JP6137463B2 - Solid catalyst component for olefin polymerization, olefin polymerization catalyst, and process for producing olefin polymer using the same - Google Patents

Description

  The present invention provides a solid catalyst component for olefin polymerization, which can obtain an olefin polymer having a wide molecular weight distribution in a high yield while maintaining high response to hydrogen when polymerizing olefins. The present invention relates to a catalyst and a method for producing an olefin polymer using the catalyst.

  Conventionally, in the polymerization of olefins, olefins are present in the presence of a solid catalyst component containing magnesium, titanium, an electron donating compound, and halogen as essential components, an organoaluminum compound and an organosilicon compound. Many olefin polymerization methods for polymerizing or copolymerizing olefins have been proposed.

  For example, Patent Document 1 (WO 2006-077945) discloses that a polyolefin having a wide molecular weight distribution can be obtained by using a specific cyclic carboxylic acid ester compound during solid catalyst synthesis. Patent Document 2 (Japanese Patent Laid-Open No. 2010-001420) discloses that when a solid product is formed by contacting a magnesium compound (a) with a tetravalent titanium halogen compound (b), the formation of the solid product is described. Olefin polymerization solid catalyst component obtained by contacting 1-cyclohexene dicarboxylic acid diester (c) so that the amount per 1 mol of magnesium compound (a) is in a specific range before and after or in the middle of It is disclosed that the catalyst can obtain an olefin polymer having a high stereoregularity, a small amount of coarse powder and a sharp particle size distribution in a high yield while having a high response to hydrogen.

WO2006-077945 JP 2010-001420 A

  However, since the catalyst of Patent Document 1 has a large steric hindrance in the vicinity of the carbonyl group adsorbed on the support, the reactivity with the alkylaluminum compound is low. There was room for improvement. Further, the catalyst of Patent Document 2 has a problem that a steric hindrance in the vicinity of the polymerization active point is homogeneous, and thus a polymer having a wide molecular weight distribution cannot be obtained yet.

  Accordingly, an object of the present invention is to provide a novel olefin polymer that can maintain a high polymerization activity and response to hydrogen when polymerizing olefins and can obtain an olefin polymer having a wide molecular weight distribution in a high yield. An object of the present invention is to provide a method for producing a solid catalyst component, a catalyst, and an olefin polymer.

  Under such circumstances, the present inventors have conducted extensive studies, and as a result, the solid catalyst component for polymerizing olefins containing titanium, magnesium, halogen and a specific cyclic ester compound has a polymerization activity and a resistance to polymerization when olefins are polymerized. The inventors have found that a variety of active species can be imparted while maintaining a high hydrogen response, and that a polymer having a broad molecular weight distribution can be obtained, and the present invention has been completed.

（式中、Ｒ^１およびＲ^２は、炭素数１〜２０の直鎖状アルキル基、炭素数３〜２０の分岐状アルキル基、ビニル基、炭素数３〜２０の直鎖状アルケニル基または分岐状アルケニル基、炭素数１〜２０の直鎖状ハロゲン置換アルキル基、炭素数３〜２０の分岐状ハロゲン置換アルキル基、炭素数３〜２０のシクロアルキル基、炭素数３〜２０のシクロアルケニル基、炭素数６〜２０の芳香族炭化水素基を示し、互いに同一であっても異なっていてもよい。Ｒ^３〜Ｒ^１０は、水素原子、ハロゲン原子、炭素数１〜２０の直鎖状アルキル基、炭素数３〜２０の分岐アルキル基、ビニル基、炭素数３〜２０の直鎖状アルケニル基または分岐アルケニル基、炭素数１〜２０の直鎖状ハロゲン置換アルキル基、炭素数３〜２０の分岐ハロゲン置換アルキル基、炭素数２〜２０の直鎖状ハロゲン置換アルケニル基、炭素数３〜２０の分岐ハロゲン置換アルケニル基、炭素数３〜２０のシクロアルキル基、炭素数３〜２０のシクロアルケニル基、炭素数３〜２０のハロゲン置換シクロアルキル基、炭素数３〜２０のハロゲン置換シクロアルケニル基、炭素数６〜２４の芳香族炭化水素基、炭素数６〜２４のハロゲン置換芳香族炭化水素基を示し、同一でも異なっていてもよく、Ｒ^３〜Ｒ^１０の中、少なくとも２つが、ハロゲン原子、炭素数１〜２０の直鎖状アルキル基、炭素数３〜２０の分岐アルキル基、ビニル基、炭素数３〜２０の直鎖状アルケニル基または分岐アルケニル基、炭素数１〜２０の直鎖状ハロゲン置換アルキル基、炭素数３〜２０の分岐ハロゲン置換アルキル基、炭素数２〜２０の直鎖状ハロゲン置換アルケニル基、炭素数３〜２０の分岐ハロゲン置換アルケニル基、炭素数３〜２０のシクロアルキル基、炭素数３〜２０のシクロアルケニル基、炭素数３〜２０のハロゲン置換シクロアルキル基、炭素数３〜２０のハロゲン置換シクロアルケニル基、炭素数６〜２４の芳香族炭化水素基または炭素数６〜２４のハロゲン置換芳香族炭化水素基である。）で表される化合物を含有することを特徴とするオレフィン類重合用固体触媒成分を提供するものである。 That is, the present invention relates to titanium, magnesium, halogen and the following general formula (1);

(In the formula, R ¹ and R ² are each a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 20 carbon atoms, or branched. Alkenyl group, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, branched halogen-substituted alkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same or different from each other, and R ^{3 to} R ¹⁰ are each a hydrogen atom, a halogen atom, or a linear alkyl group having 1 to 20 carbon atoms. Group, branched alkyl group having 3 to 20 carbon atoms, vinyl group, linear alkenyl group or branched alkenyl group having 3 to 20 carbon atoms, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms Branched halogen substituted al Group, straight chain halogen-substituted alkenyl group having 2 to 20 carbon atoms, branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, carbon A halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms. , May be the same or different, and at least two of R ^{3 to} R ¹⁰ are a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, carbon C3-C20 linear alkenyl group or branched alkenyl group, C1-C20 linear halogen-substituted alkyl group, C3-C20 branched halogen-substituted alkyl group, C2-C2 0 linear halogen-substituted alkenyl groups, branched halogen-substituted alkenyl groups having 3 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, halogen substitution having 3 to 20 carbon atoms A cycloalkyl group, a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, or a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms. It is intended to provide a solid catalyst component for polymerization of olefins, which contains

The present invention also provides the solid catalyst component, the following general formula (2);
^{_{R 11 p AlQ 3-p (}} 2)
(In the formula, R ¹¹ represents a hydrocarbyl group having 1 to 6 carbon atoms, and when there are a plurality thereof, they may be the same or different, and Q represents a hydrogen atom, a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom. And p is a real number of 0 <p ≦ 3.) An olefin polymerization catalyst characterized by being formed from an organoaluminum compound represented by the following formula:

  The present invention also provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  INDUSTRIAL APPLICABILITY According to the present invention, a novel solid catalyst component for polymerizing olefins capable of obtaining a polymer having a wide molecular weight distribution while maintaining high polymerization activity and hydrogen response, a catalyst and an olefin polymer using the component The manufacturing method of can be provided. Therefore, a polymer excellent in moldability can be produced at low cost and efficiently.

It is a flowchart figure which shows the process of preparing the polymerization catalyst of this invention.

(Description of solid catalyst component for olefin polymerization)
The solid catalyst component for polymerization of olefins of the present invention (hereinafter sometimes simply referred to as “solid catalyst component” or “component (A)”) is represented by the above general formula (magnesium, titanium, halogen, and electron donating compound). The cyclic ester represented by 1) (hereinafter sometimes simply referred to as “component (c)”) is contained as an essential component.

  In the component (A), examples of the halogen include fluorine, chlorine, bromine and iodine atoms, among which chlorine, bromine and iodine are preferable, and chlorine and iodine are particularly preferable.

  The compound of the above general formula (1) is composed of eight hydrogen atoms in which an alkoxycarbonyl group is bonded to the 1-position and the 2-position of the cyclohexene ring of 1-cyclohexene and the 3-position to 6-position of the cyclohexene ring are bonded. , 1-cyclohexene dicarboxylic acid diester having two or more substituents, at least two of which are substituted with a specific group such as a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

In R ¹ and R ² in the general formula (1), examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. , N-hexyl group, n-pentyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Preferably, it is a C1-C12 linear alkyl group. Moreover, as a C3-C20 branched alkyl group, the alkyl group which has secondary carbon or tertiary carbon, such as an isopropyl group, an isobutyl group, t-butyl group, an isopentyl group, a neopentyl group, is mentioned, for example. Preferably, it is a C3-C12 branched alkyl group.

Moreover, in R < ¹ > and R < ² >, as a C3-C20 linear alkenyl group, an allyl group, 3-butenyl group, 4-hexenyl group, 5-hexenyl group, 7-octenyl group, 10-dodecenyl group Etc. Preferably, it is a C3-C12 linear alkenyl group. Examples of the branched alkenyl group having 3 to 20 carbon atoms include an isopropenyl group, an isobutenyl group, an isopentenyl group, and a 2-ethyl-3-hexenyl group. Preferably, it is a C3-C12 branched alkenyl group.

In R ¹ and R ² , examples of the linear halogen-substituted alkyl group having 1 to 20 carbon atoms include a halogenated methyl group, a halogenated ethyl group, a halogenated n-propyl group, a halogenated n-butyl group, Examples thereof include a halogenated n-pentyl group, a halogenated n-hexyl group, a halogenated n-pentyl group, a halogenated n-octyl group, a halogenated nonyl group, and a halogenated decyl group. Preferably, it is a C1-C12 linear halogen-substituted alkyl group.

In R ¹ and R ² , examples of the branched halogen-substituted alkyl group having 3 to 20 carbon atoms include a halogenated isopropyl group, a halogenated isobutyl group, a halogenated 2-ethylhexyl group, and a halogenated neopentyl group. Preferably, it is a branched halogen-substituted alkyl group having 3 to 12 carbon atoms.

In R ¹ and R ² , examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. It is done. Preferably it is a C3-C12 cycloalkyl group.

In R ¹ and R ² , the cycloalkenyl group having 3 to 20 carbon atoms includes a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a norbornene group, and the like. Preferably it is a C3-C12 cycloalkenyl group.

In R ¹ and R ² , the aromatic hydrocarbon group having 6 to 20 carbon atoms includes phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, benzyl group, 1-phenylethyl group, 2-phenyl group. Examples include ethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group, 1,8-dimethylnaphthyl group and the like. Preferably it is a C6-C12 aromatic hydrocarbon group.

In R < ³ > -R < ¹⁰ > in the said General formula (1), as a halogen atom, each atom of a fluorine, chlorine, bromine, or iodine is mentioned, for example, Among these, Preferably it is chlorine, a bromine, or an iodine, Especially preferably, Each atom of chlorine or bromine.

^Further, in R 3 ^{to R 10,} a linear alkyl group having 1 to 20 carbon atoms, branched alkyl group having 3 to 20 carbon atoms, linear alkenyl group having 3 to 20 carbon atoms, branched C3-20 Examples of the alkenyl group, the linear halogen-substituted alkyl group having 1 to 20 carbon atoms, and the branched halogen-substituted alkyl group having 3 to 20 carbon atoms are the same as those for R ¹ and R ² .

In R ^{3 to} R ¹⁰ , examples of the linear halogen-substituted alkenyl group having 2 to 20 carbon atoms include 2-halogenated vinyl group, 3-halogenated allyl group, 3-halogenated-2-butenyl group, 4-halogen -3-butenyl group, perhalogenated 2-butenyl group, 6-halogenated-4-hexenyl group, 3-trihalogenated methyl-2-propenyl group and the like. A linear halogen-substituted alkenyl group having 2 to 12 carbon atoms is preferred.

In R ^{3 to} R ¹⁰ , the branched halogen-substituted alkenyl group having 3 to 20 carbon atoms includes 3-trihalogenated-2-butenyl group, 2-pentahalogenated ethyl-3-hexenyl group, and 6-halogenated-3. -Ethyl-4-hexenyl group, 3-halogenated isobutenyl group and the like. A branched halogen-substituted alkenyl group having 3 to 12 carbon atoms is preferred.

In R ^{3 to} R ¹⁰ , examples of the cycloalkyl group having 3 to 20 carbon atoms and the cycloalkenyl group having 3 to 20 carbon atoms are the same as those for R ¹ and R ² .

In R ^{3 to} R ¹⁰ , the halogen-substituted cycloalkyl group having 3 to 20 carbon atoms includes a halogen-substituted cyclopropyl group, a halogen-substituted cyclobutyl group, a halogen-substituted cyclopentyl group, a halogen-substituted trimethylcyclopentyl group, a halogen-substituted cyclohexyl group, and a halogen-substituted group. Examples include methylcyclohexyl group, halogen-substituted cycloheptyl group, halogen-substituted cyclooctyl group, halogen-substituted cyclononyl group, halogen-substituted cyclodecyl group, and halogen-substituted butylcyclopentyl. A halogen-substituted cycloalkyl group having 3 to 12 carbon atoms is preferred.

In R ^{3 to} R ¹⁰ , the halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms includes a halogen-substituted cyclopropenyl group, a halogen-substituted cyclobutenyl group, a halogen-substituted cyclopentenyl group, a halogen-substituted trimethylcyclopentenyl group, and a halogen-substituted cyclohexenyl group. Group, halogen-substituted methylcyclohexenyl group, halogen-substituted cycloheptenyl group, halogen-substituted cyclooctenyl group, halogen-substituted cyclononenyl group, halogen-substituted cyclodecenyl group, halogen-substituted butylcyclopentenyl and the like. A halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms is preferred.

In R ^{3 to} R ¹⁰ , examples of the aromatic hydrocarbon group having 6 to 24 carbon atoms are the same as the aromatic hydrocarbon group having 6 to 20 carbon atoms of R ¹ and R ² .

In R ^{3 to} R ¹⁰ , the halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms includes a halogenated phenyl group, a halogenated methylphenyl group, a trihalogenated methylphenyl group, a perhalogenated benzyl group, and a perhalogenated group. Examples thereof include a phenyl group, 2-phenyl, 2-halogenated ethyl group, perhalogenated naphthyl group, 4-phenyl, 2,3-dihalogenated butyl group. Preferably it is a 6-12 halogen-containing aromatic hydrocarbon group.

Moreover, in General formula (1), Preferably, in R < ³ > -R < ¹⁰ >, 2 or more and 4 or less are a halogen atom, a C1-C12 linear alkyl group, and a C3-C12 branched alkyl. Group, vinyl group, linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, linear halogen-substituted alkyl group having 1 to 12 carbon atoms, branched halogen-substituted alkyl group having 3 to 12 carbon atoms, carbon number 3 -12 linear halogen-substituted alkenyl group or branched halogen-substituted alkenyl group, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms, halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, carbon A halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the 1-cyclohexene dicarboxylic acid diester having such a substituent include 3,3-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 3,4-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 3,5-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 3,6-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 4,4-substituted-1-cyclohexene-1,2-dicarboxylic acid diester 4,5-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 4,6-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 5,5-substituted-1-cyclohexene-1,2-dicarboxylic acid Diester, 5,6-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 6,6-substituted-1- Chlohexene-1,2-dicarboxylic acid diester, 3,4,6-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, 3,3,4,6-substituted-1-cyclohexene-1,2-dicarboxylic acid diester, etc. Is mentioned.

In the general formula (1), those having one or more substituents at the 3-position and 6-position or 4-position and 5-position of the cyclohexene ring of 1-cyclohexene, preferably R ³ and R ⁹ or R ⁵ R ⁷ is a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, a linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, carbon number Those having 3 to 12 cycloalkyl groups or aromatic hydrocarbon groups having 6 to 12 carbon atoms have a good adsorption state to the solid catalyst component, and then the alkyl represented by the general formula (2) Active species formation and elimination by contact with aluminum occur in a suitable balance, thereby providing a variety of active species in the solid catalyst component and broadening the molecular weight distribution of the olefin polymer obtained by polymerization. In view of maintaining high hydrogen activity.

Further, in the general formula (1), those having 1 or 2 substituents at the 3-position and 6-position of the cyclohexene ring of 1-cyclohexene, respectively, are particularly preferred, and halogen atoms at the 3-position and 6-position of the cyclohexene ring Or 3,6-dihalogen-1-cyclohexene dicarboxylic acid diester and 3,6-dialkyl-1-cyclohexene dicarboxylic acid in which the above preferred substituents are bonded and R ¹ and R ² are alkyl groups having 1 to 8 carbon atoms Acid diesters are more preferred.

  Preferred examples of the general formula (1) include diethyl 3,6-dichloro-1-cyclohexene-1,2-dicarboxylate and di-n-propyl 3,6-dichloro-1-cyclohexene-1,2-dicarboxylate. 3,6-dichloro-1-cyclohexene-1,2-dicarboxylic acid di-n-butyl, 3,6-dichloro-1-cyclohexene-1,2-dicarboxylic acid diisobutyl, 3,6-dichloro-1-cyclohexene -1,2-dicarboxylic acid di-n-pentyl, 3,6-dichloro-1-cyclohexene-1,2-dicarboxylic acid di-n-hexyl, 3,6-dichloro-1-cyclohexene-1,2-dicarboxylic acid Di-n-octyl acid, methyl ethyl 3,6-dichloro-1-cyclohexene-1,2-dicarboxylate, 3,6-dichloro-1-cyclohexene-1 2-ethyl dicarboxylate (n-butyl), diethyl 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate, 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate di-n-propyl, 3 Di-n-butyl 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate, diisobutyl 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate, 3,6-dimethyl-1-cyclohexene-1,2 Di-n-pentyl dicarboxylate, 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid di-n-hexyl, 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid di-n -Octyl, methyl ethyl 3,6-dimethylro-1-cyclohexene-1,2-dicarboxylate, 3,6-dimethyl-1-cyclohexene-1, - Ethyl dicarboxylic acid (n- butyl) and the like. Among these compounds, diethyl 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate in that the molecular weight distribution of the obtained polymer is wide and the stereoregularity during polymerization is less likely to occur. Particularly preferred is di-n-butyl 3,6-dimethyl 1-cyclohexene-1,2-dicarboxylate. In addition, the said component (c) can be used individually by 1 type or in combination of 2 or more types.

  The solid catalyst component (A) in the present invention may contain an electron donating compound (hereinafter also referred to as component (d)) other than the compound represented by the general formula (1). Examples of such electron donating compounds (d) are organic compounds containing oxygen atoms or nitrogen atoms, such as alcohols, phenols, ethers, esters other than component (c), ketones, acid halides. Aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing Si—O—C bonds, organosilicon compounds containing Si—N—C bonds, and the like. Two or more of these electron donating compounds (d) can be used in combination.

The solid catalyst component (A) in the present invention may contain polysiloxane (hereinafter also simply referred to as “component (e)”). By using polysiloxane, the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced. Polysiloxane is a polymer having a siloxane bond (—Si—O—Si— bond) in the main chain, but is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10,000). Centistokes), more preferably 0.03 to ⁵ cm ² / s (3 to 500 centistokes), which is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Examples thereof include siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane.

  Further, the contents of titanium, magnesium, halogen atoms and component (c) in the solid catalyst component (A) in the present invention are not particularly limited, but preferably 0.1 to 10% by weight of titanium, preferably 0.8. 5 to 8.0 wt%, more preferably 1.0 to 5.0 wt%, magnesium is 10 to 40 wt%, more preferably 10 to 30 wt%, particularly preferably 13 to 25 wt%, halogen Atoms are 20 to 89% by weight, more preferably 30 to 85% by weight, particularly preferably 45 to 75% by weight, and component (c) is 0.5 to 40% by weight in total, more preferably 1 to 30% by weight in total. The total amount is particularly preferably 1 to 20% by weight.

(Description of production method of solid catalyst component (A) for olefin polymerization)
In the solid catalyst component (A) of the present invention, the following magnesium compound, titanium compound, and if necessary, a halogen compound other than the titanium compound and the component (c) of the general formula (1) are brought into contact with each other. It is prepared by.

  Examples of the magnesium compound used in the preparation of the solid catalyst component (A) of the present invention (hereinafter sometimes simply referred to as “component (a)”) include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, Examples include diaryloxymagnesium, halogenated alkoxymagnesium and fatty acid magnesium. Specific examples of the magnesium dihalide include magnesium dichloride, magnesium dibromide, magnesium diiodide, magnesium difluoride and the like.

  Dialkyl magnesium includes dimethyl magnesium, diethyl magnesium, methyl ethyl magnesium, di-n-propyl magnesium, methyl-n-propyl magnesium, ethyl-n-propyl magnesium, di-n-butyl magnesium, methyl-n-butyl magnesium, And ethyl-n-butylmagnesium. These dialkyl magnesiums can be obtained by reacting magnesium metal with a halogenated hydrocarbon compound or an alcohol.

  Examples of the halogenated alkyl magnesium include ethyl magnesium chloride, n-propyl magnesium chloride, n-butyl magnesium chloride and the like. These magnesium halides can be obtained by reacting magnesium metal with a halogenated hydrocarbon compound or an alcohol.

  As dialkoxymagnesium or diaryloxymagnesium, dimethoxymagnesium, diethoxymagnesium, di-n-propoxymagnesium, di-n-butoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxy-n-propoxymagnesium, bu-n- Toxiethoxy magnesium and the like can be mentioned. These dialkoxymagnesium or diaryloxymagnesium can be obtained by reacting metal magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

  Examples of the halogenated alkoxymagnesium include methoxymagnesium chloride, ethoxymagnesium chloride, n-propoxymagnesium chloride, and n-butoxymagnesium chloride. Examples of the fatty acid magnesium include magnesium laurate, magnesium stearate, magnesium octoate, and magnesium decanoate. Among these magnesium compounds in the present invention, dialkoxymagnesium is preferable, and among them, diethoxymagnesium and di-n-propoxymagnesium are particularly preferably used. Moreover, said magnesium compound can also be used individually or in combination of 2 or more types.

  In the present invention, when dialkoxymagnesium is used as the solid catalyst component (A), dialkoxymagnesium is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder are solved.

  The spherical dialkoxymagnesium does not necessarily need to be spherical, and an elliptical or potato-shaped one is used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is usually 3 or less, preferably 1 to 2, more preferably 1 to 1.5. is there. Such spherical dialkoxymagnesium production methods are disclosed in, for example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388. Etc.

  The average particle size of the dialkoxymagnesium is usually 1 to 200 μm, preferably 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle size is usually 1 to 200 μm, preferably 5 to 80 μm, and more preferably 10 to 60 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.

  The titanium compound (b) (hereinafter sometimes referred to as “component (b)”) used for the preparation of the component (A) in the present invention is preferably a tetravalent titanium halogen compound, and is a titanium halide or an alkoxy titanium halide. One or more compounds selected from the group can be used.

  Examples of the titanium halide include titanium tetrahalide and alkoxytitanium halide. Specific examples of titanium tetrahalide include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide. Examples of the alkoxytitanium halide include titanium tetrahalide and alkoxytitanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, and propoxy. Titanium trichloride, n-butoxy titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri- Examples thereof include n-butoxy titanium chloride. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.

  Examples of the compound (component (c)) represented by the general formula (1) used for the preparation of the component (A) are the same as the component (c) in the solid catalyst component (A).

  In addition, examples of the electron donating compound (d) other than the component (c) used for the preparation of the component (A) include the same compounds as the component (d) in the solid catalyst component (A). Specific examples of component (d) include alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and diphenyl ether. 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) phenyl carbonate, carbonic acid (2-ethoxy) Ethers such as ethyl) ethyl, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoate acid Monocarboxylic acid esters such as octyl, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, malonic acid diester, alkyl-substituted malonic acid diester, alkylidene-substituted malon Aliphatic carboxylic acid diesters such as acid diesters, succinic acid diesters, maleic acid diesters, and adipic acid diesters, aromatic dicarboxylic acid esters such as phthalic acid diesters, and ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, and benzophenone Acid halides such as phthalic acid dichloride and terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, methylamine, ethyl acetate Amines such as styrene, tributylamine, piperidine, aniline and pyridine, amides such as oleic acid amide and stearic acid amide, nitriles such as acetonitrile, benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate It is.

Moreover, as an organosilicon compound containing a Si-OC bond, the following general formula (6);
R ²¹ _s Si (OR ²² ) _4-s (6)
(In the formula, R ²¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms, cycloalkyl group, phenyl group, vinyl group, allyl group, aralkyl group, monoalkylamino group, dialkylamino group. , A cycloalkylamino group, and a polycyclic amino group, which may be the same or different, and R ²² represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group. And may be the same or different, and s is an integer of 1 to 3.). Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkyl (alkyl) alkoxysilane, (alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, Examples thereof include cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane and the like.

Moreover, as an organosilicon compound containing a Si-N-C bond, following General formula (7);
(R ²³ R ²⁴ N) _t SiR ²⁵ _4-t (7)
(Wherein R ²³ and R ²⁴ are a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or 3 carbon atoms. Or a C 6-12 aromatic hydrocarbon group, R ²³ and R ²⁴ may be the same or different, and R ²³ and R ²⁴ are bonded to each other. R ²⁵ may be a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or 3 carbon atoms. -12 cycloalkyl group, C6-C12 aromatic hydrocarbon group, C1-C12 linear alkoxy group or C3-C12 branched alkoxy group, vinyloxy group, C3-C12 Allyloxy group, aryl having 6 to 12 carbon atoms It indicates an oxy group, if R ²⁵ is plural, R ²⁵ is an aminosilane compound represented by the optionally be the same or different .t is an integer from 1 to 3.), Tetrakis ( Examples include alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, and trialkyl (alkylamino) silane.

  Among the electron donating compounds (d), esters other than ethers and component (c), particularly carboxylic acid diesters, are preferably used. Particularly, ether group-containing carbonates, alkyl-substituted malonic acid diesters, alkylidene-substituted malonic acid diesters. Phthalic acid diesters, organosilicon compounds containing Si—O—C bonds and organosilicon compounds containing Si—N—C bonds are preferred. Particularly preferably, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, methyl isopropyl phthalate, ethyl phthalate (n-propyl) Ethyl phthalate (n-butyl), ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, di-neopentyl phthalate, di-n-heptyl phthalate, bis (2-ethylhexyl) phthalate, (2-ethoxyethyl) methyl carbonate, (2-ethoxyethyl) ethyl carbonate, (2-ethoxyethyl) phenyl carbonate, dimethyl diisobutyl malonate, diethyl diisobutyl malonate, benzylidene malonate, benzylidene malonate, 1,1 -Cyclohexanedicarboxylic acid di Chill, 1,1-cyclohexanedicarboxylic acid diethyl, cyclohexyl dimethyl malonate, cyclohexyl diethyl malonate, butyl dimethyl malonate, butyl diethyl malonate, one kind or two or more of these can be used.

  In the preparation of the solid catalyst component (A) in the present invention, in addition to the above essential components, aluminum trichloride, diethoxyaluminum chloride, diisopropoxyaluminum chloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride, butoxyaluminum dichloride. Further, an aluminum compound such as triethoxyaluminum, or a metal salt of an organic acid such as sodium stearate, magnesium stearate, aluminum stearate, or the above component (e) can be used. Examples of the component (e) include the same components as the component (e) in the solid catalyst component (A).

In the preparation of the component (A), if necessary, the general formula (8);
^{_{R 26 r AlQ 3-r (}} 8)
(Wherein R ²⁶ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and r is a real number of 0 <r ≦ 3) (component) Contacting (f)) is also preferable in that the polymerization activity and stereoregularity of the resulting solid catalyst component can be improved.

  The solid catalyst component (A) is formed by bringing the component (a) and the component (b) into contact with each other to form a solid product, and a specific amount of the component before, during, or during the formation of the solid product. (C) or, if necessary, can be prepared by further contacting component (d) to component (f), and further contacting the solid product with component (b). Although it is possible to perform the treatment in the absence of the active organic solvent, it is preferable to carry out the treatment in the presence of the inert organic solvent in consideration of ease of operation.

  As the inert organic solvent used, saturated hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-diethylcyclohexane, methylcyclohexene, decalin; benzene, toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbon compounds: Halogenated hydrocarbon compounds such as orthodichlorobenzene, methylene chloride, carbon tetrachloride, dichloroethane, etc. Among them, the boiling point of heptane, ethylcyclohexane, toluene, xylene, ethylbenzene, etc. is 90- An aromatic hydrocarbon compound that is liquid at room temperature of about 150 ° C. is preferred. In particular, the activity and stereospecificity of the solid catalyst component obtained by using heptane, ethylcyclohexane, toluene, xylene, and ethylbenzene when contacting each component or for washing after the contact can be further improved.

  In the preparation of the solid catalyst component (A) of the present invention, the component (a) and the component (b) are brought into contact with each other to form a solid product, and the component (c) before, during or during the formation of the solid product. Contact. Thereafter, the solid catalyst component (A) is preferably obtained by contacting with the component (b).

  In addition, as a method for preparing the solid catalyst component (A), the magnesium compound of the above component (a) is dissolved in alcohol, titanium compound, carbonic acid or the like, and contacted with the component (b) and the component (c) or A method in which a solid product is precipitated by heat treatment or the like and the component (b) is contacted with the solid product again, or the component (a) is suspended in the component (b) or an inert hydrocarbon solvent, Furthermore, a method of obtaining a solid catalyst component (A) by contacting the component (c) and the component (b) to obtain a solid product, and bringing the solid product into contact with the component (b) and the component (c) again. It is done. In these preparations, the catalytic activity and the stereoregularity of the resulting polymer can be further improved by repeatedly contacting the component (b) and the component (c) at least once each with the solid product produced above. it can.

  Among these, the particles of the solid catalyst component obtained by the former method are almost spherical and the particle size distribution is sharp. Also in the latter method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, using a spray device. By forming particles by a so-called spray drying method in which a solution or suspension is sprayed and dried, a solid catalyst component having a spherical shape and a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture and the like are removed. The contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC is preferable. If the temperature during the reaction is less than 40 ° C., the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if it exceeds 130 ° C., evaporation of the solvent used becomes remarkable. Therefore, it becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

Below, the preparation method of a solid catalyst component (A) is illustrated.
(1) After magnesium chloride (a) is dissolved in tetraalkoxytitanium, polysiloxane is contacted to obtain a solid product, and the solid product is contacted with titanium tetrachloride (b) and component (c). A method of preparing a solid catalyst component (A) by obtaining two solid products and further contacting (b) with a second solid product.
(2) Anhydrous magnesium chloride (a) and 2-ethylhexyl alcohol are reacted to form a homogeneous solution, and then the homogeneous solution is contacted with phthalic anhydride, and then this solution is mixed with titanium tetrachloride (b) and the component (c ) Is contacted to obtain a solid product, and the solid product is further contacted with titanium tetrachloride (b) to prepare a solid catalyst component (A).
(3) An organomagnesium compound (a) is synthesized by reacting magnesium metal, butyl chloride and dibutyl ether, and the organomagnesium compound is contacted with tetrabutoxytitanium and tetraethoxytitanium to obtain a solid product. A method of preparing the solid catalyst component (A) by bringing the solid product, (b) and component (c) into contact to obtain a second solid product, and further contacting the second solid product with (b). In this case, the solid catalyst component (A) can also be prepared by preliminarily polymerizing the solid component with an organoaluminum compound, an organosilicon compound, and an olefin.
(4) An organomagnesium compound (a) such as dibutylmagnesium and an organoaluminum compound are contact-reacted with an alcohol such as butanol or 2-ethylhexyl alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution. For example, a silicon compound such as SiCl ₄ , HSiCl ₃ , polysiloxane or the like is contacted to obtain a solid product, and then the solid product is contacted with (b) and component (c) in the presence of an aromatic hydrocarbon solvent. To obtain a second solid product, and further contact (b) with the second solid product to prepare the solid catalyst component (A).
(5) Magnesium chloride (a), tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon compound to form a homogeneous solution, and after adding titanium tetrachloride (b) to the solution, the temperature is increased. The solid product is precipitated, the component (c) is contacted with the solid product, and titanium tetrachloride (b) is further contacted to obtain the solid catalyst component (A).
(6) Metal magnesium powder, alkyl monohalogen compound and iodine are contact-reacted, and then tetraalkoxytitanium, acid halide, and aliphatic alcohol are contact-reacted in the presence of an aliphatic hydrocarbon to obtain a homogeneous solution (a) After adding titanium tetrachloride (b) to the solution, the temperature was raised to precipitate a solid product, the component (c) was brought into contact with the solid product, and further titanium tetrachloride (b), component (c) ) To prepare a solid catalyst component (A).
(7) After diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon solvent, it is contacted with titanium tetrachloride (b), and then heated to contact with component (c) to form a solid. After the solid product is washed with alkylbenzene, titanium tetrachloride (b) is contacted again in the presence of alkylbenzene to prepare the solid catalyst component (A) for olefin polymerization. At this time, the solid component can also be heat-treated in the presence or absence of a hydrocarbon solvent to obtain the solid catalyst component (A).
(8) After diethoxymagnesium (a) is suspended in alkylbenzene, it is contacted with titanium tetrachloride (b) and component (c) to obtain a solid product, and the solid product is washed with alkylbenzene. Then, a method of obtaining a solid catalyst component (A) by contacting titanium tetrachloride (b) again in the presence of alkylbenzene.
(9) Co-grinding a silicon compound represented by diethoxymagnesium (a), calcium chloride and Si (OR ² ) 4 (wherein R ² represents an alkyl group or an aryl group), and the resulting pulverization A solid catalyst component (A) is prepared by suspending a solid substance in an aromatic hydrocarbon, contacting with titanium tetrachloride (b) and component (c), and then further contacting with titanium tetrachloride (b). how to.
(10) Diethoxymagnesium (a) and component (c) are suspended in alkylbenzene, the suspension is added to titanium tetrachloride (b) and reacted to obtain a solid product. A method in which a solid catalyst component (A) is obtained by washing a product with alkylbenzene and then contacting titanium tetrachloride (b) again in the presence of alkylbenzene.
(11) By contacting aliphatic magnesium (a) such as calcium halide and magnesium stearate with titanium tetrachloride (b) and component (c), and then further contacting titanium tetrachloride (b). A method for preparing the solid catalyst component (A).
(12) After diethoxymagnesium (a) is suspended in an alkylbenzene or halogenated hydrocarbon solvent, it is brought into contact with titanium tetrachloride (b), and then heated to cause component (c) to contact and react with the solid. A product is obtained, and after washing the solid product with alkylbenzene, titanium tetrachloride (b) is contacted again in the presence of alkylbenzene to prepare the solid catalyst component (A), which comprises the above suspension, A method of preparing a solid catalyst component (A) by contacting aluminum chloride at any stage of contact and contact reaction.
(13) Diethoxymagnesium (a), 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of toluene to obtain a homogeneous solution, and this solution is contacted with titanium tetrachloride (b) and component (c). To obtain a solid product, which is further dissolved in tetrahydrofuran, and then further solid product is precipitated, and this solid product is contacted with titanium tetrachloride (b) to prepare a solid catalyst component (A). how to. In this case, a silicon compound component (e) such as tetrabutoxysilane can be used in any of the contact, contact reaction, and dissolution steps.
(14) Magnesium chloride (a), an organic epoxy compound and a phosphoric acid compound are suspended in a hydrocarbon solvent such as toluene, and then heated to obtain a homogeneous solution. To this solution, phthalic anhydride and titanium tetrachloride ( b) is contacted to obtain a solid product, the solid product is contacted with component (c) and reacted, and the resulting reaction product is washed with alkylbenzene and then again tetrachloride in the presence of alkylbenzene. A method for obtaining a solid catalyst component (A) by contacting titanium (b).
(15) dialkoxymagnesium (a), titanium tetrachloride (b) and component (c) are contact-reacted in the presence of toluene, and the resulting reaction product is contacted with a silicon compound such as polysiloxane; A method of obtaining a solid catalyst component (A) by contacting titanium tetrachloride (b), then contacting a metal salt of an organic acid, and then contacting titanium tetrachloride (b) again.

  Moreover, as a preferable preparation method of the solid catalyst component (A) of the present invention, the component (a) is suspended in a liquid aromatic hydrocarbon compound such as toluene at room temperature, and then the component (b) is contacted. Thereafter, the component (c) is contacted and the component (b) is further contacted, or the component (a) is suspended in a liquid aromatic hydrocarbon compound such as toluene at room temperature, and then a specific amount of the component A method of preparing the solid catalyst component (A) by bringing the component (b) into contact with each other after contacting (c) can be mentioned.

  Furthermore, as a more preferable preparation method of the solid catalyst component (A) for olefin polymerization used in the present invention, the following methods may be mentioned: For example, dialkoxy magnesium is converted into an aromatic hydrocarbon compound that is liquid at room temperature. A suspension is formed by suspending, and then titanium tetrachloride is contacted with this suspension at -20 to 100 ° C, preferably -10 to 70 ° C, more preferably -10 to 30 ° C, and 40 to The reaction is performed at 130 ° C, more preferably at 70 to 130 ° C. At this time, component (c) is contacted at −20 to 130 ° C. before or after contacting titanium tetrachloride with the above suspension to obtain a solid reaction product. After washing this solid reaction product with a liquid aromatic hydrocarbon compound at room temperature, titanium tetrachloride and 1 to 10 times, in the presence of the aromatic hydrocarbon compound, 40 to 130 ° C., more preferably A contact reaction is carried out at 70 to 130 ° C., followed by washing with a liquid hydrocarbon compound at room temperature to obtain a solid catalyst component (A) for olefin polymerization. In either case, the solid catalyst component (A) for olefin polymerization can be preliminarily contacted with an organoaluminum compound and an organosilicon compound, or an olefin.

  In the method for preparing the solid catalyst component (A) of the present invention, the ratio of the amounts of each compound used varies depending on the preparation method, and thus cannot be defined unconditionally. 5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the total amount of component (c) added is 0.1 to 10 mol, preferably 0.1 to 1 mol, More preferably, it is 0.1-0.3 mol.

(Description of olefin polymerization catalyst)
The catalyst for olefin polymerization of the present invention (hereinafter also simply referred to as “catalyst”) includes the solid catalyst component (A), the following general formula (2);
R ¹¹ _p AlQ _3-p (2)
(In the formula, R ¹¹ represents a hydrocarbyl group having 1 to 6 carbon atoms, and when there are a plurality thereof, they may be the same or different, and Q represents a hydrogen atom, a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom. P is a real number of 0 <p ≦ 3.) And an external electron donating compound (C).

  In the organoaluminum compound (B) represented by the general formula (2) (hereinafter also referred to simply as “component (B)”), Q represents a hydrogen atom or a halogen atom, and when Q is a halogen atom, An atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned. Examples of the component (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride. Triethylaluminum and triisobutylaluminum are particularly preferable. These organoaluminums can be used alone or in combination of two or more.

  In the catalyst for olefin polymerization of the present invention, examples of the external electron donating compound (hereinafter sometimes simply referred to as “component (C)”) include organic compounds containing an oxygen atom or a nitrogen atom. For example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds, especially Si—O—C bonds And an organosilicon compound having an Si—N—C bond.

Among the above components (C), as the organosilicon compound having a Si—O—C bond, the following general formula (3);
R ¹² _q Si (OR ¹³ ) _4-q (3)
(In the formula, R ¹² represents an alkyl group having 1 to ¹² carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, and an aromatic group having 6 to 15 carbon atoms. R ¹³ represents an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon number. A cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, which may be the same or different, and q is 0 ≦ q ≦ 3)).

Moreover, as an aminosilane compound which has a Si-NC bond among the said components (C), following General formula (4);
(R ¹⁴ R ¹⁵ N) _s SiR ¹⁶ _4-s (4)
(Wherein R ¹⁴ and R ¹⁵ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group, or a carbon number. R ¹⁴ and R ¹⁵ may be the same or different, and may be bonded to each other to form a ring, and R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, a vinyl group, C3-C12 alkenyl group, C1-C20 alkoxy group, vinyloxy group, C3-C20 alkenyloxy group, C3-C20 cycloalkyl group or cycloalkyloxy group, or C6-C6 an aryl group or an aryloxy group of 20, if R ¹⁶ is plural, R ¹⁶ is represented by from the same or different .s is an integer from 1 to 3.) An aminosilane compound is mentioned.

  Examples of the organosilicon compound of the general formula (3) and the aminosilane compound of the general formula (4) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, Alkylamino) alkoxysilane, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, A trialkyl (alkylamino) silane etc. are mentioned. Specifically, n-propyltriethoxysilane, cyclopentyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis (Ethylamino) methylethylsilane, bis (ethylamino) t-butylmethylsilane, bis ( Tilamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, Examples thereof include bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, and among these, n-propyltriethoxysilane, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxy are preferable. Silane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopente Rudimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroiso) Quinolino) dimethoxysilane, diethylaminotriethoxysilane.

  Among the ethers of component (C), 1,3 diether is preferable, and 9,9-bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are particularly preferable.

(Description of production method of olefin polymers)
In the method for producing an olefin polymer of the present invention, olefins are polymerized in the presence of the polymerization catalyst.

  In the method for producing an olefin polymer of the present invention, the olefins are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., and these olefins are one kind. Alternatively, two or more can be used in combination. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  In the formation of the catalyst, the use amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound of component (B) is a component. It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per 1 mol of titanium atom in (A). The external electron donating compound of component (C) is 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of component (B). Used in a range.

  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and the solid catalyst component (A) for olefin polymerization is further added. It is desirable to contact.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Further, in the present invention, when the olefin is polymerized using the olefin polymerization catalyst containing the solid catalyst component (A), the component (B), and the component (C) for olefin polymerization (also referred to as main polymerization), the catalyst. In order to further improve the activity, stereoregularity, particle properties of the polymer to be produced, etc., it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the respective components and monomers is arbitrary, but preferably, the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the olefin. After contacting the solid catalyst component (A) for homopolymerization, an olefin such as propylene and / or one or more other olefins are contacted. When the prepolymerization is performed by combining the component (C), the component (B) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the component (C) is contacted. A method of contacting an olefin such as propylene and / or one or other two or more olefins after contacting the solid catalyst component (A) for olefin polymerization is desirable.

  When olefins are polymerized in the presence of an olefin polymerization catalyst formed according to the present invention, the response to hydrogen is high, and the resulting polymer has a broad molecular weight distribution compared to when using conventional catalysts, In addition, the stereoregularity and yield of the polymer can be maintained at a high level.

(Example)
EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

<Preparation of solid catalyst component (A1)>
A mixed solution was formed by charging 34 ml of titanium tetrachloride and 50 ml of toluene into a 500 ml round bottom flask sufficiently substituted with nitrogen gas and equipped with a stirrer. Then formed with 20 g (0.175 mol) diethoxymagnesium, 70 ml toluene and 1.4 g (4.5 mmol) di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate. The suspension was added into the mixed solution maintained at a liquid temperature of −5 ° C. Thereafter, the liquid temperature was raised from −5 ° C. to 90 ° C. During the temperature increase, di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate was added in three portions at a convenient rate of 4.2 g (13.5 mmol). The reaction was conducted at 90 ° C. with stirring for 1 hour. After the stirring was stopped, the mixture was left to stand to remove the supernatant, and the resulting solid product was washed four times with 170 ml of toluene at 90 ° C., and 130 ml of toluene at normal temperature and 20 ml of titanium tetrachloride were newly added. The reaction was allowed to proceed with stirring for 15 minutes. After completion of the reaction, the supernatant was removed, 120 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was stirred at 90 ° C. for 15 minutes. After completion of the reaction, the supernatant was removed. After repeating the previous operation, it was washed 8 times with 130 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A1). When the titanium content in the solid catalyst component (A1) was measured, the total content of 2.9% by weight of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester was 11. It was 2% by weight.

<Formation and polymerization of polymerization catalyst (Z1)>
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) and the solid catalyst component (A) as titanium atoms 0.0026 mmol was charged to form the polymerization catalyst (Z1). Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. About the obtained polymer, molecular weight distribution by polymerization activity, melt flow rate (MFR, g-PP / 10 minutes), and gel permeation chromatography (GPC) was measured by the following method. The results are shown in Table 1.

(Polymerization activity)
The polymerization activity (kg-PP / g-cat) indicating the amount of polymer produced (F) kg per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.
Polymerization activity (kg-PP / g-cat) = product polymer (F) kg / solid catalyst component g / 1 hour

[Polymer melt flow rate (MFR)]
It measured according to ASTM D1238 and JIS K7210.

[Molecular weight distribution of polymer]
The molecular weight distribution of the polymer was determined by gel permeation chromatography (GPC) (GPCV2000 manufactured by Waters) under the following conditions: the weight average molecular weight Mw and the number average molecular weight Mn ratio Mw / Mn and Z average molecular weight The ratio Mz / Mw of Mz and weight average molecular weight Mw was evaluated.
Solvent: o-dichlorobenzene (ODCB)
Temperature: 140 ° C (SEC)
Column: Shodex GPC UT-806M
Sample concentration: 1 g / liter-ODCB (50 mg / 50 ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0 ml / min

<Preparation of solid catalyst component (A2)>
Instead of 1.4 g (4.5 mmol) of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate initially added to diethoxymagnesium at a temperature of −5 ° C., 0 The amount of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate added in the middle of the temperature increase was conveniently 4.2 g (13.5 mmol). The solid catalyst component (A2) was prepared in the same manner as in Example 1 except that 2.1 g (6.3 mmol) was used instead of 2). The titanium content in the obtained solid catalyst component (A2) is 3.2% by weight, and the total content of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester is 8.7% by weight. %Met.

<Formation and polymerization of polymerization catalyst (Z2)>
A polymerization catalyst (Z2) was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component (A2) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A3)>
Instead of 1.4 g (4.5 mmol) of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate initially added to diethoxymagnesium at a temperature of −5 ° C. The amount of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate added in the middle of the temperature increase was conveniently 4.2 g (13.5 mmol). The solid catalyst component (A3) was prepared in the same manner as in Example 1 except that the amount was changed to 8.4 g (27.0 mmol). The titanium content in the obtained solid catalyst component was 2.5% by weight, and the total content of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester was 13.4% by weight. It was.

<Formation and polymerization of polymerization catalyst (Z3)>
A polymerization catalyst (Z3) was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component (A3) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Formation and polymerization of polymerization catalyst (Z4)>
A polymerization catalyst (Z4) was synthesized and polymerized in the same manner as in Example 1 except that dicyclopentyldimethoxysilane (DCPDMS) was used instead of cyclohexylmethyldimethoxysilane (CMDMS). The results are shown in Table 1.

<Preparation of solid catalyst component (A5)>
Instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate, except that di-n-butyl 3,6-dichloro-1-cyclohexene-1,2-dicarboxylate was used. The solid catalyst component (A5) was prepared in the same manner as in Example 1. The titanium content in the obtained solid catalyst component (A5) was 3.0% by weight, and the total content of 3,6-dichloro-1-cyclohexene-1,2-dicarboxylic acid diester was 13.2% by weight. %Met.

<Formation and polymerization of polymerization catalyst (Z5)>
A polymerization catalyst (Z5) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A5) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A6)>
The procedure was carried out except that diethyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate was added in the same mole instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate. In the same manner as in Example 1, the solid catalyst component (A6) was prepared. The titanium content in the obtained solid catalyst component was 2.7% by weight, and the total content of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester was 12.5% by weight. It was.

<Formation and polymerization of polymerization catalyst (Z6)>
A polymerization catalyst (Z6) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A6) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Formation and polymerization of polymerization catalyst (Z7)>
A polymerization catalyst (Z7) was prepared in the same manner as in Example 1 except that the solid catalyst component (A6) was used instead of the solid catalyst component (A1), and dicyclopentyldimethoxysilane was used instead of cyclohexylmethyldimethoxysilane. ) Was synthesized and polymerized. The results are shown in Table 1.

<Formation and polymerization of polymerization catalyst (Z8)>
A polymerization catalyst (Z8) was synthesized and polymerized in the same manner as in Example 1 except that diethylaminotriethoxysilane (DEATES) was used instead of cyclohexylmethyldimethoxysilane (CMDMS). The results are shown in Table 1.

<Formation and polymerization of polymerization catalyst (Z9)>
A polymerization catalyst (Z9) was synthesized and polymerized in the same manner as in Example 1 except that dicyclopentylbis (ethylamino) silane (DCPEAS) was used instead of cyclohexylmethyldimethoxysilane (CMDMS). The results are shown in Table 1.

<Preparation of solid catalyst component (A10)>
Instead of using di-n-butyl 4,5-dimethyl-1-cyclohexene-1,2-dicarboxylate instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate Prepared a solid catalyst component (A10) in the same manner as in Example 1. The titanium content in the obtained solid catalyst component was 2.4% by weight, and the total content of 4,5-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester was 14.2% by weight. It was.

<Formation and polymerization of polymerization catalyst (Z10)>
A polymerization catalyst (Z10) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A10) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A11)>
Instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate, di-n-butyl 3,3,6,6-tetramethyl-1-cyclohexene-1,2-dicarboxylate was used. A solid catalyst component (A11) was prepared in the same manner as in Example 1 except that the same mole was used. The titanium content in the obtained solid catalyst component was 3.3% by weight, and the total content of 3,3,6,6-tetramethyl-1-cyclohexene-1,2-dicarboxylic acid diester was 10. It was 9% by weight.

<Formation and polymerization of polymerization catalyst (Z11)>
A polymerization catalyst (Z11) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A11) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A12)>
A mixed solution was formed by charging 34 ml of titanium tetrachloride and 50 ml of toluene into a 500 ml round bottom flask sufficiently substituted with nitrogen gas and equipped with a stirrer. The suspension formed using 20 g (0.175 mol) of diethoxymagnesium, 70 ml of toluene and 1.1 g (4.5 mmol) of dimethyl diisobutylmalonate was then kept at the liquid temperature of −5 ° C. Added in solution. Thereafter, the liquid temperature was raised from −5 ° C. to 90 ° C. During the temperature rising, di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate was added in portions in three portions, conveniently in an amount of 4.2 g (13.5 mmol) and added at 90 ° C. for 1 hour. The reaction was carried out with stirring. After the stirring was stopped, the mixture was left to stand to remove the supernatant, and the resulting solid product was washed four times with 170 ml of toluene at 90 ° C., and 130 ml of toluene at normal temperature and 20 ml of titanium tetrachloride were newly added. The reaction was allowed to proceed with stirring for 15 minutes. After completion of the reaction, the supernatant was removed, 120 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was stirred at 90 ° C. for 15 minutes. After completion of the reaction, the supernatant was removed. After repeating the previous operation, it was washed 8 times with 130 ml of n-heptane at 40 ° C. to obtain a solid catalyst component (A12). The titanium content in the solid catalyst component is 3.1% by weight, and the content of dimethyl diisobutylmalonate and the total content of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester are respectively 2.5 wt% and 8.2 wt%.

<Formation and polymerization of polymerization catalyst (Z12)>
A polymerization catalyst (Z12) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A12) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A13)>
A solid catalyst component (A13) was prepared in the same manner as in Example 12 except that the same molar amount of diethyl benzylidenemalonate was used instead of dimethyl diisobutylmalonate. The titanium content in the obtained solid catalyst component was 2.7% by weight, the content of diethyl benzylidene malonate and the total content of 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester were , 1.7% by weight and 8.9% by weight, respectively.

<Formation and polymerization of polymerization catalyst (Z13)>
A polymerization catalyst (Z13) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A13) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

<Preparation of solid catalyst component (A14)>
A solid catalyst component (A14) was prepared in the same manner as in Example 12 except that the same mole of (2-ethoxyethyl) ethyl carbonate was used instead of dimethyl diisobutylmalonate. The obtained solid catalyst component had a titanium content of 2.7% by weight, a content of (2-ethoxyethyl) ethyl carbonate and 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylic acid diester. The total content was 1.7% by weight and 8.9% by weight, respectively.

<Formation and polymerization of polymerization catalyst (Z14)>
A polymerization catalyst (Z14) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (A14) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

(Comparative Example 1)
<Preparation of solid catalyst component (a1)>
Example 1 except that instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate, the same molar amount of di-n-butyl 1-cyclohexene-1,2-dicarboxylate was used. The solid catalyst component (a1) was prepared in the same manner as described above. The titanium content in the obtained solid catalyst component was 2.8% by weight, and the total content of 1-cyclohexene-1,2-dicarboxylic acid diester was 14.1 wt%.

<Formation and polymerization of polymerization catalyst (z1)>
A polymerization catalyst (z1) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (a1) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

(Comparative Example 2)
<Preparation of solid catalyst component (a2)>
The solid catalyst component (a2) was obtained in the same manner as in Example 1 except that the same mole of di-n-butyl phthalate was used instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate. ) Was prepared. The titanium content in the obtained solid catalyst component was 3.0% by weight, and the total content of phthalic acid diester was 13.5% by weight.

<Formation and polymerization of polymerization catalyst (z2)>
A polymerization catalyst (z2) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (a2) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

(Comparative Example 3)
<Preparation of solid catalyst component (a3)>
Instead of using di-isobutyl 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylate instead of di-n-butyl 3,6-dimethyl-1-cyclohexene-1,2-dicarboxylate, A solid catalyst component (a3) was prepared in the same manner as in Example 1. The titanium content in the solid catalyst component was measured to be 2.3% by weight, and the total content of 3-methyl-6-n-propylcyclohexane-1,2-dicarboxylic acid diester was 15.3% by weight. %Met.

<Formation and polymerization of polymerization catalyst (z3)>
A polymerization catalyst (z3) was synthesized and polymerized in the same manner as in Example 1 except that the solid catalyst component (a3) was used instead of the solid catalyst component (A1). The results are shown in Table 1.

  In Table 1, “CMDMS” means cyclohexylmethyldimethoxysilane, “DCPDMS” means dicyclopentyldimethoxysilane, “DEATES” means diethylaminotriethoxysilane, and “DCPEAS” means dicyclopentylbis (ethylamino) silane. .

  From the results in Table 1, the solid catalyst component and the polymerization catalyst containing the compound represented by the above general formula (1) are compared with the case where a conventional catalyst is used when polymerizing olefins using them. The polymerization activity is high, and the molecular weight distribution of the obtained polymer is wide. Moreover, it turns out that the hydrogen response at the time of superposition | polymerization is high and molding processability is favorable.

Claims (7)

Titanium, magnesium, halogen and the following general formula (1);

(In the formula, R ¹ and R ² are each a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 20 carbon atoms, or branched. Alkenyl group, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, branched halogen-substituted alkyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms Represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be the same or different from each other, and R ^{3 to} R ¹⁰ are each a hydrogen atom, a halogen atom, or a linear alkyl group having 1 to 20 carbon atoms. Group, branched alkyl group having 3 to 20 carbon atoms, vinyl group, linear alkenyl group or branched alkenyl group having 3 to 20 carbon atoms, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms Branched halogen substituted al Group, straight chain halogen-substituted alkenyl group having 2 to 20 carbon atoms, branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, carbon A halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, and a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms. , May be the same or different, and at least two of R ^{3 to} R ¹⁰ are a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, carbon C3-C20 linear alkenyl group or branched alkenyl group, C1-C20 linear halogen-substituted alkyl group, C3-C20 branched halogen-substituted alkyl group, C2-C2 0 linear halogen-substituted alkenyl groups, branched halogen-substituted alkenyl groups having 3 to 20 carbon atoms, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, halogen substitution having 3 to 20 carbon atoms A cycloalkyl group, a halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 24 carbon atoms, or a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms. A solid catalyst component for olefin polymerization, comprising: In the general formula (1), among R ^{3 to} R ¹⁰ , 2 or more and 4 or less are a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, or a vinyl group. A linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, a branched halogen-substituted alkyl group having 3 to 12 carbon atoms, and a straight chain having 3 to 12 carbon atoms. Chain halogen-substituted alkenyl group or branched halogen-substituted alkenyl group, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms, halogen-substituted cycloalkyl group having 3 to 12 carbon atoms, 3 to 12 carbon atoms 2. The solid catalyst component for olefin polymerization according to claim 1, which is a halogen-substituted cycloalkenyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. In the general formula (1), R ³ and R ⁹ or R ⁵ and R ⁷ are each a halogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, carbon The linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Solid catalyst component for polymerizing olefins. The solid catalyst component for olefin polymerization according to any one of claims 1 to 3,
The following general formula (2);
R ¹¹ _p AlQ _3-p (2)
(In the formula, R ¹¹ represents a hydrocarbyl group having 1 to 6 carbon atoms, and when there are a plurality thereof, they may be the same or different, and Q represents a hydrogen atom, a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom. And p is a real number of 0 <p ≦ 3.) An olefin polymerization catalyst characterized by being formed from an organoaluminum compound represented by the following formula: The external electron donating compound is represented by the following general formula (3):
R ¹² _q Si (OR ¹³ ) _4-q (3)
(In the formula, R ¹² represents an alkyl group having 1 to ¹² carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, and an aromatic group having 6 to 15 carbon atoms. an aromatic hydrocarbon group having a hydrocarbon group or a substituted group, if R ¹² there are a plurality, R ¹² together to the plurality of the same or may be different .R ¹³ is from 1 to 4 carbon atoms An alkyl group, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms or a fragrance having 7 to 12 carbon atoms In the case where a plurality of R ¹³ are present, the plurality of R ¹³ may be the same or different, and q is an integer of 0 ≦ q ≦ 3. Organosilicon compound And the general formula (4);
(R ¹⁴ R ¹⁵ N) _s SiR ¹⁶ _4-s (4)
(Wherein R ¹⁴ and R ¹⁵ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkenyl group, or a carbon number. R ¹⁴ and R ¹⁵ may be the same or different, and may be bonded to each other to form a ring, and R ¹⁶ is an alkyl group having 1 to 20 carbon atoms, a vinyl group, C3-C12 alkenyl group, C1-C20 alkoxy group, vinyloxy group, C3-C20 alkenyloxy group, C3-C20 cycloalkyl group or cycloalkyloxy group, or C6-C6 an aryl group or an aryloxy group of 20, if R ¹⁶ is plural, R ¹⁶ is represented by from the same or different .s is an integer from 1 to 3.) 5. The olefin polymerization catalyst according to claim 4, wherein the catalyst is one or more selected from aminosilane compounds. The external electron donating compound is represented by the following general formula (5):
R ¹⁷ OCH ₂ CR ¹⁸ R ¹⁹ CH ₂ OR ²⁰ (5)
(Wherein R ¹⁸ and R ¹⁹ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkenyl group. , An aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or 2 carbon atoms Represents a dialkylamino group having ˜12, which may be the same or different and may be bonded to each other to form a ring, R ¹⁷ and R ²⁰ are each an alkyl group having 1 to 12 carbon atoms, a vinyl group, 3 carbon atoms; -12 alkenyl group, cycloalkyl group having 3 to 6 carbon atoms, aromatic hydrocarbon group having 6 to 12 carbon atoms, halogen-substituted aromatic hydrocarbon group or a substituted carbon group having 7 to 12 carbon atoms 5. The catalyst for olefin polymerization according to claim 4, which is a diether compound represented by the following formula:   A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 4 to 6.

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