tends to be slightly higher than that of a conventional electron donor compound.

The cyclic ester compound (B1-a) having a diester structure as described above has isomers such as cis and trans, and any structure has an effect meeting the object of the present invention. Higher body content is preferred, and higher trans isomer content tends to have higher activity and stereoregularity of the resulting polymer, as well as the effect of broadening the molecular weight distribution. The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%.

[Cyclic ester compound (B1-b)]
The cyclic ester compound (B1-b) has a plurality of carboxylic acid ester groups and is represented by the following formula (2c).

In formula (2c), n is an integer of 5 to 10, preferably an integer of 5 to 7, particularly preferably 6. C ^a and C ^b represent carbon atoms.

The carbon-carbon bonds in the cyclic skeleton are preferably all single bonds, but other than the C ^a -C ^a bond and the C ^a -C ^b bond when R ⁵ is a hydrogen atom in the cyclic skeleton. Any single bond may be replaced with a double bond.

R ⁴ and R ⁵ are each independently COOR ¹ or a hydrogen atom, and R ⁴ and R ⁵
At least one of these is COOR ¹ , and each R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms.

A plurality of R ^{1 s} are each independently a monovalent carbon atom having 1 to 20, preferably 1 to 10, more preferably 2 to 8, more preferably 4 to 8 and particularly preferably 4 to 6 carbon atoms. It is a hydrogen group. As this hydrocarbon group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, Hexadecyl group, octadecyl group, eicosyl group and the like can be mentioned. Among them, n-butyl group, isobutyl group, hexyl group and octyl group are preferable, and n-butyl group and isobutyl group produce an olefin polymer having a wide molecular weight distribution. This is particularly preferable because it can be performed.

As such a cyclic ester compound (B1-b),
Diethyl cyclohexane-1,2-dicarboxylate,
Di-n-propyl cyclohexane-1,2-dicarboxylate,
Diisopropylcyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexylcyclohexane-1,2-dicarboxylate didecyl,
Cyclohexane-1,3-dicarboxylate diethyl,
Cyclohexane-1,3-dicarboxylate diisobutyl,
Diethyl cyclopentane-1,2-dicarboxylate,
Diisopropyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Cycloheptane-1,2-dicarboxylate diheptyl,
Didecyl cyclopentane-1,2-dicarboxylate,
Diethyl cyclopentane-1,3-dicarboxylate,
Cyclopentane-1,3-dicarboxylate diisobutyl,
Diethyl cycloheptane-1,2-dicarboxylate,
Diisopropyl cycloheptane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
Diheptyl cycloheptane-1,2-dicarboxylate,
Didecyl cycloheptane-1,2-dicarboxylate,
Diethyl cycloheptane-1,3-dicarboxylate,
Diisobutyl cycloheptane-1,3-dicarboxylate,
Diethyl cyclooctane-1,2-dicarboxylate,
Diethyl cyclodecane-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylate diethyl,
Di-n-propyl 4-cyclohexene-1,2-dicarboxylate,
Diisopropyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-butyl 4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylic acid dihexyl;
4-cyclohexene-1,2-dicarboxylate diheptyl,
Dioctyl 4-cyclohexene-1,2-dicarboxylate,
Didecyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,3-dicarboxylate diethyl,
Diisobutyl 4-cyclohexene-1,3-dicarboxylate,
Diethyl 3-cyclopentene-1,2-dicarboxylate,
Diisopropyl 3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3-cyclopentene-1,2-dicarboxylate,
Diheptyl 3-cyclopentene-1,2-dicarboxylate,
Didecyl 3-cyclopentene-1,2-dicarboxylate,
Diethyl 3-cyclopentene-1,3-dicarboxylate,
Diisobutyl 3-cyclopentene-1,3-dicarboxylate,
4-cycloheptene-1,2-dicarboxylate diethyl,
4-cycloheptene-1,2-dicarboxylate diisopropyl,
4-cycloheptene-1,2-dicarboxylate diisobutyl,
4-cycloheptene-1,2-dicarboxylic acid diheptyl,
Didecyl 4-cycloheptene-1,2-dicarboxylate,
4-cycloheptene-1,3-dicarboxylate diethyl,
Dicyclobutyl 4-cycloheptene-1,3-dicarboxylate,
Diethyl 5-cyclooctene-1,2-dicarboxylate,
Examples include diethyl 6-cyclodecene-1,2-dicarboxylate.

Moreover, the dicarboxylic acid ester of the cyclic diol compound corresponding to these can also be mentioned as a suitable compound. As such a compound, in particular,
Cyclohexyl-1,2-diacetate,
Cyclohexyl-1,2-dibutanate,
Cyclohexyl-1,2-dibenzoate,
Cyclohexyl-1,2-ditoluate,
The compound having a diester structure as described above has isomers such as cis and trans, and any structure has an effect that meets the object of the present invention.
The ratio of the trans form of the cis form and the trans form is preferably 51% or more. A more preferred lower limit is 55%, even more preferred is 60%, and particularly preferred is 65%. On the other hand, the preferable upper limit is 100%, more preferably 90%, still more preferably 85%, and particularly preferably 79%. The reason why a cyclic ester compound having a trans isomer ratio within this range is unclear, but it is presumed that the variation of the stereoisomer is in a region suitable for wide molecular weight distribution.

  In particular, the trans purity of cyclohexane 1,2-dicarboxylic acid diester in which n = 6 in the above formula (2c) is in the above range.

  If the trans purity is less than 51%, the effect of wide molecular weight distribution, activity, stereospecificity and the like may be insufficient. On the other hand, if the trans purity exceeds 79%, the effect of wide molecular weight distribution may be insufficient. That is, if the trans purity is within the above range, it is advantageous to achieve both a high level of both the effect of broadening the molecular weight distribution of the polymer obtained and the activity of the catalyst and the high stereoregularity of the polymer obtained. There are many.

As the cyclic ester compound (B1-b), a compound having a cycloalkane-1,2-dicarboxylic acid diester structure represented by the following formula (2d) is particularly preferable, and in particular, a cyclohexane-1,2-dicarboxylic acid diester. n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Diisobutyl cyclopentane-1,2-dicarboxylate,
Diheptyl cyclopentane-1,2-dicarboxylate,
Diisobutyl cycloheptane-1,2-dicarboxylate,
Cycloheptane-1,2-dicarboxylic acid diheptyl and the like are preferable.

[In formula (2d), n and R ¹ are the same as described above (that is, as defined in formula (2c)), and a single bond in the cyclic skeleton (provided that a C ^a -C ^a bond and a C ^a -C except for the ^b binding.) may be replaced with a double bond. ]
Among the above compounds,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylate dihexyl,
Diheptyl cyclohexane-1,2-dicarboxylate,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Is more preferable. The reason is not only the catalyst performance but also that these compounds can be produced relatively inexpensively using the Diels Alder reaction.

These compounds may be used alone or in combination of two or more. Further, these cyclic ester compounds (B1-a) and (B1-b) may be used in combination as long as the object of the present invention is not impaired.
Combination molar ratio of cyclic ester compound (B1-a) and cyclic ester compound (B1-b) (cyclic ester compound (B1-a) / (cyclic ester compound (B1-a) + cyclic ester compound (B1-b))) × 100 (mol%)) is preferably 10 mol% or more. More preferably, it is 30 mol% or more, More preferably, it is 40 mol% or more, Most preferably, it is 50 mol% or more. A preferred upper limit is 99 mol%, preferably 90 mol%. More preferably, it is 85 mol%, Most preferably, it is 80 mol%.

  The cyclic ester compounds (B1-a) and (B1-b) may be formed in the process of preparing the solid titanium catalyst component (I). For example, when the solid titanium catalyst component (I) is prepared, the carboxylic anhydride or carboxylic dihalide corresponding to the cyclic ester compounds (B1-a) and (B1-b) and the corresponding alcohol are substantially By providing the contacting step, the cyclic ester compounds (B1-a) and (B1-b) can be contained in the solid titanium catalyst component.

[Diether Compound (C)]
Examples of the diether compound (C) include compounds having two or more ether bonds existing through a plurality of atoms (hereinafter sometimes referred to as “polyether”). Examples of the polyether include compounds in which atoms present between ether bonds are carbon, silicon, oxygen, nitrogen, sulfur, phosphorus, boron, or two or more selected from these. Among these, a compound in which a relatively bulky substituent is bonded to an atom between ether bonds and a plurality of carbon atoms are contained in an atom present between two or more ether bonds is preferable. For example, a polyether compound represented by the following formula is preferred.

In the above formula (3), m is an integer of 1 to 10, more preferably an integer of 3 to 10, and particularly preferably 3 to 5. R ¹¹ , R ¹² , R ^{31 to} R ³⁶ are each independently at least one selected from a hydrogen atom or carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron and silicon. A substituent having a seed element.

Preferably the R ^11, R ^12, a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms, preferably about R ³¹ to R ³⁶ hydrogen atom or a carbon atom It is a hydrocarbon group of number 1-6.

Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 -An ethylhexyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, Preferably they are an ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group.

Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group, preferably a hydrogen atom and a methyl group.

Arbitrary R ¹¹ , R ¹² , R ^{31 to} R ³⁶ , preferably R ¹¹ and R ¹² may jointly form a ring other than a benzene ring, and an atom other than carbon is contained in the main chain. May be.

As specific compounds having two or more ether bonds as described above,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane,
2-methyl-2-propyl-1,3-dimethoxypropane,
2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2,2-bis (2-cyclohexylethyl) -1,3-dimethoxypropane,
2-methyl-2-isobutyl-1,3-dimethoxypropane,
2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2,2-diisobutyl-1,3-diethoxypropane,
2,2-diisobutyl-1,3-dibutoxypropane,
2-isobutyl-2-isopropyl-1,3-dimethoxypropane,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-di-t-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-diisopropyl-1,4-diethoxybutane,
2,4-diisopropyl-1,5-dimethoxypentane,
2,4-diisobutyl-1,5-dimethoxypentane,
2,4-diisoamyl-1,5-dimethoxypentane,
3-methoxymethyltetrahydrofuran,
3-methoxymethyldioxane,
1,2-diisobutoxypropane,
1,2-diisobutoxyethane,
1,3-diisoamyloxyethane,
1,3-diisoamyloxypropane,
1,3-diisoneopentyloxyethane,
1,3-dineopentyloxypropane,
2,2-tetramethylene-1,3-dimethoxypropane,
2,2-pentamethylene-1,3-dimethoxypropane,
2,2-hexamethylene-1,3-dimethoxypropane,
1,2-bis (methoxymethyl) cyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane,
2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,
Etc. can be illustrated.

  Of these, 1,3-diethers are preferred, and in particular, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane are preferred.

[Titanium Compound (Liquid Titanium Compound (D))]
Examples of the titanium compound (liquid titanium compound (D)) used for the preparation of the solid titanium catalyst component (I) according to the present invention include, for example, JP-A-58-83006 and JP-A-56-811 (patents). Titanium compounds described in Documents 1, 2) can be mentioned, and specifically, for example, the following general formula:
Ti (OR) _g X _4-g
(R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 4)
The tetravalent titanium compound shown by these can be mentioned. More specifically,
Titanium tetrahalides such as TiCl ₄ and TiBr ₄ ;
_{Ti (OCH 3) Cl 3,} Ti (OC 2 H 5) Cl 3, Ti (O n-C 4 H 9) Cl 3, Ti (OC 2 H 5) Br 3, Ti (O isoC 4 H 9) Br Trihalogenated alkoxytitanium such as ₃ ;
Dihalogenated alkoxytitanium such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ;
_{Ti (OCH 3) 3 Cl,} Ti (O n-C 4 H 9) 3 Cl, monohalogenated alkoxy titanium such as _{Ti (OC 2 H 5) 3} Br;
Examples thereof include tetraalkoxy titanium such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (OC ₄ H ₉ ) ₄ , and Ti (O 2 -ethylhexyl) ₄ .

  Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more.

[Electron donor (E)]
In preparation of the solid titanium catalyst component (I) of the present invention, an electron donor (E) may be used in addition to the ester compound (B) and the diether compound (C). Examples of the electron donor (E) include acid halides, acid amides, nitriles, acid anhydrides, and organic acid esters other than the ester compound (B) described below.

Specifically, acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride;
Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide;
Nitriles such as acetonitrile, benzonitrile, trinitrile;
Acid anhydrides such as acetic anhydride, phthalic anhydride, benzoic anhydride;
Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, benzoic acid Methyl, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate And organic acid esters having 2 to 18 carbon atoms such as ethyl anisate, ethyl ethoxybenzoate, γ-butyllactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate. Examples of organic acid esters include known polyvalent carboxylic acid esters.

Specific examples of such polycarboxylic acid esters include diethyl succinate, dibutyl succinate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, Diethyl malonate, diethyl dibutyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, di-2-ethylhexyl fumarate, diethyl itaconate, dioctyl citraconic acid, etc. Aliphatic polycarboxylic acid ester, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisophthalate Lopyl, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, phthalic acid Aromatic polycarboxylic acid esters such as diphenyl, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitic acid, dibutyl trimellitic acid; and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid Can do. However, in the above, it may be preferable to avoid using a polyfunctional aromatic compound or to keep it to the minimum necessary for reasons of safety and health.

  Other examples of polyvalent carboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. And esters of chain dicarboxylic acids.

  In the present invention, two or more electron donors (E) can be used in combination. In the present invention, the electron donor (E) as exemplified above may be finally contained in the solid titanium catalyst component. Therefore, you may use the other compound which can produce | generate these compounds in the process of preparing a solid titanium catalyst component. In this case, other compounds can also be used so that two or more kinds of electron donors are generated.

[Preparation of solid titanium catalyst component (I)]
For the preparation of the solid titanium catalyst component (I) of the present invention, a known method can be used without limitation except that the ester compound (B) and the diether compound (C) are used. Specific examples of the method include the following methods (P-1) to (P-4).

  (P-1) An inert hydrocarbon solvent comprising a solid adduct comprising a magnesium compound and a catalyst component (F) described later, a cyclic ester compound (B) and a diether compound (C), and a titanium compound in a liquid state A method of contacting in suspension in the presence of coexistence.

  (P-2) A solid adduct composed of a magnesium compound and a catalyst component (F) described later, a cyclic ester compound (B) and a diether compound (C), and a titanium compound in a liquid state are divided into a plurality of times. How to contact.

  (P-3) An inert hydrocarbon solvent comprising a solid adduct comprising a magnesium compound and a catalyst component (F) described later, a cyclic ester compound (B) and a diether compound (C), and a titanium compound in a liquid state The method of making it contact in a suspended state in coexistence, and making it contact in several steps.

  (P-4) A method in which a magnesium compound in a liquid state composed of a magnesium compound and a catalyst component (F) described later, a titanium compound in a liquid state, a cyclic ester compound (B), and a diether compound (C) are brought into contact.

  According to the above methods (P-1) to (P-4), the magnesium compound, the ester compound (B), the diether compound (C), and the titanium compound in a liquid state react to have solid olefin polymerization performance. While forming the catalyst component, the particle aggregation proceeds, and a solid titanium catalyst component having an extremely wide range of particle diameters with an average particle diameter of 1 to 50 μm can be obtained.

  The lower limit of the preferable average particle diameter of the solid titanium catalyst component (I) of the present invention obtained by the methods (P-1) to (P-4) is 5 μm, more preferably 8 μm, and particularly preferably 10 μm. The preferred upper limit is 45 μm, particularly preferably 40 μm.

  Moreover, as a method of preparing the solid titanium catalyst component (I) of the present invention, an ester compound (B) and a diether compound (C) are used as an electron donor, and the ester compound (B) is converted into a liquid titanium compound (D The known liquid state magnesium compound and the liquid state titanium compound are brought into contact with each other except that the step of contacting the liquid magnesium compound (A) with the liquid state titanium compound (D) prior to or in combination with the liquid titanium compound (D) is essential. Thus, a method for obtaining a solid titanium catalyst component can be used without limitation. More preferably, after contacting the liquid magnesium compound (A) and the ester compound (B) prior to the liquid titanium compound (D), they may be the same as or different from the ester compound (B). There is a step of contacting the good ester compound (B1) with the diether compound (C). Examples of these methods include the following methods (P-5) to (P-14).

  (P-5) A method in which a liquid titanium compound (A), a mixture of an ester compound (B) and a diether compound (C) are brought into contact with the liquid titanium compound (D) to precipitate a solid titanium composite.

  (P-6) A method in which a liquid titanium compound (A), an ester compound (B), and a mixture of a diether compound (C) and a liquid titanium compound (D) are contacted to precipitate a solid titanium composite. At this time, the liquid titanium compound (D) may be contacted in a plurality of times.

  (P-7) A method in which a liquid titanium compound (A), a mixture of an ester compound (B) and a diether compound (C) are contacted with a liquid titanium compound (D) to precipitate a solid titanium composite. At this time, the electron donor (E) may be contacted in an optional step as necessary.

  (P-8) A method of depositing a solid titanium composite by contacting a mixture of a liquid magnesium compound (A) and an ester compound (B) with a liquid titanium compound (D). Further, the ester compound (B1) and the diether compound (C) may be contacted in an arbitrary step.

  (P-9) A method of depositing a solid titanium composite by contacting a liquid titanium compound (D) with a mixture of a liquid magnesium compound (A) and an ester compound (B). Further, the ester compound (B1), the diether compound (C), and the electron donor (E) may be brought into contact with each other as necessary.

  (P-10) A method of depositing a solid titanium composite by contacting a liquid titanium compound (D) with a mixture of a liquid magnesium compound (A) and an ester compound (B). Further, the ester compound (B1), the diether compound (C), and the electron donor (E) may be brought into contact with each other as necessary. At this time, the liquid titanium compound (D) may be contacted in a plurality of times.

  (P-11) A method in which a mixture of a liquid magnesium compound (A) and an ester compound (B) is contacted with a liquid titanium compound (D) to precipitate a solid titanium composite. Further, the diether compound (C) may be contacted in any step.

  (P-12) A method of depositing a solid titanium composite by bringing a mixture of a liquid magnesium compound (A) and an ester compound (B) into contact with a liquid titanium compound (D). Furthermore, you may make a diether compound (C) and an electron donor (E) contact in an arbitrary process as needed.

  (P-13) A method of depositing a solid titanium composite by bringing a mixture of a liquid magnesium compound (A) and an ester compound (B) into contact with a liquid titanium compound (D). Furthermore, you may make a diether compound (C) and an electron donor (E) contact in an arbitrary process as needed. At this time, the liquid titanium compound (D) may be contacted in a plurality of times.

  (P-14) A method in which a liquid magnesium compound (A) is contacted with a contact product or mixture of an ester compound (B) and a liquid titanium compound (D) to precipitate a solid titanium composite. At this time, the ester compound (B1), the diether compound (C) and the electron donor (E) may be brought into contact with each other as necessary, and the liquid titanium compound (D) is brought into contact in several steps. May be.

  Among the methods described above, a method of using the liquid magnesium compound (A) and the ester compound (B) as a premixed liquid is preferable. Moreover, after making a liquid titanium compound (D) contact, it is preferable to make an ester compound (B1) and a diether compound (C) contact further.

  According to the above methods (P-5) to (P-14), the liquid magnesium compound (A), the ester compound (B), the diether compound (C), and the liquid titanium compound (D) react to produce olefin polymerization performance. A solid titanium catalyst component having a very wide range of particle diameters with an average particle diameter of 1 to 50 μm can be obtained. Usually, in order to produce a solid titanium catalyst component having a large particle size, a production process of a carrier or a magnesium compound having a large particle size is often required. The production of the carrier and the magnesium compound often requires a dedicated facility, which causes an increase in fixed costs. On the other hand, the method of bringing the liquid magnesium compound (A) into contact with the liquid titanium compound (D) causes the particle aggregation to proceed simultaneously during the reaction, so that manufacturing equipment such as a carrier is substantially unnecessary. Can be reduced.

  The lower limit of the preferable average particle diameter of the solid titanium catalyst component (I) of the present invention obtained by the methods (P-5) to (P-14) is 3 μm, more preferably 5 μm, and particularly preferably 10 μm. The preferred upper limit is 45 μm, particularly preferably 40 μm.

  The solid titanium catalyst component (I) of the present invention has a halogen / titanium (atomic ratio) of 2 to 100, preferably 4 to 90, and a magnesium / titanium (atomic ratio) of 2 to 100, preferably 4. It is desirable to be ~ 50. The ester compound (B) / titanium (molar ratio) is 0 to 100, preferably 0.01 to 10. Diether compound (C) / titanium (molar ratio) is 0 to 100, preferably 0.01 to 10. The content of the component that may contain the electron donor (E) described above is such that the electron donor (E) / titanium (molar ratio) is 0.01 to 100, preferably 0.2 to 10. It is. Further, when two types of ester compound (B) and ester compound (B1) are used, (B) + (B1) / titanium (molar ratio) is 0 to 100, preferably 0.01 to 10, (B) / Titanium (molar ratio) and (B1) / titanium (molar ratio) are both 0 to 100, preferably 0.01 to 10.

  The catalyst component (F) described later has a catalyst component (F) / titanium atom (molar ratio) of 0 to 100, preferably 0 to 10.

  Here, as a preferable ratio of the ester compound (B) and the diether compound (C), the upper limit of the value (mol%) of 100 × diether compound (C) / (cyclic ester compound (B) + diether compound (C)) Is 70 mol%, preferably 50 mol%, more preferably 30 mol%. Moreover, a minimum is 2.5 mol%, Preferably it is 5 mol%, More preferably, it is 7.5 mol%.

Moreover, as a preferable molar ratio of the ester compound (B) and magnesium, the value (molar ratio) of the ester compound (B) / magnesium is 0 to 0.50, preferably 0.01 to 0.40, more preferably. It is 0.05-0.30. Furthermore, as a preferable molar ratio of the diether compound (C) and magnesium, the value (molar ratio) of the diether compound (C) / magnesium is 0 to 0.20, preferably 0.005 to 0.15, more preferably. 0.01
~ 0.10.
The more detailed preparation conditions for the solid titanium catalyst component (I) use an ester compound (B) and a diether compound (C) as electron donors, and a step of bringing them into contact with a magnesium compound in a liquid state is essential. Other than the above, for example, conditions described in JP-A-58-83006 and JP-A-56-811 (Patent Documents 1 and 2) can be preferably used.

[Catalyst component (F)]
In the above methods (P-1) to (P-4), the catalyst component (F) used for the formation of the solid adduct or the liquid magnesium compound is a temperature range of about room temperature to about 300 ° C. A known compound capable of solubilizing the magnesium compound is preferably, for example, alcohol, aldehyde, amine, carboxylic acid, and a mixture thereof. Examples of these compounds include compounds described in detail in JP-A-57-63310 and JP-A-5-170843.

More specifically, the alcohol having the above-described solubilizing ability of magnesium compound is methanol, ethanol, propanol, butanol, isobutanol, ethylene glycol, 2-methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, Aliphatic alcohols such as 2-ethylhexanol, decanol, dodecanol;
Cycloaliphatic alcohols such as cyclohexanol and methylcyclohexanol;
Aromatic alcohols such as benzyl alcohol and methylbenzyl alcohol;
Examples thereof include aliphatic alcohols having an alkoxy group such as n-butyl cellosolve.

  Examples of the carboxylic acid include organic carboxylic acids having 7 or more carbon atoms such as caprylic acid and 2-ethylhexanoic acid. Examples of the aldehyde include aldehydes having 7 or more carbon atoms such as capric aldehyde and 2-ethylhexyl aldehyde.

  Examples of the amine include amines having 6 or more carbon atoms such as heptylamine, octylamine, nonylamine, laurylamine, 2-ethylhexylamine.

  As said catalyst component (F), said alcohol is preferable, and especially ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol, etc. are preferable.

  The amount of the magnesium compound and the catalyst component (F) used in preparing the solid adduct or the liquid magnesium compound varies depending on the type, contact conditions, and the like. It is used in an amount of 0.1 to 20 mol / liter, preferably 0.5 to 5 mol / liter per unit volume of F). Further, if necessary, a medium inert to the solid adduct can be used in combination. As said medium, a well-known hydrocarbon compound, such as heptane, octane, decane, is mentioned as a preferable example.

The composition ratio of magnesium and catalyst component (F) in the resulting solid adduct or liquid magnesium compound varies depending on the type of compound used, but cannot be specified unconditionally, but with respect to 1 mol of magnesium in the magnesium compound. The catalyst component (F) is preferably in the range of 2.0 mol or more, more preferably 2.2 mol or more, further preferably 2.3 mol or more, particularly preferably 2.4 mol or more and 5 mol or less. .

  The ester compound (B), diether compound (C) and catalyst component (F) as described above may be considered to belong to a component called an electron donor by those skilled in the art. The above-mentioned electron donor component has the effect of increasing the stereoregularity of the resulting polymer while maintaining the high activity of the catalyst, the effect of controlling the composition distribution of the resulting copolymer, the particle shape of the catalyst particles, It is known to show the effect of controlling the particle size and the effect of controlling the hydrogen responsiveness.

  The ester compound (B) is considered to exhibit an effect of controlling the molecular weight distribution by itself being an electron donor.

  In addition, as an example of the manufacturing method of said solid adduct, after mixing a magnesium compound and a catalyst component (F) and dissolving a magnesium compound in a catalyst component (F), it emulsifies with said inert medium. -It can be obtained by cooling and solidifying.

[Olefin polymerization catalyst]
The catalyst for olefin polymerization according to the present invention contains the solid titanium catalyst component (I) thus obtained, and preferably a metal selected from Group 1, Group 2 and Group 13 of the periodic table. And an organometallic compound catalyst component (II). As such an organometallic compound catalyst component (II), for example, an organoaluminum compound, a complex alkylated product of a Group 1 metal and aluminum, an organometallic compound of a Group 2 metal, or the like can be used. Among these, an organoaluminum compound is preferable.

  Specific examples of the organometallic compound catalyst component (II) include organometallic compound catalyst components described in known documents such as EP585869A1.

  In addition, the olefin polymerization catalyst of the present invention can use an electron donor (III) as necessary together with the organometallic compound catalyst component (II). The electron donor (III) is preferably an organosilicon compound. Examples of the organosilicon compound include those represented by the following general formula.

R _n Si (OR ′) _4-n
(In the formula, R and R ′ are hydrocarbon groups, and 0 <n <4)
Specific examples of the organosilicon compound represented by the above general formula include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, and dicyclohexyldimethoxysilane. , Cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxy Silane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane; tricyclopentylmethoxysilane Dicyclopentyl methylmethoxysilane, dicyclopentyl ethyl silane, is cyclopentyl dimethylethoxysilane used.

  Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane and the like are preferably used. These organosilicon compounds can be used in combination of two or more.

In addition, diether compounds (C) and electron donors (used as solid titanium catalyst components)
E). In particular, known polyethers introduced as an example thereof can be cited as preferred examples.

  In addition, in this invention, the catalyst for olefin polymerization can contain the other component useful for olefin polymerization as needed other than each above components. For example, antistatic agents, particle aggregating agents, storage stabilizers and the like can be mentioned.

[Olefin polymerization method]
The olefin polymerization method according to the present invention is characterized in that olefin polymerization is performed using the olefin polymerization catalyst of the present invention.

  In the olefin polymerization method of the present invention, the main polymerization (Polymerization) can be performed in the presence of a prepolymerization catalyst obtained by prepolymerization of an olefin in the presence of the olefin polymerization catalyst of the present invention. . This prepolymerization is carried out by prepolymerizing the olefin in an amount of 0.1 to 1000 g, preferably 0.3 to 500 g, particularly preferably 1 to 200 g, per 1 g of the olefin polymerization catalyst.

  In the prepolymerization, a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization can be used. The concentration of the solid titanium catalyst component (I) in the prepolymerization is usually about 0.001 to 200 mmol, preferably about 0.01 to 50 mmol, and particularly preferably about 0.1 to 50 mmol in terms of titanium atom per liter of the liquid medium. A range of 1 to 20 mmol is desirable.

  The amount of the organometallic compound catalyst component (II) in the prepolymerization is such that 0.1 to 1000 g, preferably 0.3 to 500 g of polymer is produced per 1 g of the solid titanium catalyst component (I). The amount is usually about 0.1 to 300 mol, preferably about 0.5 to 100 mol, particularly preferably 1 to 50 mol, per mol of titanium atom in the solid titanium catalyst component (I). desirable.

  In the prepolymerization, an electron donor (III) or the like can be used as necessary. In this case, these components are added in an amount of 0.1 to 50 mol per mol of titanium atom in the solid titanium catalyst component (I). , Preferably 0.5-30 mol, more preferably 1-10 mol.

  The prepolymerization can be performed under mild conditions by adding an olefin and the above catalyst components to an inert hydrocarbon medium.

In this case, specific examples of the inert hydrocarbon medium used include aliphatic hydrocarbons such as propane, butane, heptane, heptane, heptane, octane, decane, dodecane, and kerosene;
Cycloaliphatic hydrocarbons such as cycloheptane, cycloheptane, methylcycloheptane;
Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, or mixtures thereof.

  Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. The prepolymerization can be carried out continuously using the olefin itself as a solvent, but when an inert hydrocarbon medium is used in this way, the prepolymerization is preferably carried out batchwise.

  On the other hand, the prepolymerization can be carried out using the olefin itself as a solvent, or the prepolymerization can be carried out in a substantially solvent-free state. In this case, it is preferable to perform preliminary polymerization continuously.

  The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described later. Specifically, propylene is preferable.

  The temperature during the prepolymerization is usually within the range of about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C.

  Next, the main polymerization (Polymerization) performed after passing through the pre-polymerization or without going through the pre-polymerization will be described.

  Examples of the olefin that can be used in the polymerization include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl- 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like can be mentioned, but propylene, 1-butene, 1-pentene, 4 -Methyl-1-pentene or the like is preferably used. In addition to these, aromatic vinyl compounds such as styrene and allylbenzene; and alicyclic vinyl compounds such as vinylcycloheptane can also be used. It is also possible to use two or more of these compounds in combination. Furthermore, compounds having polyunsaturated bonds such as conjugated dienes and non-conjugated dienes such as dienes such as cyclopentene, cycloheptene, norbornene, tetracyclododecene, isoprene and butadiene are used as polymerization raw materials together with ethylene and α-olefin. You can also.

  In the present invention, the prepolymerization and the main polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods.

  When the main polymerization takes the form of slurry polymerization, the reaction solvent can be an inert hydrocarbon used during the above-described prepolymerization, or a liquid olefin at the reaction temperature.

  For the main polymerization in the polymerization method of the present invention, the solid titanium catalyst component (I) is usually about 0.0001 to 0.5 mmol, preferably about 0.00, in terms of titanium atoms per liter of polymerization volume. Used in an amount of 005 to 0.1 mmol. Further, the organometallic compound catalyst component (II) is usually about 1 to 2000 mol, preferably about 5 to 500 mol in terms of metal atom, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. Used in various amounts. When the electron donor (III) is used, 0.001 to 50 mol, preferably 0.01 to 30 mol, and particularly preferably 0.001 mol, per mol of the metal atom of the organometallic compound catalyst component (II). Used in an amount of 05 to 20 mol.

  If hydrogen is used during the main polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer having a high melt flow rate can be obtained.

In the main polymerization in the present invention, the polymerization temperature of the olefin is usually about 20 to 100 ° C., preferably about 50 to 90 ° C., and the pressure is usually atmospheric pressure to 100 kg / cm ² , preferably about ^{2 to} 50 kg / cm ² . Set to cm ² . In the polymerization method of the present invention, the polymerization can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

  The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer.

When olefin polymerization, particularly propylene polymerization, is performed using the olefin polymerization catalyst as described above, the decane insoluble component content is 70% or more, preferably 85% or more, particularly preferably 90% or more. High propylene polymer is obtained.

  Furthermore, according to the olefin polymerization method of the present invention, a polyolefin having a wide molecular weight distribution, particularly polypropylene, can be obtained without performing multi-stage polymerization, even by polymerization with a small number of stages, for example, single-stage polymerization. In the olefin polymerization method of the present invention, in particular, the ratio of the component having a higher molecular weight is higher than that of the conventional olefin polymer having the same melt flow rate (MFR), and (especially the solid component and It is characterized in that an olefin polymer having a low ratio of components having a low molecular weight is often obtained. This characteristic can be confirmed by gel permeation chromatography (GPC) measurement described later, and a polymer having both a high Mw / Mn value and a high Mz / Mw value can be obtained.

  Polypropylene obtained by using a conventional solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor is an index of molecular weight distribution obtained by GPC measurement, for example, in a region where MFR is 1 to 10 g / 10 min. In general, the Mw / Mn value was 5 or less and the Mz / Mw value was less than 4. However, when the method for producing an olefin polymer of the present invention was used, the Mw / Mn value was obtained under the same polymerization conditions as described above. Can be obtained from 6 to 30, preferably 7 to 20. Preferably, an olefin polymer having an Mz / Mw value of 4 to 15, more preferably 4.5 to 10 can be obtained. In particular, according to the method for producing an olefin polymer of the present invention, a polymer having a high Mz / Mw value is often obtained. The upper limit of the Mz / Mn value is preferably 300, more preferably 250, and particularly preferably 200. In particular, in the method for producing the polypropylene resin, a polymer having a high Mz / Mw value and Mz / Mn value is often obtained.

  Polypropylene having a high Mw / Mn value is commonly known to those skilled in the art to be excellent in moldability and rigidity. On the other hand, a high Mz / Mw value indicates a high content ratio of components having a high molecular weight, and it is expected that the resulting polypropylene has a high melt tension and a high possibility of being excellent in moldability.

  If the olefin polymerization method of the present invention is used, a polymer having a wide molecular weight distribution can be obtained without performing multi-stage polymerization, so that there is a possibility that the polymer production apparatus can be further simplified. In addition, when applied to a conventional multistage polymerization method, it is expected that a polymer having better melt tension and moldability can be obtained.

  As another method for obtaining a polymer having a wide molecular weight distribution, there are methods of dissolving and mixing or melting and kneading polymers having different molecular weights. However, the polymer obtained by these methods is relatively complicated. May not be sufficiently improved in melt tension and moldability. This is presumably because polymers having different molecular weights are basically difficult to mix. On the other hand, the polymer obtained by the olefin polymerization method of the present invention has a high melt tension and excellent moldability because polymers of different molecular weights in a very wide range are mixed at the catalyst level, that is, at the nano level. It is expected that

  Furthermore, the olefin polymerization method of the present invention is characterized in that an olefin polymer with controlled stereoregularity is obtained. This feature can be confirmed by measuring the amount of decane-soluble component described later, and an olefin polymer having a small amount of decane-soluble component can be obtained.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.

In the following examples, the bulk specific gravity, melt flow rate, decane soluble (insoluble) component amount, and molecular weight distribution of the propylene polymer were measured by the following methods.
(1) Bulk specific gravity (BD):
It measured according to JIS K-6721.
(2) Melt flow rate (MFR):
In accordance with ASTM D1238E, the measurement temperature was 190 ° C.
(3) Amount of decane soluble (insoluble) component:
A glass container is charged with about 3 grams of propylene polymer (measured to the unit of 10 ^-4 grams, b grams), 500 ml of decane, a small amount of heat-resistant stabilizer in decane, and in a nitrogen atmosphere. While stirring with a stirrer, the temperature is raised to 150 ° C. in 2 hours to dissolve the propylene polymer. After maintaining at this temperature for 2 hours, it is gradually cooled to 23 ° C. over 8 hours. The liquid containing the obtained propylene polymer precipitate is filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. A 100 ml portion of the filtrate is collected and dried under reduced pressure to obtain a portion of the decane soluble component, and the weight is measured to the unit of 10 ^-4 grams (a gram).
After this operation, the amount of decane soluble component is determined by the following formula.

Decane-soluble component content = 100 × (500 × a) / (100 × b)
Decane insoluble component content = 100-100 × (500 × a) / (100 × b)
As the compounds corresponding to the ester compound (B) and ester compound (B1) of the present invention, Azuma Co., Ltd. synthetic products were used unless otherwise specified. The isomer purity of the trans isomer and cis isomer is 95% or more unless otherwise specified.
(4) Molecular weight distribution (Mw / Mn, Mz / Mw):
Liquid chromatograph: Waters ALC / GPC 150-C plus type (suggested refractometer detector integrated type)
Column: Tosoh Corporation GMH6-HT × 2 and GMH6-HTL × 2 were connected in series.
Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
Calibration curve creation method: Sample concentration using standard polystyrene sample: 0.10% (w / w)
Sample solution volume: 500 μl
The Mw / Mn value and the Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes [Example 1]
(Preparation of solid titanium catalyst component (α1))
Anhydrous magnesium chloride (75 g), decane (280.3 g) and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution, and then cyclohexane-1,2-dicarboxylate n-propyl (15.15) was added to this solution. 1 g was added and further stirred and mixed at 130 ° C. for 1 hour.
After cooling the homogeneous solution thus obtained to room temperature, 38 ml of this uniform solution was charged dropwise into 100 ml of titanium tetrachloride maintained at −24 ° C. over 45 minutes with stirring at a stirring rotational speed of 350 rpm. After the completion of charging, the temperature of the mixed solution was raised to 80 ° C. over 6.7 hours. When the temperature reached 80 ° C., diisobutyl cyclohexane 1,2-dicarboxylate (trans ratio 78%) was added to Mg in the mixed solution. 0.05 mole times the atom was added. The temperature was raised again to 100 ° C. over 20 minutes. When the temperature reached 100 ° C., 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added in an amount of 0.025 mol times Mg atoms. While maintaining 100 ° C., the mixture was kept under stirring at the same temperature for 35 minutes. After the completion of the reaction, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 100 ° C. for 35 minutes. After completion of the reaction, the solid portion was again collected by hot filtration, and sufficiently washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [α1] prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [α1] thus obtained was 3.1% by mass of titanium, 17% by mass of magnesium, 9.4% by mass of n-propylcyclohexane-1,2-dicarboxylate, cyclohexane 1, They were 10.2% by mass of diisobutyl 2-dicarboxylate, 2.2% by mass of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, and 1.7% by mass of 2-ethylhexyl alcohol residue.

(Main polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a polymerization vessel having an internal volume of 2 liters, 0.5 mmol of triethylaluminum, 0.017 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (α1) were added to titanium atoms. 0.004 mmol was added in terms of conversion, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 1 shows the activity, bulk specific gravity, MFR, and amount of decane insoluble components.

[Example 2]
Polymerization of propylene was performed in the same manner as in Example 1 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 1.

[Example 3]
Polymerization of propylene was carried out in the same manner as in Example 1 except that the amount of cyclohexylmethyldimethoxysilane was changed to 0.1 mmol. The results are shown in Table 1.

[Example 4]
Polymerization of propylene was carried out in the same manner as in Example 1 except that the amount of hydrogen was 7.5 NL and cyclohexylmethyldimethoxysilane was 0.1 mmol. The results are shown in Table 1.

[Example 5]
Polymerization of propylene was carried out in the same manner as in Example 3 except that cyclohexylmethyldimethoxysilane was changed to dicyclopentyldimethoxysilane. The results are shown in Table 1.

[Example 6]
Polymerization of propylene was performed in the same manner as in Example 5 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 1.

[Example 7]
Polymerization of propylene was conducted in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane was not added. The results are shown in Table 1.

[Example 8]
(Preparation of solid titanium catalyst component (α2))
Anhydrous magnesium chloride (75 g), decane (280.3 g) and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution, and then cyclohexane-1,2-dicarboxylate n-propyl (15.15) was added to this solution. 1 g was added and further stirred and mixed at 130 ° C. for 1 hour.
After cooling the homogeneous solution thus obtained to room temperature, 38 ml of this uniform solution was charged dropwise into 100 ml of titanium tetrachloride maintained at −24 ° C. over 45 minutes with stirring at a stirring rotational speed of 350 rpm. After the completion of charging, the temperature of the mixed solution was raised to 80 ° C. over 6.7 hours. When the temperature reached 80 ° C., diisobutyl cyclohexane 1,2-dicarboxylate (trans ratio 78%) was added to Mg in the mixed solution. Added 0.025 moles of atoms. The temperature was raised again to 100 ° C. over 20 minutes. When the temperature reached 100 ° C., 2-isopropyl-2-isobutyl-1,3-dimethoxypropane was added in an amount of 0.05 mol times Mg atoms. While maintaining 100 ° C., the mixture was kept under stirring at the same temperature for 35 minutes. After the completion of the reaction, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 100 ° C. for 35 minutes. After completion of the reaction, the solid portion was again collected by hot filtration, and sufficiently washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [α1] prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [α1] thus obtained was 3.1% by weight of titanium, 18% by weight of magnesium, 9.2% by weight of n-propylcyclohexane-1,2-dicarboxylate, cyclohexane 1, They were 5.0% by mass of diisobutyl 2-dicarboxylate, 4.6% by mass of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, and 1.8% by mass of 2-ethylhexyl alcohol residue.

(Main polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (α2) were added to the titanium atom. 0.004 mmol was added in terms of conversion, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 1 shows the activity, bulk specific gravity, MFR, and amount of decane insoluble components.

[Example 9]
Polymerization of propylene was carried out in the same manner as in Example 8 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 1.

[Example 10]
Polymerization of propylene was carried out in the same manner as in Example 8, except that cyclohexylmethyldimethoxysilane was changed to dicyclopentyldimethoxysilane. The results are shown in Table 1.

[Example 11]
Propylene was polymerized in the same manner as in Example 8 except that cyclohexylmethyldimethoxysilane was changed to dicyclopentyldimethoxysilane and the hydrogen amount was 7.5 NL. The results are shown in Table 1.

[Comparative Example 1]
(Preparation of solid titanium catalyst component (β1))
Anhydrous magnesium chloride (75 g), decane (280.3 g) and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution, and then cyclohexane-1,2-dicarboxylate n-propyl (15.15) was added to this solution. 1 g was added and further stirred and mixed at 130 ° C. for 1 hour.
After cooling the homogeneous solution thus obtained to room temperature, 38 ml of this uniform solution was charged dropwise into 100 ml of titanium tetrachloride maintained at −24 ° C. over 45 minutes with stirring at a stirring rotational speed of 350 rpm. After the completion of charging, the temperature of the mixed solution was raised to 110 ° C. over 7.2 hours. Dicyclobutyl 1,2-dicarboxylate (trans ratio 78%) was added to 0.075 mol of Mg atoms in the mixed solution. Doubled. While maintaining 110 ° C., the mixture was kept under stirring at the same temperature for 35 minutes. After the completion of the reaction, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 100 ° C. for 35 minutes. After completion of the reaction, the solid portion was again collected by hot filtration, and sufficiently washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [β1] prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [β1] thus obtained was 2.8% by mass of titanium, 17% by mass of magnesium, 9.6% by mass of n-propylcyclohexane-1,2-dicarboxylate, cyclohexane 1, They were 9.7% by mass of diisobutyl 2-dicarboxylate and 1.2% by mass of 2-ethylhexyl alcohol residue.

(Main polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (β1) were added to the titanium atom. 0.004 mmol was added in terms of conversion, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 1 shows the activity, bulk specific gravity, MFR, and amount of decane insoluble components.

[Comparative Example 2]
Polymerization of propylene was performed in the same manner as in Comparative Example 1 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 1.

[Comparative Example 3]
(Preparation of solid titanium catalyst component (β2))
Anhydrous magnesium chloride 75 g, decane 280.3 g and 2-ethylhexyl alcohol 308.3 g were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution, and then 17.5 g of phthalic anhydride was added to the solution. The mixture was stirred for 1 hour.
After cooling the uniform solution thus obtained to room temperature, 38 ml of this uniform solution was charged dropwise into 100 ml of titanium tetrachloride maintained at −24 ° C. over 45 minutes with stirring at a rotational speed of 200 rpm. After completion of the charging, the temperature of the mixed solution was raised to 110 ° C. over 7.2 hours, and diisobutyl phthalate was added to the mixed solution by 0.25 mole times Mg atoms. While maintaining 110 ° C., the mixture was kept under stirring at the same temperature for 120 minutes. After completion of the reaction, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 110 ° C. for 120 minutes. After completion of the reaction, the solid portion was again collected by hot filtration, and sufficiently washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [β2] prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [β2] thus obtained was 2.6% by mass of titanium, 18% by mass of magnesium, 12.3% by mass of diisobutyl phthalate and 1.0% by mass of 2-ethylhexyl alcohol residue. Met.

(Main polymerization)
After adding 500 g of propylene and 0.8 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (β2) were added. 0.004 mmol was added in terms of titanium atoms, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 1 shows the activity, bulk specific gravity, MFR, and amount of decane insoluble components.

[Comparative Example 4]
Polymerization of propylene was performed in the same manner as in Comparative Example 3 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 1.

[Comparative Example 5]
(Preparation of solid titanium catalyst component (β3))
Anhydrous magnesium chloride (75 g), decane (280.3 g) and 2-ethylhexyl alcohol (308.3 g) were heated and reacted at 130 ° C. for 3 hours to obtain a homogeneous solution. 19.9 g of propane was added, and further stirred and mixed at 130 ° C. for 1 hour.
After cooling the uniform solution thus obtained to room temperature, 38 ml of this uniform solution was charged dropwise into 100 ml of titanium tetrachloride maintained at −24 ° C. over 45 minutes with stirring at a rotational speed of 200 rpm. After the completion of charging, the temperature of the mixed solution was raised to 110 ° C. over 7.2 hours. While maintaining 110 ° C., the mixture was kept under stirring at the same temperature for 120 minutes. After completion of the reaction, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated again at 110 ° C. for 120 minutes. After completion of the reaction, the solid portion was again collected by hot filtration, and sufficiently washed with 100 ° C. decane and hexane until no free titanium compound was detected in the washing solution. The solid titanium catalyst component [β3] prepared by the above operation was stored as a decanslurry, but a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [β3] thus obtained was 3.2 mass% titanium, 17 mass% magnesium, 14.3 mass% 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, and The amount of 2-ethylhexyl alcohol residue was 1.8% by mass.

(Main polymerization)
After adding 500 g of propylene and 0.8 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and a solid titanium catalyst component (β3) were added. 0.002 mmol was added in terms of titanium atoms, and the temperature in the polymerization vessel was quickly raised to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 1 shows the activity, bulk specific gravity, MFR, and amount of decane insoluble components.

[Comparative Example 6]
Polymerization of propylene was carried out in the same manner as in Comparative Example 5, except that cyclohexylmethyldimethoxysilane was not added. The results are shown in Table 1.

[Example 12]
(Preparation of solid titanium catalyst component (α1))
A high-speed stirring apparatus (made by Tokushu Kika Kogyo Co., Ltd. (TK Homomixer M type)) with an internal volume of 2 liters was sufficiently purged with nitrogen. 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. Next, 1 liter of purified decane that had been cooled to −10 ° C. in advance was put into this suspension using a Teflon (registered trademark) tube having an inner diameter of 5 mm while stirring at a high speed so as not to cause precipitation. Transferred to a 2 liter glass flask (with a stirrer). The solid produced by the transfer was filtered and washed thoroughly with purified n-heptane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride. This solid adduct was suspended in decane, and 23 mmol of the above solid adduct in terms of magnesium atom was introduced into 100 ml of titanium tetrachloride maintained at −20 ° C. with stirring and mixed. A liquid was obtained. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl cyclohexane-1,2-dicarboxylate (cis isomer, trans isomer mixture) was converted to 1 mol of magnesium atom of the solid adduct. Was added in an amount of 0.175 mol, and the temperature was raised to 110 ° C. in 40 minutes. When the temperature reached 110 ° C., 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was further added in an amount of 0.05 mol with respect to 1 mol of magnesium atom in the solid adduct, and the temperature was changed to 110 ° C. These were reacted by holding for 90 minutes with stirring.

After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated to 110 ° C. and stirred for 45 minutes. These were allowed to react by holding. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component (α1) prepared by the above operation was stored as a decane suspension, but a part of this was dried for the purpose of examining the catalyst composition.

The composition of the solid titanium catalyst component (α1) thus obtained was 2.8% by mass of titanium, 18% by mass of magnesium, 58% by mass of chlorine, 12.0% by mass of diisobutyl cyclohexane 1,2-dicarboxylate, 2 -It was 2.5 mass% of isobutyl-2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a polymerization vessel having an internal volume of 2 liters, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (α1) were added to titanium atoms. 0.004 mmol was added in terms of conversion, and the temperature in the polymerization vessel was quickly raised to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 2 shows the activity, MFR, decane insoluble component amount, and Mw / Mn.

[Example 13]
Polymerization of propylene was performed in the same manner as in Example 12 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Example 14]
Polymerization of propylene was carried out in the same manner as in Example 12 except that cyclohexylmethyldimethoxysilane was not added. The results are shown in Table 2.

[Example 15]
(Preparation of solid titanium catalyst component (α2))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.15 mol with respect to 1 mol of magnesium atom of the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.05 mol with respect to 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α2) was 2.9% by mass of titanium, 18% by mass of magnesium, 57% by mass of chlorine, 11.4% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- It was 3.0 mass% of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α2) was used. The results are shown in Table 2.

[Example 16]
Polymerization of propylene was performed in the same manner as in Example 15 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Example 17]
(Preparation of solid titanium catalyst component (α3))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.10 mol with respect to 1 mol of magnesium atom of the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.15 mol with respect to 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α3) was 2.7% by mass of titanium, 19% by mass of magnesium, 56% by mass of chlorine, 9.0% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- It was 6.3% by mass of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α3) was used. The results are shown in Table 2.

[Example 18]
Polymerization of propylene was performed in the same manner as in Example 17 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.
[Example 19]
(Preparation of solid titanium catalyst component (α4))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.075 mol with respect to 1 mol of magnesium atom of the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.075 mol per 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α4) was 2.6% by mass of titanium, 19% by mass of magnesium, 57% by mass of chlorine, 9.5% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- The amount was 4.1% by mass of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α4) was used. The results are shown in Table 2.

[Example 20]
Polymerization of propylene was performed in the same manner as in Example 19 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.
[Example 21]
(Preparation of solid titanium catalyst component (α5))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.05 mol with respect to 1 mol of magnesium atom of the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.05 mol with respect to 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α5) was 3.0% by mass of titanium, 19% by mass of magnesium, 57% by mass of chlorine, 7.0% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- The amount was 6.6% by mass of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α5) was used. The results are shown in Table 2.

[Example 22]
Polymerization of propylene was performed in the same manner as in Example 21 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Example 23]
(Preparation of solid titanium catalyst component (α6))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.05 mol with respect to 1 mol of magnesium atom of the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.15 mol with respect to 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α6) was 2.8% by mass of titanium, 19% by mass of magnesium, 57% by mass of chlorine, 7.2% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- It was 8.3% by mass of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α6) was used. The results are shown in Table 2.

[Example 24]
Polymerization of propylene was performed in the same manner as in Example 23 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Example 25]
(Preparation of solid titanium catalyst component (α7))
Cyclohexane-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture) was added in an amount of 0.025 mol to 1 mol of magnesium atom in the solid adduct, and further 2-isobutyl-2-isopropyl A catalyst was prepared in the same manner as in Example 12 except that -1,3-dimethoxypropane was added in an amount of 0.125 mol per 1 mol of magnesium atom in the solid adduct.

  The composition of the obtained solid titanium catalyst component (α7) was 3.0% by mass of titanium, 19% by mass of magnesium, 57% by mass of chlorine, 6.1% by mass of diisobutyl cyclohexane-1,2-dicarboxylate, 2-isobutyl- It was 9.8 mass% of 2-isopropyl-1,3-dimethoxypropane.

(Main polymerization)
Polymerization was carried out in the same manner as in Example 12 except that the solid titanium catalyst component (α7) was used. The results are shown in Table 2.

[Example 26]
Polymerization of propylene was performed in the same manner as in Example 25 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Comparative Example 7]
(Preparation of solid titanium catalyst component (β1))
A high-speed stirring apparatus (made by Tokushu Kika Kogyo Co., Ltd. (TK Homomixer M type)) with an internal volume of 2 liters was sufficiently purged with nitrogen. 3 g of S20 (sorbite distearate manufactured by Kao Corporation) was added, the system was heated while stirring this suspension, and the suspension was stirred at 120 ° C. and 800 rpm for 30 minutes. Next, 1 liter of purified decane that had been cooled to −10 ° C. in advance was put into this suspension using a Teflon (registered trademark) tube having an inner diameter of 5 mm while stirring at a high speed so as not to cause precipitation. Transferred to a 2 liter glass flask (with a stirrer). The solid produced by the transfer was filtered and washed thoroughly with purified n-heptane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with respect to 1 mol of magnesium chloride. This solid adduct was suspended in decane, and 23 mmol of the above solid adduct in terms of magnesium atom was introduced into 100 ml of titanium tetrachloride maintained at −20 ° C. with stirring and mixed. A liquid was obtained. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl cyclohexane-1,2-dicarboxylate (cis isomer, trans isomer mixture) was converted to 1 mol of magnesium atom of the solid adduct. Was added in an amount of 0.15 mol, and the temperature was raised to 110 ° C. over 40 minutes. These were reacted by holding at 110 ° C. with stirring for 90 minutes.

  After completion of the reaction for 90 minutes, the solid part was collected by hot filtration, and the solid part was resuspended in 100 ml of titanium tetrachloride, and then heated to 110 ° C. and stirred for 45 minutes. These were allowed to react by holding. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and washed sufficiently with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.

  The solid titanium catalyst component (β1) prepared by the above operation was stored as a decane suspension, and a part of this was dried for the purpose of examining the catalyst composition.

  The composition of the solid titanium catalyst component (β1) thus obtained was 2.6 mass% titanium, 19 mass% magnesium, 56 mass% chlorine, and 14.5 mass% diisobutylcyclohexane 1,2-dicarboxylate. It was.

(Main polymerization)
After adding 500 g of propylene and 1 NL of hydrogen at room temperature to a 2 liter polymerizer, 0.5 mmol of triethylaluminum, 0.1 mmol of cyclohexylmethyldimethoxysilane, and solid titanium catalyst component (β1) were added to the titanium atom. 0.004 mmol was added in terms of conversion, and the inside of the polymerization vessel was quickly heated to 70 ° C. After polymerization at 70 ° C. for 1 hour, the reaction was stopped with a small amount of methanol, and propylene was purged. Further, the obtained polymer particles were dried under reduced pressure at 80 ° C. overnight. Table 2 shows the activity, MFR, decane insoluble component amount, and Mw / Mn.

[Comparative Example 8]
Polymerization of propylene was performed in the same manner as in Comparative Example 7 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Comparative Example 9]
(Preparation of solid titanium catalyst component (β2))
Instead of cycloiso-1,2-dicarboxylate diisobutyl (cis isomer, trans isomer mixture), 2-isobutyl-2-isopropyl-1,3-dimethoxypropane was added in an amount of 0.1 to 1 mol of magnesium atom in the solid adduct. A catalyst component (β2) was prepared in the same manner as in Comparative Example 7 except that it was added in an amount of 15 mol.

  The composition of the obtained solid titanium catalyst component (β2) was 2.8% by mass of titanium, 19% by mass of magnesium, 57% by mass of chlorine, and 14.0% by mass of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane. Met.

  Further, propylene was polymerized in the same manner as in Comparative Example 7 using the catalyst component (β2). The results are shown in Table 2.

[Comparative Example 10]
Polymerization of propylene was performed in the same manner as in Comparative Example 9 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

[Comparative Example 11]
Polymerization of propylene was carried out in the same manner as in Comparative Example 9 except that cyclohexylmethyldimethoxysilane was not added. The results are shown in Table 2.

[Comparative Example 12]
(Preparation of solid titanium catalyst component (β3))
Comparison except that diisobutyl phthalate was added in an amount of 0.15 mol per 1 mol of magnesium atom of the solid adduct instead of diisobutyl cyclohexane-1,2-dicarboxylate (cis isomer, trans isomer mixture) The catalyst component (β3) was prepared in the same manner as in Example 7.

  The composition of the obtained solid titanium catalyst component (β3) was 2.6 mass% titanium, 19 mass% magnesium, 58 mass% chlorine, and 7.6 mass% diisobutylphthalate. Further, propylene was polymerized in the same manner as in Comparative Example 7 using the catalyst component (β3). The results are shown in Table 2.

[Comparative Example 13]
Polymerization of propylene was performed in the same manner as in Comparative Example 12 except that the amount of hydrogen was 7.5 NL. The results are shown in Table 2.

  If the solid titanium catalyst component (I), the olefin polymerization catalyst, and the olefin polymerization method of the present invention are used, it can be expected that production of impact copolymers that require high stereoregularity and high flow is facilitated. Furthermore, since it does not contain any polyfunctional aromatic compound, it can provide a catalyst that can cope with the above-mentioned safety and hygiene regulations. Therefore, the industrial utility value is very high.

Claims (12)

Solid titanium catalyst component (I) containing titanium, magnesium, halogen and an ester compound (B) specified by the following formula (1) and a diether compound (C) specified by the following formula (3).

(In the formula (1), R ² and R ³ are each independently COOR ¹ or R, and at least one of R ² and R ³ is COOR ¹ ;
The single bond in the skeleton may be replaced with a double bond,
A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms,
A plurality of R's are each independently an atom selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. Or a plurality of Rs may be bonded to each other to form a ring, and a double bond is present in the ring skeleton formed by bonding of R to each other. Or a heteroatom may be contained.
In the formula (3), m is an integer of 1 to 10, and R ¹¹ , R ¹² , R ^{31 to} R ³⁶ are each independently a hydrogen atom, or carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine. , A substituent having at least one element selected from nitrogen, sulfur, phosphorus, boron and silicon. )   A magnesium compound (A) having no reducing ability in a liquid state is converted into an ester compound (B) specified by the formula (1), a diether compound (C) specified by the formula (3), a liquid titanium compound ( (However, the ester compound (B) is a magnesium compound having no reducing ability in a liquid state prior to the liquid titanium compound (D) or simultaneously with the liquid titanium compound (D)). The solid titanium catalyst component (I) according to claim 1, which is brought into contact with A). The solid titanium catalyst component (I) according to claim 1 or 2, wherein the ester compound (B) is a compound having a structure represented by the following formula (2).

(In Formula (2), n is an integer of 5-10,
R ² and R ³ are each independently COOR ¹ or R ′, and at least one of R ² and R ³ is COOR ¹ ;
The single bond in the cyclic skeleton may be replaced with a double bond,
A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms,
A is

Or a heteroatom,
A plurality of R ′ are independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A plurality of R ′ may be bonded to each other to form a ring, and in the ring skeleton formed by R ′ being bonded to each other, A double bond or a hetero atom may be contained. )   4. The solid titanium catalyst component (I) according to claim 3, wherein n = 6 in the formula (2). The solid titanium catalyst component (I) according to claim 3 or 4, wherein in the formula (2), R ² is COOR ¹ and R ³ is R '.   After contacting the magnesium compound (A) having no reducing ability in a liquid state with the ester compound (B) represented by the formula (1) before the liquid titanium compound (D), the ester compound is further added. (B) obtained by contacting the ester compound (B1) specified by the formula (1), which may be the same as or different from the formula (3), and the diether compound (C) specified by the formula (3) The solid titanium catalyst component (I) according to claim 2, wherein the titanium compound (D) may be contacted in a plurality of times. The solid titanium catalyst component (I) according to claim 6, wherein the ester compound (B) and the ester compound (B1) have a cyclic structure specified by the following formula (2).

(In Formula (2), n is an integer of 5-10,
R ² and R ³ are each independently COOR ¹ or R ′, and at least one of R ² and R ³ is COOR ¹ ;
The single bond in the cyclic skeleton may be replaced with a double bond,
A plurality of R ¹ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms,
A is

Or a heteroatom,
A plurality of R ′ are independently selected from a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a nitrogen-containing group, an oxygen-containing group, a phosphorus-containing group, a halogen-containing group and a silicon-containing group. A plurality of R ′ may be bonded to each other to form a ring, and in the ring skeleton formed by R ′ being bonded to each other, A double bond or a hetero atom may be contained. )   In the said Formula (2), it is n = 6, The solid titanium catalyst component (I) of Claim 7 characterized by the above-mentioned. The solid titanium according to claim 7 or 8, wherein, in the formula (2), R ² is COOR ¹ and R ³ is R '. R ^{1 of the} ester compound (B) is each independently a monovalent hydrocarbon group having 2 to 3 carbon atoms, and R ^{1 of the} ester compound (B1) is independently 1 to 20 carbon atoms.
The solid titanium catalyst component (I) according to any one of claims 7 to 9, which is a monovalent hydrocarbon group. Solid titanium catalyst component (I) according to any one of claims 1 to 10,
An organometallic compound (II);
An olefin polymerization catalyst containing an electron donor (III) as required.   An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 11.