JP2008024751A - Solid titanium catalyst component, olefin polymerization catalyst and olefin polymerization process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an olefin polymerization catalyst which can obtain an olefin polymer having a broad molecular distribution even by one-stage polymerization. <P>SOLUTION: The olefin polymerization catalyst comprises a solid titanium catalyst component comprising titanium, magnesium, a halogen and, if necessary, an electron donor, an organometallic compound catalyst component, and an alicyclic compound specified by the chemical formula. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an olefin polymerization catalyst preferably used for the polymerization of α-olefins having 3 or more carbon atoms. Furthermore, the present invention relates to an olefin polymerization method using the olefin polymerization catalyst.

Conventionally, as a catalyst used for producing 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, “homopolymerization” and “copolymerization” may be collectively referred to as “polymerization”.)
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 comprising compounds are widely known.
The latter catalyst exhibits high activity for polymerization of α-olefins such as propylene and butene-1 in addition to ethylene. Moreover, the obtained α-olefin polymer 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 promoter component, When a catalyst comprising a silicon compound having at least one Si-OR (wherein R is a hydrocarbon group) is used, excellent polymerization activity and stereospecificity are exhibited. -63310 (Patent Document 1) and the like.

  Polymers obtained using the above catalysts often have a narrower molecular weight distribution than polymers obtained with Ziegler-Natta catalysts. It is known that polymers having a narrow molecular weight distribution tend to have “low melt fluidity”, “low melt tension”, “poor formability”, “slightly low rigidity”, and the like. On the other hand, various high-speed molding techniques such as a high-speed stretching technique aiming at improving the productivity of stretched films have evolved from the viewpoint of productivity improvement and cost reduction.

  When trying to stretch a polymer having a relatively narrow molecular weight distribution as described above, for example, at high speed, there is a case where necking-in or fluttering of the film becomes more remarkable due to insufficient melt tension, making it difficult to improve productivity. Therefore, a polymer having a higher melt tension is required from the market.

In order to solve such a problem, a method of producing polymers having different molecular weights by multistage polymerization to widen the molecular weight distribution of the polymer (Japanese Patent Laid-Open No. 5-170843 (Patent Document 2), etc.) A catalyst using an electron donor (Japanese Patent Laid-Open No. 3-7703 (Patent Document 3)) or a catalyst using an succinic acid ester having an asymmetric carbon as an electron donor contained in a solid titanium catalyst component (International Publication No. There are many reports such as the 01/057099 pamphlet (Patent Document 4), the International Publication No. 00/63261 pamphlet (Patent Document 5) and the International Publication No. 02/30998 pamphlet (Patent Document 6)).
JP 57-63310 A Japanese Patent Laid-Open No. 5-170843 JP-A-3-7703 International Publication No. 01/057099 Pamphlet International Publication No. 00/63261 pamphlet International Publication No. 02/30998 Pamphlet JP 2001-114811 A Japanese Patent Laid-Open No. 2003-40918

  However, the above catalyst is a catalyst that has an insufficient effect of widening the molecular weight distribution of the olefin polymer, or has been studied by the present inventors to widen the molecular weight distribution by increasing the low molecular weight component. On the other hand, these catalysts have been evaluated by the market that the melt tension of the olefin polymer cannot be improved sufficiently, and from the market, the molecular weight distribution has been made by a simpler process from the viewpoint of cost reduction. There has been a long-awaited appearance of a catalyst that can produce an olefin polymer.

  In addition, the olefin polymer manufacturer is required to provide a catalyst for olefin polymerization that can achieve a broad molecular weight distribution by combining the conventional olefin polymerization catalyst with other components, rather than the risk during production due to the change in the solid titanium catalyst component. May be lower.

  Accordingly, an object of the present invention is to provide an olefin polymerization catalyst which can easily produce an olefin polymer having a broad molecular weight distribution, a high melt tension, and suitable for high-speed stretching and high-speed molding.

  As a result of intensive studies, the present inventors have found that an olefin polymerization catalyst containing carbon, oxygen, hydrogen, a specific compound having an alicyclic structure, an organometallic compound catalyst component, and a solid titanium catalyst component has a molecular weight distribution. It was found that a wide olefin polymer can be produced, and the present invention was completed.

The olefin polymerization catalyst of the present invention is
A solid titanium catalyst component (I) comprising titanium, magnesium, halogen and optionally an electron donor; and
Organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table and alicyclic compound (III) specified by the following formula
And an olefin polymerization catalyst.

[In Formula (1), n is an integer of 5-10.
R ¹ is a substituent containing at least carbon, oxygen, and hydrogen.
R ² and R ³ are each independently an R ¹ group or R, and at least one of R ² and R ³ is an R ¹ group.
Single bonds in the cyclic skeleton (excluding C ^a -C ^a bonds) may be replaced with double bonds.
A plurality of Rs are each independently an atom or group 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. And may be bonded to each other to form a ring.
R may be contained a double bond in the skeleton of the ring formed by bonding to each other, in the ring skeleton, if it contains C ^a to R ¹ group is attached two or more, the The number of carbon atoms forming the ring skeleton is 5 to 10. ].

  In the formula (1), it is preferable that all the bonds between carbon atoms in the cyclic skeleton are single bonds.

  In the formula (1), the cyclic skeleton is preferably composed of 6 carbon atoms.

  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.

The solid titanium catalyst component, the olefin polymerization catalyst, and the olefin polymerization method of the present invention are suitable for producing an olefin polymer having high stereoregularity and a wide molecular weight distribution with high activity.
In addition, if the solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method of the present invention are used, an olefin polymer having excellent rigidity in addition to moldability such as high-speed stretchability and high-speed moldability can be produced. Can be expected.

Hereinafter, the olefin polymerization catalyst and the olefin polymerization method according to the present invention will be described in more detail.
The olefin polymerization catalyst of the present invention contains a solid titanium catalyst component (I), an organometallic compound catalyst component (II), and a specific alicyclic compound. First, each component will be described.

[Solid titanium catalyst component (I)]
The solid titanium catalyst component (I) used in the present invention is characterized by containing titanium, magnesium, halogen and, if necessary, an electron donor. As this solid titanium catalyst component (I), a known solid titanium catalyst component can be used without limitation. The example of the manufacturing method of such a solid titanium catalyst component is as follows.

  In the preparation of the solid titanium catalyst component (I) of the present invention, there are many examples in which a magnesium compound and a titanium compound are used.

<Magnesium compound>
As such a magnesium compound, specifically,
Magnesium halides such as magnesium chloride and magnesium bromide;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, phenoxy magnesium chloride;
Alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, 2-ethylhexoxymagnesium;
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.

  Of these, magnesium compounds containing halogen are preferred. Magnesium halides, particularly magnesium chloride, are 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.

<Titanium compound>
Examples of titanium compounds include general formulas;

Ti (OR) _g X _4-g

(R is a hydrocarbon group, X is a halogen atom, and g is 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 ) Trihalogenated alkoxytitanium such as Br ₃ ;
Dihalogenated alkoxytitanium such as Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ ;
Monohalogenated alkoxytitanium such as Ti (OCH ₃ ) ₃ Cl, Ti (O—n—C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br;
Examples thereof include tetraalkoxytitanium 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.

  Examples of the magnesium compound and titanium compound as described above may include compounds described in detail in Patent Document 1, Patent Document 2, and the like.

  Specific examples of preferable methods for preparing the solid titanium catalyst component (I) used in the present invention include the following methods (P-1) to (P-4).

(P-1) An inert hydrocarbon solvent comprising a solid adduct comprising an electron donor component (a) such as a magnesium compound and alcohol, an electron donor component (b) described later, and a titanium compound in a liquid state A method of contacting in suspension in the presence of coexistence.
(P-2) A method in which a solid adduct comprising a magnesium compound and an electron donor component (a), an electron donor component (b), and a titanium compound in a liquid state are contacted in a plurality of times.
(P-3) A solid adduct comprising a magnesium compound and an electron donor component (a), an electron donor component (b), and a liquid titanium compound are suspended in the presence of an inert hydrocarbon solvent. The method of making it contact in a state and contacting in multiple times.
(P-4) A method of bringing a liquid magnesium compound comprising a magnesium compound and an electron donor component (a) into contact with a liquid titanium compound and an electron donor component (b).

The preferred reaction temperature is in the range of −30 ° C. to 150 ° C., more preferably −25 ° C. to 130 ° C., still more preferably −25 to 120 ° C.
The production of the above solid titanium catalyst component can also be carried out in the presence of a known medium, if necessary. Examples of the medium include aromatic hydrocarbons such as toluene having a slight polarity, and known aliphatic hydrocarbons and alicyclic hydrocarbon compounds such as heptane, octane, decane, and cyclohexane. Group hydrocarbons are preferred examples.

  When the reaction is carried out in the above range, both the effect of obtaining a polymer having a wide molecular weight distribution and the activity and the stereoregularity of the obtained polymer can be achieved at a higher level.

(Electron donor component (a))
As the electron donor component (a) used for forming the solid adduct or the magnesium compound in a liquid state, a known compound that can solubilize the magnesium compound in a temperature range of about room temperature to about 300 ° C. is preferable. For example, alcohol, aldehyde, amine, carboxylic acid and a mixture thereof are preferable. Examples of these compounds include compounds described in detail in Patent Document 1 and Patent Document 2.

More specifically, alcohols having the above-described solubilizing ability of magnesium compounds include 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-butylcellosolve.

  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 aldehydes 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 the electron donor component (a), the above alcohols are preferable, and ethanol, propanol, butanol, isobutanol, hexanol, 2-ethylhexanol, decanol and the like are particularly preferable.

  The amount of the magnesium compound and the electron donor component (a) used in preparing the solid adduct or the liquid state 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 (a). 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 the electron donor component (a) in the obtained solid adduct or liquid magnesium compound varies depending on the type of compound used, and thus cannot be defined unconditionally. On the other hand, the electron donor component (a) is preferably in a range of 2 mol or more, more preferably 2.3 mol or more, still more preferably 2.7 mol or more and 5 mol or less.

<Aromatic carboxylic acid ester and / or compound having two or more ether bonds via a plurality of carbon atoms>
Particularly preferred examples of the electron donor used as necessary for the solid titanium catalyst component (I) used in the present invention include aromatic carboxylic acid esters and / or two or more ethers via a plurality of carbon atoms. A compound having a bond (hereinafter also referred to as “electron donor component (b)”) may be contained.

  As the electron donor component (b), known aromatic carboxylic acid esters and polyether compounds that have been preferably used for conventional olefin polymerization catalysts, for example, Patent Document 2 and JP-A No. 2001-354714 are described. The used compounds can be used without limitation.

  Specific examples of the aromatic carboxylic acid ester include aromatic polycarboxylic acid esters such as phthalic acid esters, in addition to aromatic carboxylic acid monoesters such as benzoic acid esters and toluic acid esters. Among these, aromatic polycarboxylic acid esters are preferable, and phthalic acid esters are more preferable. As the phthalates, phthalic acid alkyl esters such as ethyl phthalate, n-butyl phthalate, isobutyl phthalate, hexyl phthalate and heptyl phthalate are preferable, and diisobutyl phthalate is particularly preferable.

  More specifically, examples of the polyether compound include compounds represented by the following formula (3).

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

When m is 2 or more, a plurality of R ¹¹ and R ¹² may be the same or different. Arbitrary R ^{11 to} R ³⁶ , preferably R ¹¹ and R ¹² may jointly form a ring other than a benzene ring.

Some specific examples of such compounds include:
2-isopropyl-1,3-dimethoxypropane,
2-s-butyl-1,3-dimethoxypropane,
Monosubstituted dialkoxypropanes such as 2-cumyl-1,3-dimethoxypropane;
2-isopropyl-2-isobutyl-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane,
2-methyl-2-cyclohexyl-1,3-dimethoxypropane,
2-methyl-2-isobutyl-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,
2,2-di-s-butyl-1,3-dimethoxypropane,
2,2-dineopentyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2-substituted dialkoxypropanes such as 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane

2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-dicyclohexyl-1,4-diethoxybutane,
2,3-diisopropyl-1,4-diethoxybutane
2,4-diphenyl-1,5-dimethoxypentane,
2,5-diphenyl-1,5-dimethoxyhexane,
2,4-diisopropyl-1,5-dimethoxypentane,
2,4-diisobutyl-1,5-dimethoxypentane,
Dialkoxyalkanes such as 2,4-diisoamyl-1,5-dimethoxypentane,
2-methyl-2-methoxymethyl-1,3-dimethoxypropane,
2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,
Trialkoxyalkanes such as 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
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.

  These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Furthermore, the alicyclic compound (III) described later can also be used as the electron donor component (b).

In the solid titanium catalyst component (I) used in the present invention, the halogen / titanium (atomic ratio) (that is, the number of moles of halogen atom / number of moles of titanium atom) is 2 to 100, preferably 4 to 90. Is desirable,
In the electron donor component (a) and the electron donor component (b), the electron donor component (a) / titanium atom (molar ratio) is desirably 0 to 100, preferably 0 to 10, and the electron donor. The component (b) / titanium atom (molar ratio) is 0-100, preferably 0-10.

  Magnesium / titanium (atomic ratio) (that is, the number of moles of magnesium atoms / the number of moles of titanium atoms) is 2 to 100, preferably 4 to 50.

  The content of the electron donor component (a) and the electron donor component (b) is preferably 20% by weight or less, more preferably 10% by weight with respect to 100% by weight of the electron donor component (b). It is as follows.

  As a more detailed preparation condition of the solid titanium catalyst component (I), for example, EP585869A1 (European Patent Application Publication No. 0585869) and the above-mentioned Patent Document 2 are described except that the electron donor component (b) is used. The following conditions can be preferably used.

  Next, the organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table will be described.

<Organic metal compound catalyst component (II)>
As the organometallic compound catalyst component (II), a compound containing a Group 13 metal, 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 is used. Can do. 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 the above-mentioned EP585869A1.

Next, alicyclic compound (III) is demonstrated.
<Alicyclic compound (III)>
The alicyclic compound (III) is represented by the following formula (1).

[In Formula (1), n is an integer of 5-10, Preferably it is an integer of 5-7, Most preferably, it is 6. C ^a represents a carbon atom.
A plurality of R ¹ are each independently a substituent containing at least carbon, oxygen and hydrogen. Examples of such a substituent include a carboxylic acid ester group, an oxycarbonylalkyl group, and an alkoxy group, and a carboxylic acid ester group and an oxycarbonylalkyl group are preferable.
R ² and R ³ are each independently R ¹ or R, and at least one of R ² and R ³ is an R ¹ group.
Single bonds in the cyclic skeleton (excluding C ^a -C ^a bonds) may be replaced with double bonds.
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 s} bonded to the R ¹ group are contained, the number of carbon atoms constituting the skeleton of the ring 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

Examples of the alicyclic compound (III) include the following cyclic ester compounds.
Cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate di-n-propyl,
Cyclohexane-1,2-dicarboxylate diisopropyl,
Cyclohexane-1,2-dicarboxylate di-n-butyl,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylic acid dihexyl,
Cyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate 2-ethylhexylcyclohexane-1,2-dicarboxylate didecyl,
Cyclohexane-1,3-dicarboxylate diethyl,
Cyclohexane-1,3-dicarboxylate diisobutyl,

Diethyl cyclopentane-1,2-dicarboxylate,
Cycloisopropyl-1,2-dicarboxylate,
Cyclopentane-1,2-dicarboxylate diisobutyl,
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,
Cycloheptane-1,2-dicarboxylate diisopropyl,
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,
4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-cyclohexene-1,2-dicarboxylate,
4-cyclohexene-1,2-dicarboxylate diisobutyl,
4-cyclohexene-1,2-dicarboxylate 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,
4-cyclohexene-1,3-dicarboxylate diisobutyl,

Diethyl 3-cyclopentene-1,2-dicarboxylate,
3-cyclopentene-1,2-dicarboxylate diisopropyl,
Diisobutyl 3-cyclopentene-1,2-dicarboxylate,
3-cyclopentene-1,2-dicarboxylate diheptyl,
Didecyl 3-cyclopentene-1,2-dicarboxylate,
Diethyl 3-cyclopentene-1,3-dicarboxylate,
3-cyclopentene-1,3-dicarboxylate diisobutyl,

4-cycloheptene-1,2-dicarboxylate diethyl,
4-cycloheptene-1,2-dicarboxylate diisopropyl,
4-cycloheptene-1,2-dicarboxylate diisobutyl,
4-cycloheptene-1,2-dicarboxylate diheptyl,
Didecyl 4-cycloheptene-1,2-dicarboxylate,
4-cycloheptene-1,3-dicarboxylate diethyl,
4-cycloheptene-1,3-dicarboxylate diisobutyl,

Diethyl 5-cyclooctene-1,2-dicarboxylate,
A compound having no substituent in the cyclic structure such as

Diethyl 3-methylcyclohexane-1,2-dicarboxylate,
Di-n-propyl 3-methylcyclohexane-1,2-dicarboxylate,
3-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methylcyclohexane-1,2-dicarboxylate,
3-methylcyclohexane-1,2-dicarboxylate diisobutyl,
3-methylcyclohexane-1,2-dicarboxylate dihexyl,
3-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methylcyclohexane-1,2-dicarboxylate,
2-methylhexyl 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,
4-methylcyclohexane-1,2-dicarboxylic acid di-n-propyl,
4-methylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate diisobutyl,
4-hexylcyclohexane-1,2-dicarboxylate dihexyl,
4-methylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 4-methylcyclohexane-1,2-dicarboxylate,
4-methylcyclohexane-1,2-dicarboxylate 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,
3,4-dimethylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Diisobutyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
3,4-dimethylcyclohexane-1,2-dicarboxylate dihexyl,
Diheptyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Dioctyl 3,4-dimethylcyclohexane-1,2-dicarboxylate,
Di-2-ethylhexyl 3,4-dimethylcyclohexane-1,2-dicarboxylate
Didecyl 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,
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,
3,6-diphenylcyclohexane-1,2-dicarboxylate diisopropyl,
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,

3-methyl 6-ethylcyclohexane-1,2-dicarboxylate diethyl,
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,
3-methyl 6-ethylcyclohexane-1,2-dicarboxylate diisobutyl,
3-methyl 6-ethylcyclohexane-1,2-dicarboxylate dihexyl,
3-methyl 6-ethylcyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl 3-methyl 6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl 6-ethylcyclohexane-1,2-dicarboxylate di-2-ethylhexyl,
Didecyl 3-methyl 6-ethylcyclohexane-1,2-dicarboxylate,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate diethyl,
Di-n-propyl 3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate diisobutyl,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate dihexyl;
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate diheptyl,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate dioctyl,
3-methyl 6-n-propylcyclohexane-1,2-dicarboxylate di-2-ethylhexyl;
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-dicarboxylate 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-dicarboxylate 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,
Diheptyl 3,4-dimethylcyclopentane-1,2-dicarboxylate,
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,
3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate diethyl,
Di-n-propyl 3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate,
3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate,
3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate diisobutyl,
3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate dihexyl;
3-methyl 5-n-propylcyclopentane 1,2-dicarboxylate dioctyl,
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-dicarboxylate 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-dicarboxylate 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,
3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate,
Di-n-propyl 3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate,
3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate,
3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate diisobutyl,
3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate dihexyl;
3-methyl 7-n-propylcycloheptane 1,2-dicarboxylate dioctyl,
Didecyl 3-methyl-7-n-propylcycloheptane 1,2-dicarboxylate,

Diethyl 3-methylcyclooctane-1,2-dicarboxylate,
Diethyl 3-methylcyclodecane-1,2-dicarboxylate,
Isobutyl 3-vinylcyclohexane-1,2-dicarboxylate,
Isobutyl 3,6-diphenylcyclohexane-1,2-dicarboxylate,
Ethyl 3,6-dicyclohexylcyclohexane-1,2-dicarboxylate,
Norbornane-2,3-dicarboxylate diisobutyl,
Tetracyclododecane-2,3-dicarboxylate diisobutyl
3-methyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 3-methyl-4-cyclohexene-1,2-dicarboxylate,
3-methyl 4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3-methyl 4-cyclohexene-1,2-dicarboxylate,
3-methyl 4-cyclohexene-1,2-dicarboxylate diisobutyl,
3-methyl 4-cyclohexene-1,2-dicarboxylate dihexyl,
3-methyl 4-cyclohexene-1,2-dicarboxylate diheptyl,
Dioctyl 3-methyl-4-cyclohexene-1,2-dicarboxylate,
Dimethyl 2-cyclohexene-1,2-dicarboxylate di-2-ethylhexyl,
Didecyl 3-methyl-4-cyclohexene-1,2-dicarboxylate,
4-methyl 4-cyclohexene-1,3-dicarboxylate,
4-methyl 4-cyclohexene-1,3-dicarboxylate diisobutyl,
4-methyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 4-methyl 4-cyclohexene-1,2-dicarboxylate,
4-methyl 4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 4-methyl 4-cyclohexene-1,2-dicarboxylate,
4-methyl 4-cyclohexene-1,2-dicarboxylate diisobutyl,
4-methyl 4-cyclohexene-1,2-dicarboxylate dihexyl,
4-methyl 4-cyclohexene-1,2-dicarboxylate diheptyl,
Dioctyl 4-methyl 4-cyclohexene-1,2-dicarboxylate,
4-methyl 4-cyclohexene-1,2-dicarboxylate di-2-ethylhexyl,
Didecyl 4-methyl-4-cyclohexene-1,2-dicarboxylate,
5-methyl 4-cyclohexene-1,3-dicarboxylate,
Diisobutyl 5-methyl-4-cyclohexene-1,3-dicarboxylate,
3,4-dimethyl 4-cyclohexene-1,2-dicarboxylate,
Di-n-propyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,4-dimethyl 4-cyclohexene-1,2-dicarboxylate diisopropyl,
Di-n-butyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diisobutyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,4-dimethyl 4-cyclohexene-1,2-dicarboxylate dihexyl,
Diheptyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Dioctyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
3,2-Dimethyl-4-cyclohexene-1,2-dicarboxylate di-2-ethylhexyl
Didecyl 3,4-dimethyl-4-cyclohexene-1,2-dicarboxylate,
Diethyl 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-dicarboxylate 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,
3-hexyl 4-cyclohexene-1,2-dicarboxylate diethyl,
3-hexyl 4-cyclohexene-1,2-dicarboxylate diisobutyl,
3,6-dihexyl 4-cyclohexene-1,2-dicarboxylate,
3-hexyl 6-pentyl 4-cyclohexene-1,2-dicarboxylate diisobutyl,

Diethyl 3-methyl 3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3-methyl 3-cyclopentene-1,2-dicarboxylate,
3-methyl-3-cyclopentene-1,2-dicarboxylate diheptyl,
Didecyl 3-methyl-3-cyclopentene-1,2-dicarboxylate,
4-methyl 3-cyclopentene-1,3-dicarboxylate,
4-methyl 3-cyclopentene-1,3-dicarboxylate diisobutyl,
4-methyl 3-cyclopentene-1,2-dicarboxylate diethyl,
4-methyl 3-cyclopentene-1,2-dicarboxylate diisobutyl,
4-methyl 3-cyclopentene-1,2-dicarboxylate diheptyl,
Didecyl 4-methyl 3-cyclopentene-1,2-dicarboxylate,
Diethyl 5-methyl-3-cyclopentene-1,3-dicarboxylate,
Diisobutyl 5-methyl 3-cyclopentene-1,3-dicarboxylate,
Diethyl 3,4-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3,4-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Diheptyl 3,4-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Didecyl 3,4-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Diethyl 3,5-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Diisobutyl 3,5-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Diheptyl 3,5-dimethyl-3-cyclopentene-1,2-dicarboxylate,
Didecyl 3,5-dimethyl-3-cyclopentene-1,2-dicarboxylate,
3-hexyl 3-cyclopentene-1,2-dicarboxylate diethyl,
3,5-dihexyl 3-cyclopentene-1,2-dicarboxylate diethyl,
3-hexyl 5-pentyl 3-cyclopentene-1,2-dicarboxylate diisobutyl,
3-methyl 4-cycloheptene-1,2-dicarboxylate,
3-methyl 4-cycloheptene-1,2-dicarboxylate diisobutyl,
3-methyl 4-cycloheptene-1,2-dicarboxylate diheptyl,
Didecyl 3-methyl-4-cycloheptene-1,2-dicarboxylate,
4-methyl 4-cycloheptene-1,3-dicarboxylate,
4-methyl 4-cycloheptene-1,3-dicarboxylate diisobutyl,
4-methyl 4-cycloheptene-1,2-dicarboxylate,
4-methyl 4-cycloheptene-1,2-dicarboxylate diisobutyl,
4-methyl 4-cycloheptene-1,2-dicarboxylate diheptyl,
Didecyl 4-methyl-4-cycloheptene-1,2-dicarboxylate,
5-methyl 4-cycloheptene-1,3-dicarboxylate,
Diisobutyl 5-methyl 4-cycloheptene-1,3-dicarboxylate,

3,4-dimethyl 4-cycloheptene-1,2-dicarboxylate,
Diisobutyl 3,4-dimethyl-4-cycloheptene-1,2-dicarboxylate,
Diheptyl 3,4-dimethyl-4-cycloheptene-1,2-dicarboxylate,
Didecyl 3,4-dimethyl-4-cycloheptene-1,2-dicarboxylate,
3,7-dimethyl 4-cycloheptene-1,2-dicarboxylate diethyl,
Diisobutyl 3,7-dimethyl 4-cycloheptene-1,2-dicarboxylate,
Diheptyl 3,7-dimethyl-4-cycloheptene-1,2-dicarboxylate,
Didecyl 3,7-dimethyl-4-cycloheptene-1,2-dicarboxylate,
3-hexyl 4-cycloheptene-1,2-dicarboxylate,
3,7-dihexyl 4-cycloheptene-1,2-dicarboxylate,
3-hexyl 7-pentyl 4-cycloheptene-1,2-dicarboxylate diisobutyl,
3-methyl 5-cyclooctene-1,2-dicarboxylate diethyl,
Diethyl 3-methyl 6-cyclodecene-1,2-dicarboxylate,
Isobutyl 3-vinyl-4cyclohexene-1,2-dicarboxylate,
Isobutyl 3,6-diphenyl-4cyclohexene-1,2-dicarboxylate,
Ethyl 3,6-dicyclohexyl-4cyclohexene-1,2-dicarboxylate,
2-norbornene-5,6-dicarboxylate diisobutyl,
Examples thereof include diisobutyl 2-tetracyclododecene-7,8-dicarboxylate.

Among the above compounds, di-n-butyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylate diisobutyl,
Cyclohexan-1,2-dicarboxylic acid dihexyl,
Cyclohexane-1,2-dicarboxylate diheptyl,
Dioctyl cyclohexane-1,2-dicarboxylate,
Cyclohexane-1,2-dicarboxylic acid 2-ethylhexyl,
Cyclopentane-1,2-dicarboxylate diisobutyl,
Cycloheptane-1,2-dicarboxylate diheptyl,
Diisobutyl cycloheptane-1,2-dicarboxylate,
Cycloheptane-1,2-dicarboxylate diheptyl 3,6-dimethylcyclohexane 1,2-dicarboxylate diisobutyl,
3,6-dimethylcyclohexane 1,2-dicarboxylic acid di-n-hexyl;
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,
Di-n-hexyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
Di-n-octyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate,
3,6-diethylcyclohexane 1,2-dicarboxylate diisobutyl,
3,6-diethylcyclohexane 1,2-dicarboxylic acid di-n-hexyl;
More preferred is di-n-octyl 3,6-diethylcyclohexane 1,2-dicarboxylate. The reason is not only high 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.

Moreover, the compound which has an oxycarbonyl alkyl group in an alicyclic structure can also be illustrated. Specifically, cyclohexyl 1,2-diacetate,
Cyclohexyl 1,2-dipropionate,
Cyclohexyl 1,2-dibutanate,
Cyclohexyl 1,2-dihexanate,
Cyclohexyl 1,2-dioctanoate,
Cyclohexyl 1,2-didecate,
Cyclohexyl 1,2-dibenzoate,
Cyclohexyl 1,2-ditoluate,
Cyclohexyl 1,3-diacetate,
Cyclohexyl 1,3-dipropionate,
Cyclohexyl 1,3-dibutanate,
Cyclohexyl 1,3-dihexanate,
Cyclohexyl 1,3-dioctanoate,
Cyclohexyl 1,3-didecate,
Cyclohexyl 1,3-dibenzoate,
Cyclohexyl 1,3-ditoluate,
Cyclopentyl 1,2-diacetate,
Cyclopentyl 1,2-dibutanate,
Cyclopentyl-1,2-dibenzoate,
Cyclopentyl 1,2-ditoluate,
Cycloheptyl 1,2-diacetate,
Cycloheptyl 1,2-dibutanate,
Cycloheptyl 1,2-dibenzoate,
Cycloheptyl 1,2-ditoluate,

3-methylcyclohexyl 1,2-diacetate,
3-methylcyclohexyl 1,2-dipropionate,
3-methylcyclohexyl 1,2-dibutanate,
3-methylcyclohexyl 1,2-dihexanate,
3-methylcyclohexyl 1,2-dioctanoate,
3-methylcyclohexyl 1,2-didecate,
3-methylcyclohexyl 1,2-dibenzoate,
3-methylcyclohexyl 1,2-ditoluate,
4-methylcyclohexyl 1,3-diacetate,
4-n-propylcyclohexyl 1,3-dibutanate,
4-methylcyclohexyl 1,3-dibenzoate,
4-n-propylcyclohexyl 1,3-ditoluate,
3-methylcyclopentyl 1,2-diacetate,
3-n-propylcyclopentyl 1,2-dibutanate,
3-methylcyclopentyl 1,2-dibenzoate,
3-n-propylcyclopentyl 1,2-ditoluate,
3-methylcycloheptyl 1,2-diacetate,
3-n-propylcycloheptyl 1,2-dibutanate,
3-methylcycloheptyl 1,2-dibenzoate,
3-n-propylcycloheptyl 1,2-ditoluate,
3,6-dimethylcyclohexyl 1,2-diacetate,
3-methyl 6-propyl cyclohexyl 1,2-dibutanate,
3,6-dimethylcyclohexyl 1,2-dibenzoate,
3-methyl 6-propyl cyclohexyl 1,2-ditoluate,
3,5-dimethylcyclopentyl 1,2-diacetate,
3-methyl 5-propylcyclopentyl 1,2-dibutanate,
3,7-dimethylcycloheptyl 1,2-dibenzoate,
3-methyl 7-propylcycloheptyl 1,2-ditoluate,
4-cyclohexenyl 1,2-diacetate,
3-methyl 4-cyclohexenyl 1,2-dibutanate,
4-cyclohexenyl 1,2-dibenzoate,
3-n-propyl 4-cyclohexenyl 1,2-ditoluate,
4-cycloheptenyl 1,2-diacetate,
3-methyl 4-cycloheptenyl 1,2-dibutanate,
4-cycloheptenyl 1,2-dibenzoate,
3-n-propyl 4-cycloheptenyl 1,2-ditoluate,
Etc.

In addition to the above dicarbonate,
・ Oxycarbonylmethyl, 2-oxycarbonylbutyl 3,6-dimethylcyclohexane, 1-oxycarbonylmethyl 2-oxycarbonylbutylcyclohexane,
1-oxycarbonylmethyl 2-oxycarbonylphenylcyclohexane,
Mention may also be made of asymmetric compounds such as 1-oxycarbonylmethyl 2-oxycarbonylphenyl 3-methyl 6-propylcyclohexane.

Among these,
3-methylcyclohexyl 1,2-diacetate,
3-methylcyclohexyl 1,2-dipropionate,
3-methylcyclohexyl 1,2-dibutanate,
3-methylcyclohexyl 1,2-dihexanate,
3-methylcyclohexyl 1,2-dioctanoate,
3-methylcyclohexyl 1,2-didecate,
3-methylcyclohexyl 1,2-dibenzoate,
3-methylcyclohexyl 1,2-ditoluate,
3,6-dimethylcyclohexyl 1,2-diacetate,
3-methyl 6-propyl cyclohexyl 1,2-dibutanate,
3,6-dimethylcyclohexyl 1,2-dibenzoate,
3-methyl 6-propyl cyclohexyl 1,2-ditoluate,
Etc.

In the compound having the above structure, isomers such as cis and trans derived from a plurality of R ¹ groups in Formula 1 exist. Any structure has an effect meeting the object of the present invention, but a higher trans isomer content is preferred.

  In the method for producing an olefin polymer of the present invention, a polymer having a wide molecular weight distribution can be obtained. The reason for this is currently unknown, but the following causes are presumed.

It is known that the cyclic hydrocarbon structure forms various three-dimensional structures such as a chair type and a boat type. Furthermore, if the cyclic structure has a substituent, the possible three-dimensional structure variations are further increased. In addition, if the C ^a -C ^a bond connecting ^a plurality of ester groups (R ¹ groups) is a single bond, the possible variation of the three-dimensional structure is widened. The ability to take such a variety of three-dimensional structures leads to the formation of a variety of active species on the solid titanium catalyst component (I). As a result, when olefin polymerization is performed using the solid titanium catalyst component (I), olefin polymers having various molecular weights can be produced at one time, that is, an olefin polymer having a wide molecular weight distribution can be produced. it can.

  In addition to the alicyclic compound (III), the electron donor component (a) and the electron donor component (b), as well as the known electron donor component (c), unless the object of the present invention is impaired. You may use it in combination.

Such an electron donor component (c) is preferably an organosilicon compound. Examples of the organosilicon compound include a compound represented by the following general formula (4).

R _n Si (OR ′) _4-n (4)

(In the formula, R and R ′ are hydrocarbon groups, and n is an integer of 0 <n <4.)
Specific examples of the organosilicon compound represented by the general formula (4) include diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, Dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltrimethoxysilane, 2-methyl Cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane, dicyclo Lopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, cyclopentyldimethylethoxysilane and the like are used.

  Of these, vinyltriethoxysilane, diphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, and dicyclopentyldimethoxysilane are preferably used.

In addition, a silane compound represented by the following formula (5) described in International Publication No. 2004/016662 pamphlet is also a preferable example of the organosilicon compound.

Si (OR ^a ) ₃ (NR ^b R ^c ) (5)

In the formula (5), R ^a is a hydrocarbon group having 1 to 6 carbon atoms, and examples of ^Ra include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, particularly preferably. A C2-C6 hydrocarbon group is mentioned. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

In formula (5), R ^b is a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and examples of R ^b include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. . Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, an n-pentyl group, an iso-pentyl group, and a cyclopentyl group. , N-hexyl group, cyclohexyl group, octyl group and the like, among which ethyl group is particularly preferable.

In Formula (5), R ^c is a hydrocarbon group having 1 to 12 carbon atoms, and examples of R ^c include an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Specific examples include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group, iso-pentyl group, cyclopentyl group, n- A hexyl group, a cyclohexyl group, an octyl group, etc. are mentioned, Among these, an ethyl group is particularly preferable.

Specific examples of the compound represented by the above formula (5) include
Dimethylaminotriethoxysilane,
Diethylaminotriethoxysilane,
Diethylaminotrimethoxysilane,
Diethylaminotriethoxysilane,
Diethylaminotri-n-propoxysilane,
Di-n-propylaminotriethoxysilane,
Methyl n-propylaminotriethoxysilane,
t-butylaminotriethoxysilane,
Ethyl n-propylaminotriethoxysilane,
Ethyl iso-propylaminotriethoxysilane,
Mention may be made of methylethylaminotriethoxysilane.

Another example of the organosilicon compound is a compound represented by the following formula (6).

RNSi (OR ^a ) ₃ (6)

In the formula (6), RN represents a cyclic amino group. Examples of the cyclic amino group include a perhydroquinolino group, a perhydroisoquinolino group, a 1,2,3,4-tetrahydroquinolino group, 2,3,4-tetrahydroisoquinolino group, octamethyleneimino group and the like can be mentioned. Specifically as a compound represented by the said Formula (6),
(Perhydroquinolino) triethoxysilane,
(Perhydroisoquinolino) triethoxysilane,
(1,2,3,4-tetrahydroquinolino) triethoxysilane,
(1,2,3,4-tetrahydroisoquinolino) triethoxysilane,
Examples include octamethyleneiminotriethoxysilane.

  These organosilicon compounds can be used in combination of two or more.

  Other useful compounds as the electron donor component (c) are described as examples of the compound having two or more ether bonds through the carbon atom or a plurality of carbon atoms (the electron donor component (b)). Preferred polyether compounds are also mentioned as preferred examples.

  Among these polyether compounds, 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.

  These compounds can be used alone or in combination of two or more.

  The olefin polymerization catalyst of the present invention may contain other components useful for olefin polymerization as necessary in addition to the above components. Examples of other components include a carrier such as silica, an antistatic agent, a particle flocculant, and a storage stabilizer.

  The catalyst for olefin polymerization of the present invention is a solid titanium catalyst component (I). An organometallic compound catalyst component (II) and an alicyclic compound (III) are contained.

  The preparation method of the catalyst for olefin polymerization of the present invention can be any known method, and is not particularly limited. For example, the solid titanium catalyst component (I), the organometallic compound catalyst component (II), and the alicyclic compound (III) may be contacted to form an olefin polymerization catalyst, and then contacted with the olefin to polymerize the olefin. . In addition, the solid titanium catalyst component (I), the organometallic compound catalyst component (II), and the alicyclic compound (III) are brought into contact with each other in the presence of the olefin to collectively form the olefin polymerization catalyst and the polymerization of the olefin. The method of performing can be mentioned.

There is no particular limitation on the contact order of the solid titanium catalyst component (I), the organometallic compound catalyst component (II), and the alicyclic compound (III),
a. A method in which the solid titanium catalyst component (I), the organometallic compound catalyst component (II), and the alicyclic compound (III) are simultaneously contacted,
b. A method of contacting the solid titanium catalyst component (I) after contacting the organometallic compound catalyst component (II) and the alicyclic compound (III);
c. A preferred example is a method of bringing the alicyclic compound (III) into contact with the solid titanium catalyst component (I) and the organometallic compound catalyst component (II).

  The preparation of the olefin polymerization catalyst of the present invention is preferably carried out in the presence of a medium such as an inert hydrocarbon, which will be described later in the olefin polymerization method and preparation of a prepolymerization catalyst.

[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 present invention, “polymerization” may include the meaning of copolymerization such as random copolymerization and block copolymerization in addition to homopolymerization.

In the olefin polymerization method of the present invention, the main polymerization can also be performed in the presence of a prepolymerization catalyst obtained by prepolymerizing an α-olefin in the presence of the olefin polymerization catalyst of the present invention. It is. This prepolymerization is performed by prepolymerizing α-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 concentration higher than that 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, particularly preferably 0, in terms of titanium atom per liter of the liquid medium. Desirably, the range is from 1 to 20 mmol.

  The amount of the organometallic compound catalyst component (II) in the prepolymerization should be 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). Is desirable.

  In the prepolymerization, the alicyclic compound (III), the electron donor component (c) and the like can be used as necessary. These components are used in an amount of 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol, per mol of titanium atom in the solid titanium catalyst component (I). .

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, as the inert hydrocarbon medium used, specifically,
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene;
Alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, methylcycloheptane, cyclooctane, methylcyclooctane;
Aromatic hydrocarbons such as benzene, toluene, xylene;
Halogenated hydrocarbons such as ethylene chloride and chlorobenzene,
Alternatively, a mixture thereof can be used.
Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons. Thus, when using an inert hydrocarbon medium, it is preferable to perform prepolymerization by a batch type.

  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 about -20 to + 100 ° C, preferably about -20 to + 80 ° C, more preferably 0 to + 40 ° C.

  Next, the main polymerization carried out after passing through the pre-polymerization or without going through the pre-polymerization will be described.

  Examples of olefins that can be used in the polymerization (ie, polymerized) include α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, Linear olefins such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 4-methyl-1-pentene, 3-methyl-1-pentene And branched olefins such as 3-methyl-1-butene, and propylene, 1-butene, 1-pentene and 4-methyl-1-pentene are preferred. Propylene, 1-butene, and 4-methyl-1-pentene are particularly preferable from the viewpoint of easily exhibiting the merit of a polymer having a wide molecular weight distribution in a highly rigid resin.

Along with these α-olefins, aromatic vinyl compounds such as ethylene, styrene and allylbenzene; and alicyclic vinyl compounds such as vinylcyclohexane and vinylcycloheptane can also be used. 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 raw materials for polymerization together with ethylene and α-olefin. You can also. These compounds may be used alone or in combination of two or more. (Hereinafter, the olefin used together with the above ethylene or “α-olefin having 3 to 20 carbon atoms” is also referred to as “other olefin”.)
Among the other olefins, ethylene and aromatic vinyl compounds are preferable. Further, other olefins such as ethylene may be used in combination as long as the amount is a small amount, for example, 10% by weight or less, preferably 5% by weight or less, out of the total amount of olefins of 100% by weight.

  In the present invention, the prepolymerization and the main polymerization can be performed by any of a liquid phase polymerization method such as a bulk polymerization method, a solution polymerization and a suspension polymerization, or a gas phase polymerization method.

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

  In 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, in terms of titanium atom per liter of polymerization volume. Used in an amount of 0.005 to 0.1 mmol. The organometallic compound catalyst component (II) is usually used in an amount of about 1 to 2000 mol, preferably about 5 to 500 mol, per 1 mol of titanium atom in the prepolymerization catalyst component in the polymerization system. Used. The alicyclic compound (III) is used in an amount of 0.001 to 50 mol, preferably 0.01 to 30 mol, particularly preferably 0.05 to 20 mol, relative to the organometallic compound catalyst component (II). Used in

  If the main polymerization is performed in the presence of hydrogen, 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 200 ° C, preferably about 30 to 100 ° C, more preferably 50 to 90 ° C. The pressure is usually set to normal pressure to 100 kgf / cm ² (9.8 MPa), preferably about ^{2 to} 50 kgf / cm ² (0.20 to 4.9 MPa). In the polymerization method of the present invention, the polymerization can be carried out by 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. By performing such multistage polymerization, it is possible to further widen the molecular weight distribution of the olefin polymer.

  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 even 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 called a solid component). ) It is characteristic 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.

  When the olefin polymerization method of the present invention is used, an olefin polymer having an Mw / Mn value of 6 to 30, preferably 7 to 20 can be obtained under the same polymerization conditions as described above. Further, 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 olefin polymerization method of the present invention, a polymer having a high Mz / Mw 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 having different molecular weights in a very wide range are mixed at the catalyst level, that is, at the nano level. It is expected that

  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:
It measured according to JIS K-6721.
(2) Melt flow rate (MFR):
According to ASTM D1238E, the measurement temperature was 230 ° C. in the case of a propylene polymer and 260 ° C. in the case of a 4-methyl 1-pentene polymer.
(3) Amount of decane soluble (insoluble) component:
About 3 grams of propylene polymer (measured to a unit of 10 ^-4 grams. This weight was expressed as b (grams) in the following formula), 500 ml of decane, and soluble in decane. A small amount of a heat-resistant stabilizer was charged, and the mixture was heated to 150 ° C. in 2 hours while stirring with a stirrer in a nitrogen atmosphere to dissolve the propylene polymer. Slowly cooled to ° C. The liquid containing the resulting propylene polymer precipitate was filtered under reduced pressure using a 25G-4 standard glass filter manufactured by Iwata Glass Co., Ltd. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a part of the decane-soluble component, and this weight was measured to the unit of 10 ⁻⁴ grams (this weight was expressed as a (gram) in the following equation). .) After this operation, the amount of decane soluble component was determined by the following formula.

Decane-soluble component content = 100 × (500 × a) / (100 × b)
Decane insoluble component content = 100-100 x (500 x a) / (100 x b)
(4) Molecular weight distribution:
Liquid chromatograph: Waters ALC / GPC 150-C plus type (with suggested refractometer detector)
Column: Two GMH6-HT and two GMH6-HTL manufactured by Tosoh Corporation were connected in series.

Mobile phase medium: o-dichlorobenzene Flow rate: 1.0 ml / min Measurement temperature: 140 ° C.
Calibration curve creation method: Standard polystyrene sample concentration: 0.10% (w / w)
Sample solution volume: 500 μl
Mw / Mn value and Mz / Mw value were calculated by analyzing the obtained chromatogram by a known method. The measurement time per sample was 60 minutes.

(Preparation of solid titanium catalyst component (A))
A high-speed stirring apparatus (made by Tokushu Kika Kogyo Co., Ltd.) having an internal volume of 2 liters was sufficiently purged with nitrogen. 3 g of sorbitan distearate (manufactured by sorbitan) 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.

The above solid adduct suspended in 30 ml of decane was introduced into 200 ml of titanium tetrachloride in which 46.2 mmol in terms of magnesium atom was maintained at −20 ° C. with stirring, and the whole amount was introduced. The mixture was heated to 80 ° C. over 5 hours, and when it reached 80 ° C., diisobutyl phthalate was added in an amount of 0.15 moles per mole of magnesium atoms in the solid adduct. The temperature was raised to 120 ° C. in 40 minutes. The temperature was held at 120 ° 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 200 ml of titanium tetrachloride, and then heated to 130 ° C. and stirred for 45 minutes. Hold while. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and sufficiently washed with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.
The solid titanium catalyst component (A) was obtained by the above operation.

(Preliminary polymerization)
In a 200 ml glass four-necked reactor with a stirrer, 50 ml of purified hexane, 1.5 mmol of triethylaluminum, and 0.5 mmol of solid titanium catalyst (A) were added in terms of titanium atoms in a nitrogen atmosphere. Propylene was fed to the reactor for 1 hour at a rate of 6 liters per hour. The temperature was kept at 20 ° C.
When the supply of propylene was completed, the inside of the reactor was purged with nitrogen, and after washing operation consisting of removing the supernatant and adding purified hexane twice, resuspended in purified decane and transferred to the catalyst bottle. A prepolymerized catalyst component (B) was obtained.

(polymerization)
A polymerization vessel having an internal volume of 1 liter, which was sufficiently purged with nitrogen, was charged with 400 ml of purified heptane at room temperature, 0.8 mmol of triethylaluminum in a propylene atmosphere at 40 ° C., 0.16 mmol of diisobutyl trans-cyclohexanedicarboxylate and 0.08 mmol of the pre-catalyst component (B) was added in terms of titanium atoms. Next, the temperature was raised to 60 ° C., 0.1 NL of hydrogen was added, and the temperature was raised to 70 ° C., followed by propylene polymerization for 1 hour. The pressure during the polymerization was maintained at 0.5 MPa as a gauge pressure. After completion of the polymerization, the slurry containing the purified solid was filtered and dried under reduced pressure at 80 ° C. overnight. The results are shown in Table 1.

(Comparative Example 1)
(polymerization)
Polymerization of propylene was carried out in the same manner as in Example 1 except that 0.4 mmol of triethylaluminum and 0.08 mmol of cyclohexylmethyldimethoxysilane were used instead of diisobutyl trans-cyclohexanedicarboxylate. The results are shown in Table 1.

(Preparation of solid titanium catalyst component (C))
In the same manner as in Example 1, the above solid adduct suspended in 30 ml of decane was introduced into 200 ml of titanium tetrachloride in which 46.2 mmol in terms of magnesium atom was maintained at −20 ° C., with stirring, and the whole amount was introduced. The mixture was heated to 80 ° C. over 5 hours, and when the temperature reached 80 ° C., diisobutyl trans-cyclohexanedicarboxylate was added in an amount of 0.175 mol per 1 mol of magnesium atom in the solid adduct. The temperature was increased to 100 ° C. over 20 minutes. The temperature was held at 100 ° 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 200 ml of titanium tetrachloride, and then heated to 100 ° C. and stirred for 45 minutes. Hold while. After completion of the reaction for 45 minutes, the solid part was again collected by hot filtration, and sufficiently washed with decane and heptane at 100 ° C. until no free titanium compound was detected in the washing solution.
The solid titanium catalyst component (C) was obtained by the above operation.

(Preliminary polymerization)
Preliminary polymerization of propylene was performed in the same manner as in Example 1 except that the solid titanium catalyst component (C) was used instead of the solid titanium catalyst component (A) to obtain a prepolymerization catalyst component (D).

(Main polymerization)
Propylene was polymerized in the same manner as in Example 1 except that the prepolymerization catalyst component (D) was used instead of the prepolymerization catalyst component (B). The results are shown in Table 1.

(Comparative Example 2)
(polymerization)
Propylene was polymerized in the same manner as in Comparative Example 1 except that the prepolymerization catalyst component (D) was used instead of the prepolymerization catalyst component (B). The results are shown in Table 1.

  It can be seen that the polypropylene obtained by using the olefin polymerization catalyst and olefin polymerization method of the present invention is a polymer having a wide molecular weight distribution. In particular, when PPs having substantially the same MFR value are compared, it is characteristic that the Mz / Mw value indicating that the content of the component having a high molecular weight is high is high.

Claims (4)

A solid titanium catalyst component (I) comprising titanium, magnesium, halogen and optionally an electron donor; and
Organometallic compound catalyst component (II) containing a metal element selected from Group 1, Group 2 and Group 13 of the periodic table and alicyclic compound (III) specified by the following formula
And an olefin polymerization catalyst.
[In Formula (1), n is an integer of 5-10.
R ¹ is a substituent containing at least carbon, oxygen, and hydrogen.
R ² and R ³ are each independently an R ¹ group or R, and at least one of R ² and R ³ is an R ¹ group.
Single bonds in the cyclic skeleton (excluding C ^a -C ^a bonds) may be replaced with double bonds.
A plurality of Rs are each independently an atom or group 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. And may be bonded to each other to form a ring.
R may be contained a double bond in the skeleton of the bound formed by ring together, in the ring skeleton, if it contains C ^a to R ¹ are bonded two or more, the ring The number of carbon atoms constituting the skeleton is 5-10. ].   2. The olefin polymerization catalyst according to claim 1, wherein in the formula (1), all the bonds between carbon atoms in the cyclic skeleton are single bonds.   In the said Formula (1), the said cyclic | annular frame | skeleton consists of 6 carbon atoms, The catalyst for olefin polymerization of Claim 1 characterized by the above-mentioned. An olefin polymerization method comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to claim 1.