JP6054690B2 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

  The present invention provides a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, which can obtain an olefin polymer having an appropriate molecular weight distribution in a high yield while maintaining high polymerization activity and stereoregularity. The present invention relates to a method for producing an olefin polymer.

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

  For example, JP-A-57-63310 (Patent Document 1) discloses a solid titanium catalyst component on which a specific electron donor is supported, an organoaluminum compound as a promoter component, and at least one Si-OR ( In the formula, it is described that excellent polymerization activity and stereospecificity are exhibited when a silicon compound having R is a hydrocarbon group.

  As the specific electron donating component, JP-A-58-83006 (Patent Document 2) discloses a phthalate ester.

  However, the solid catalyst component carrying these electron donors has room for improvement in both polymerization activity and stereoregularity. On the other hand, as another trial, Japanese Patent Publication No. 2005-539108 (Patent Document 3) discloses a solid catalyst component using a succinate ester, International Publication No. 2006/077945 (Patent Document 4), International Publication No. 2011/071237. The publication (Patent Document 5) discloses a solid catalyst component using a cyclic ester having a structure similar to that of a succinic acid ester, and an olefin polymer having a wide molecular weight distribution can be obtained from these solid catalyst components. It is shown.

  Japanese Patent Application Laid-Open No. 2005-187550 (Patent Document 6) discloses a technique using 1,3-diether as an internal electron donor or an external electron donor. From such a catalyst system, an olefin having a narrow molecular weight distribution is disclosed. Similar polymers have been shown to be obtained.

JP 57-63310 A JP 58-83006 A JP 2005-539108 A International Publication No. 2006/077945 International Publication No. 2011/071237 JP 2005-187550 A

  Catalysts used for stereoregular polymerization of olefins must have a balance of various polymerization performances such as activity, stereoregularity, molecular weight distribution, sustained activity, MFR controllability (hydrogen responsiveness), and bulk density. Because the required performance varies depending on the application, various solid catalyst components having different characteristics and catalysts are required. When solid catalyst components such as the above prior art are used, the activity or stereoregularity is insufficient, or some solid catalyst components can be produced only with a polymer having a narrow molecular weight distribution or a polymer having a wide molecular weight distribution. However, it has a problem that it is difficult to control the molecular weight distribution of the resulting olefin polymer in an appropriate range. The molecular weight distribution of a polymer used for general purposes is required to be controllable, for example, in the range of about 4 to 6 in terms of Mw / Mn value, and other performance is excellent in that range, that is, crystallinity of a certain degree or more. It is said that a solid catalyst component exhibiting a high polymerization activity to some extent is most practical.

  Accordingly, an object of the present invention is to meet the above-mentioned needs by providing a novel polymer having a high Mw / Mn molecular weight distribution that does not impair moldability and high polymerization activity capable of obtaining a highly stereoregular olefin polymer. It is an object to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the same.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained solid titanium catalyst component (I) containing cyclic cycloalkene dicarboxylic acid diesters containing titanium, magnesium, halogen and a specific aromatic ring. The olefin polymerization catalyst as an essential component has high stereoregularity and high polymerization activity, and the molecular weight distribution is 4 to 6 in terms of Mw / Mn value depending on the steric structure including the substituent of the above compound. The present inventors have found that it can be controlled within a range, and have completed the present invention.

（式中、Ｒ^１〜Ｒ^７は、水素原子、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、結合末端が炭素原子である炭素数２〜２４の窒素原子含有炭化水素基、結合末端が炭素原子である炭素数２〜２４の酸素原子含有炭化水素基、結合末端が炭素原子である炭素数２〜２４のリン含有炭化水素基、または炭素数１〜２４のケイ素含有炭化水素基を示し、同一でも異なっていてもよく、但し、Ｒ^１およびＲ^２が水素原子であるもの、該炭素数２〜２４の窒素原子含有炭化水素基は、結合末端がＣ＝Ｎ基であるもの、該炭素数２〜２４の酸素原子含有炭化水素基は、結合末端がカルボニル基であるもの、該炭素数２〜２４のリン含有炭化水素基は、結合末端がＣ＝Ｐ基であるものをそれぞれ除く。Ｒ^３〜Ｒ^７は、隣接するものと環を形成してもよい。）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);

^(Wherein, R 1 to R ⁷ is a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, branched alkyl group having 3 to 20 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 20 carbon atoms Or a branched alkenyl group, a C1-C20 linear halogen-substituted alkyl group, a C3-C20 branched halogen-substituted alkyl group, a C2-C20 linear halogen-substituted alkenyl group, a C3-C20 Branched halogen-substituted alkenyl groups, cycloalkyl groups having 3 to 20 carbon atoms, cycloalkenyl groups having 3 to 20 carbon atoms, halogen-substituted cycloalkyl groups having 3 to 20 carbon atoms, halogen-substituted cycloalkenyl groups having 3 to 20 carbon atoms An aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms whose bond terminal is a carbon atom, and a bond end An oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms, wherein the bond terminal is a carbon atom, a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 24 carbon atoms. Which may be the same or different, provided that R ¹ and R ² are hydrogen atoms, the nitrogen atom-containing hydrocarbon group having ² to 24 carbon atoms is one in which the bond terminal is a C═N group, The oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms has a carbonyl group at the bonding end, and the phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms has a C = P group at the bonding end. And R ^{3 to} R ⁷ may form a ring with the adjacent ones.) And provide a solid catalyst component for olefin polymerization characterized by containing a compound represented by the following formula:

The present invention also provides (I) the solid catalyst component, (II) the following general formula (2);
R ⁸ _p AlQ _3-p (2)
(In the formula, R ⁸ 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. Wherein p is a real number of 0 <p ≦ 3.) And (III) an olefin polymerization catalyst characterized by being formed from an external electron donating compound It is.

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

  By using the solid catalyst component for olefin polymerization and the catalyst for olefin polymerization of the present invention, an olefin polymer having a high stereoregularity and an appropriate molecular weight distribution that is neither wide nor narrow can be obtained in a high yield. Can do.

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 “component (I)”) is represented by the above general formula (1) as magnesium, titanium, halogen, and an electron-donating compound. An electron donating compound (hereinafter sometimes simply referred to as “component (A)”) as an essential component.

  Examples of the halogen include fluorine, chlorine, bromine and iodine atoms. Among them, chlorine, bromine and iodine are preferable, and chlorine and iodine are particularly preferable.

Examples of the linear alkyl group having 1 to 20 carbon atoms of R ^{1 to} R ⁷ in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, Examples include 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 in said R < ¹ > -R < ⁷ >, for example, the alkyl which has secondary carbon or tertiary carbon, such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, neopentyl group, etc. Groups. Preferably it is a C3-C12 branched alkyl group.

Examples of the linear alkenyl group having 3 to 20 carbon atoms in the ^R 1 to R ^7, allyl, 3-butenyl, 4-hexenyl, 5-hexenyl, 7-octenyl, 10-dodecenyl Etc. Preferably it is a C3-C12 linear alkenyl group. Examples of the branched alkenyl group having 3 to 20 carbon atoms include isopropenyl group, isobutenyl group, isopentenyl group, 2-ethyl, 3-hexenyl group and the like. A branched alkenyl group having 3 to 12 carbon atoms is preferred.

Examples of the linear halogen-substituted alkyl group having 1 to 20 carbon atoms in R ^{1 to} R ⁷ include a halogenated methyl group, a halogenated ethyl group, a halogenated n-propyl group, and a halogenated n-butyl group. Halogenated n-pentyl group, halogenated n-hexyl group, halogenated n-pentyl group, halogenated n-octyl group, halogenated nonyl group, halogenated decyl group, halogen substituted undecyl group, halogen substituted dodecyl group, etc. Can be mentioned. Preferably, it is a C1-C12 linear halogen-substituted alkyl group. 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.

Examples of the linear halogen-substituted alkenyl group having 2 to 20 carbon atoms in R ^{1 to} R ⁷ include a 2-halogenated vinyl group, a 3-halogenated allyl group, a 3-halogenated-2-butenyl group, 4 -Halogenated-3-butenyl group, perhalogenated-2-butenyl group, 6-halogenated-4-hexenyl group, 3-trihalogenated methyl-2-propenyl group and the like. A halogen-substituted alkenyl group having 2 to 12 carbon atoms is preferred. Examples of the branched halogen-substituted alkenyl group having 3 to 20 carbon atoms include 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 can be mentioned. A branched halogen-substituted alkenyl group having 3 to 12 carbon atoms is preferred.

Further, the cycloalkyl group having 3 to 20 carbon atoms in the R ¹ to R ^7, cyclopropyl group, cyclobutyl group, cyclopentyl group, tetramethyl cyclopentyl group, a cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group , Cyclononyl group, cyclodecyl group, butylcyclopentyl group and the like. Preferably it is a C3-C12 cycloalkyl group. Moreover, as a C3-C20 cycloalkenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a norbornene group, etc. are mentioned. Preferably it is a C3-C12 cycloalkenyl group.

Examples of the halogen-substituted cycloalkyl group having 3 to 20 carbon atoms in R ^{1 to} R ⁷ include a halogen-substituted cyclopropyl group, a halogen-substituted cyclobutyl group, a halogen-substituted cyclopentyl group, a halogen-substituted trimethylcyclopentyl group, a halogen-substituted cyclohexyl group, Examples include halogen-substituted 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.

Examples of the halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms in R ^{1 to} R ⁷ include 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. Examples include a denenyl group, a halogen-substituted methylcyclohexenyl group, a halogen-substituted cycloheptenyl group, a halogen-substituted cyclooctenyl group, a halogen-substituted cyclononenyl group, a halogen-substituted cyclodecenyl group, and a halogen-substituted butylcyclopentenyl. A halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms is preferred.

Examples of the aromatic hydrocarbon group having 6 to 24 carbon atoms in R ^{1 to} R ⁷ include a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a benzyl group, a 1-phenylethyl group, and 2-phenyl. Examples include ethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group, 1,8-dimethylnaphthyl group and the like. Preferably it is a C6-C12 aromatic hydrocarbon group.

Examples of the halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms in R ^{1 to} R ⁷ include a halogenated phenyl group, a halogenated methylphenyl group, a trihalogenated methylphenyl group, a perhalogenated benzyl group, a perhalogenated group. Examples thereof include a halogenated phenyl group, 2-phenyl, 2-halogenated ethyl group, perhalogenated naphthyl group, 4-phenyl, 2,3-dihalogenated butyl group and the like. A halogen-substituted aromatic hydrocarbon group having 6 to 12 carbon atoms is preferred.

In the halogen substituted alkyl group, halogen substituted alkenyl group, halogen substituted cycloalkyl group, halogen substituted cycloalkenyl group, and halogen substituted aromatic hydrocarbon group in R ^{1 to} R ⁷ , the halogen species include fluorine, chlorine, Examples thereof include bromine and iodine, preferably fluorine, chlorine or bromine.

Further, in R ^{1 to} R ⁷ , a nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms in which the bond terminal is a carbon atom (however, for R ¹ and R ² , the bond terminal is a C═N group) Are, for example, methylaminomethyl group, dimethylaminomethyl group, ethylaminomethyl group, diethylaminomethyl group, propylaminomethyl group, dipropylaminomethyl group, methylaminoethyl group, dimethylaminoethyl group, ethyl Aminoethyl group, diethylaminoethyl group, propylaminoethyl group, dipropylaminoethyl group, butylaminoethyl group, dibutylaminoethyl group, pentylaminoethyl group, dipentylaminoethyl group, hexylaminoethyl group, hexylmethylaminoethyl group, Heptylmethylaminoethyl group, diheptylamino Alkylaminoalkyl groups such as methyl, octylmethylaminomethyl, dioctylaminoethyl, nonylaminomethyl, dinonylaminomethyl, decylaminomethyl, didecylamino, cyclohexylaminomethyl, and dicyclohexylaminomethyl; phenyl Arylaminoalkyl groups or alkylarylaminoalkyl groups such as aminomethyl group, diphenylaminomethyl group, ditolylaminomethyl group, dinaphthylaminomethyl group, methylphenylaminoethyl group; polycyclic aminoalkyl group; anilino group, dimethylamino Amino group-containing aromatic hydrocarbon group such as phenyl group, bisdimethylaminophenyl group; iminoal such as methyliminomethyl, ethyliminoethyl, propylimino, butylimino, phenylimino A kill group etc. are mentioned. Preferably it is a C2-C12 nitrogen atom containing hydrocarbon group. Note that the binding end ^refers to the atom or group having a carbon ^{side R} 3 to R ⁷ are attached at the oxygen atom ^side, R 3 to R ^{7 which R} 1, ^{R 2} are attached at R 1, ^{R 2} .

Further, in the R ¹ to R ^7, binding end an oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms is a carbon atom (provided that the R ¹ and R ^2, except for those binding end is a carbonyl group ) For example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, isopropoxymethyl group, isobutoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, isopropoxy Ether group-containing hydrocarbon groups such as ethyl group and isobutoxyethyl group; aryloxyalkyl groups such as phenoxymethyl group, methylphenoxymethyl group, dimethylphenoxymethyl group and naphthoxymethyl group; methoxyphenyl group, ethoxyphenyl group and the like An alkoxyaryl group; acetoxymethyl group And the like. Preferably it is a C2-C12 oxygen atom containing hydrocarbon group. Note that the binding end ^refers to the atom or group having a carbon ^{side R} 3 to R ⁷ are attached at the oxygen atom ^side, R 3 to R ^{7 which R} 1, ^{R 2} are attached at R 1, ^{R 2} .

Further, in R ^{1 to} R ⁷ , a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms in which the bond terminal is a carbon atom (provided that R ¹ and R ² are those in which the bond terminal is a C═P group). (Excluding dimethylphosphinemethyl group, dibutylphosphinomethyl group, dicyclohexylphosphinomethyl group, dimethylphosphineethyl group, dibutylphosphinoethyl group, dicyclohexylphosphinoethyl group, etc.); Examples thereof include diarylphosphinoalkyl groups such as phosphinomethyl group and ditolylphosphinomethyl group; phosphino group-substituted aryl groups such as dimethylphosphinophenyl group and diethylphosphinophenyl group. A phosphorus-containing hydrocarbon group having 2 to 12 carbon atoms is preferred. Note that the binding end ^refers to the atom or group having a carbon ^{side R} 3 to R ⁷ are attached at the oxygen atom ^side, R 3 to R ^{7 which R} 1, ^{R 2} are attached at R 1, ^{R 2} .

Examples of the silicon-containing hydrocarbon group having 1 to 24 carbon atoms in R ^{1 to} R ⁷ include a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxyalkyl group, a hydrocarbon-substituted silylalkyl group, and a hydrocarbon-substituted silylaryl. Specific examples include hydrocarbon substitution such as phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl, etc. Silyl group; siloxy hydrocarbon group such as trimethylsiloxymethyl group, trimethylsiloxyethyl group, trimethylsiloxyphenyl group, hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; silicon-substituted alkyl group such as trimethylsilylmethyl; Like silicon-substituted aryl group such as trimethyl silyl phenyl and the like. Preferably, it is a C1-C12 silicon-containing hydrocarbon group.

Particularly preferred groups of R ^{1 to} R ⁷ 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, and a linear alkenyl having 3 to 12 carbon atoms. Group, 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, linear halogen-substituted alkenyl group having 3 to 12 carbon atoms Group, branched halogen-substituted alkenyl group having 3 to 12 carbon atoms, cycloalkyl group having 4 to 12 carbon atoms, cycloalkenyl group having 4 to 12 carbon atoms, halogen-substituted cycloalkyl group having 4 to 12 carbon atoms, and 4 to 4 carbon atoms 12 halogen-substituted cycloalkenyl groups or C 6-12 aromatic hydrocarbon groups. However, R ¹ and R ² exclude a hydrogen atom.

More preferable groups of R ¹ and R ² are a linear alkyl group having 1 to 6 carbon atoms and a branched alkyl group having 3 to 6 carbon atoms, and more preferable groups of R ^{3 to} R ⁷ are a hydrogen atom, C1-C6 linear alkyl group, C3-C6 branched alkyl group, C4-C6 cycloalkyl group, C4-C6 cycloalkenyl group, or C6-C12 aromatic It is a hydrocarbon group.

  Preferred specific examples of the component (A) represented by the general formula (1) include dimethyl indene-1,2-dicarboxylate, diethyl indene-1,2-dicarboxylate, and diene-1,2-dicarboxylic acid. N-propyl, indene-1,2-dicarboxylate diisopropyl, indene-1,2-dicarboxylate di-n-butyl, indene-1,2-dicarboxylate diisobutyl, indene-1,2-dicarboxylate di-t -Butyl, indene-1,2-dicarboxylic acid di-n-pentyl, indene-1,2-dicarboxylic acid di-n-hexyl, indene-1,2-dicarboxylic acid di-n-octyl, indene-1,2 -Di-n-decyl dicarboxylate, dicyclohexyl indene-1,2-dicarboxylate, diphenyl indene-1,2-dicarboxylate,

  Dimethyl 3-methylindene-1,2-dicarboxylate, diethyl 3-methylindene-1,2-dicarboxylate, di-n-propyl 3-methylindene-1,2-dicarboxylate, 3-methylindene-1, 2-dicarboxylic acid diisopropyl, 3-methylindene-1,2-dicarboxylic acid di-n-butyl, 3-methylindene-1,2-dicarboxylic acid diisobutyl, 3-methylindene-1,2-dicarboxylic acid di-t -Butyl,

  4-methylindene-1,2-dicarboxylic acid dimethyl, 4-methylindene-1,2-dicarboxylic acid diethyl, 4-methylindene-1,2-dicarboxylic acid di-n-propyl, 4-methylindene-1, 2-dicarboxylic acid diisopropyl, 4-methylindene-1,2-dicarboxylic acid di-n-butyl, 4-methylindene-1,2-dicarboxylic acid diisobutyl, 4-methylindene-1,2-dicarboxylic acid di-t -Butyl,

  Dimethyl 5-methylindene-1,2-dicarboxylate, diethyl 5-methylindene-1,2-dicarboxylate, di-n-propyl 5-methylindene-1,2-dicarboxylate, 5-methylindene-1, 2-dicarboxylate diisopropyl, 5-methylindene-1,2-dicarboxylate di-n-butyl, 5-methylindene-1,2-dicarboxylate diisobutyl, 5-methylindene-1,2-dicarboxylate di-t -Butyl,

  Dimethyl 6-methylindene-1,2-dicarboxylate, diethyl 6-methylindene-1,2-dicarboxylate, di-n-propyl 6-methylindene-1,2-dicarboxylate, 6-methylindene-1, 2-dicarboxylic acid diisopropyl, 6-methylindene-1,2-dicarboxylic acid di-n-butyl, 6-methylindene-1,2-dicarboxylic acid diisobutyl, 6-methylindene-1,2-dicarboxylic acid di-t -Butyl,

  Dimethyl 7-methylindene-1,2-dicarboxylate, diethyl 7-methylindene-1,2-dicarboxylate, di-n-propyl 7-methylindene-1,2-dicarboxylate, 7-methylindene-1, 2-dicarboxylic acid diisopropyl, 7-methylindene-1,2-dicarboxylic acid di-n-butyl, 7-methylindene-1,2-dicarboxylic acid diisobutyl, 7-methylindene-1,2-dicarboxylic acid di-t -Butyl,

  4-ethylindene-1,2-dicarboxylate dimethyl, 4-n-propylindene-1,2-dicarboxylate dimethyl, 4-isopropylindene-1,2-dicarboxylate dimethyl, 4-n-butylindene-1, Dimethyl 2-dicarboxylate, dimethyl 4-isobutylindene-1,2-dicarboxylate, dimethyl 4-t-butylindene-1,2-dicarboxylate, dimethyl 4-phenylindene-1,2-dicarboxylate, 4-cyclohexyl Dimethyl indene-1,2-dicarboxylate,

  4-ethylindene-1,2-dicarboxylate diethyl, 4-n-propylindene-1,2-dicarboxylate diethyl, 4-isopropylindene-1,2-dicarboxylate diethyl, 4-n-butylindene-1, Diethyl 2-dicarboxylate, diethyl 4-isobutylindene-1,2-dicarboxylate, diethyl 4-t-butylindene-1,2-dicarboxylate, diethyl 4-phenylindene-1,2-dicarboxylate, 4-cyclohexyl Diethyl indene-1,2-dicarboxylate,

  Dimethyl 3-ethylindene-1,2-dicarboxylate, dimethyl 3-n-propylindene-1,2-dicarboxylate, dimethyl 3-isopropylindene-1,2-dicarboxylate, 3-n-butylindene-1, Dimethyl 2-dicarboxylate, dimethyl 3-isobutylindene-1,2-dicarboxylate, dimethyl 3-t-butylindene-1,2-dicarboxylate, dimethyl 3-phenylindene-1,2-dicarboxylate, 3-cyclohexyl Dimethyl indene-1,2-dicarboxylate,

  Diethyl 3-ethylindene-1,2-dicarboxylate, diethyl 3-n-propylindene-1,2-dicarboxylate, diethyl 3-isopropylindene-1,2-dicarboxylate, 3-n-butylindene-1, Diethyl 2-dicarboxylate, diethyl 3-isobutylindene-1,2-dicarboxylate, diethyl 3-t-butylindene-1,2-dicarboxylate, diethyl 3-phenylindene-1,2-dicarboxylate, 3-cyclohexyl Diethyl indene-1,2-dicarboxylate,

  Dimethyl 3,4-dimethylindene-1,2-dicarboxylate, dimethyl 3,5-dimethylindene-1,2-dicarboxylate, dimethyl 3,6-dimethylindene-1,2-dicarboxylate, 3,7-dimethyl Dimethyl indene-1,2-dicarboxylate, dimethyl 4,5-dimethylindene-1,2-dicarboxylate, dimethyl 4,6-dimethylindene-1,2-dicarboxylate, 4,7-dimethylindene-1,2 Dimethyl dicarboxylate, dimethyl 5,6-dimethylindene-1,2-dicarboxylate, dimethyl 5,7-dimethylindene-1,2-dicarboxylate, dimethyl 6,7-dimethylindene-1,2-dicarboxylate,

  Dimethyl 3,4,5-trimethylindene-1,2-dicarboxylate, dimethyl 3,4,6-trimethylindene-1,2-dicarboxylate, dimethyl 3,4,7-trimethylindene-1,2-dicarboxylate Dimethyl 3,5,6-trimethylindene-1,2-dicarboxylate, dimethyl 3,5,7-trimethylindene-1,2-dicarboxylate, 3,6,7-trimethylindene-1,2-dicarboxylic acid Dimethyl,

  Dimethyl 4,5,6-trimethylindene-1,2-dicarboxylate, dimethyl 4,5,7-trimethylindene-1,2-dicarboxylate, dimethyl 4,6,7-trimethylindene-1,2-dicarboxylate Dimethyl 5,6,7-trimethylindene-1,2-dicarboxylate,

  Dimethyl 3,4,5,6-tetramethylindene-1,2-dicarboxylate, dimethyl 3,4,5,7-tetramethylindene-1,2-dicarboxylate, 4,5,6,7-tetramethyl Dimethyl indene-1,2-dicarboxylate, dimethyl 4,4,5,6,7-pentamethylindene-1,2-dicarboxylate,

  Diethyl 3,4-dimethylindene-1,2-dicarboxylate, diethyl 3,5-dimethylindene-1,2-dicarboxylate, diethyl 3,6-dimethylindene-1,2-dicarboxylate, 3,7-dimethyl Diethyl indene-1,2-dicarboxylate, diethyl 4,5-dimethylindene-1,2-dicarboxylate, diethyl 4,6-dimethylindene-1,2-dicarboxylate, 4,7-dimethylindene-1,2 -Diethyl dicarboxylate, diethyl 5,6-dimethylindene-1,2-dicarboxylate, diethyl 5,7-dimethylindene-1,2-dicarboxylate, diethyl 6,7-dimethylindene-1,2-dicarboxylate,

  Diethyl 3,4,5-trimethylindene-1,2-dicarboxylate, diethyl 3,4,6-trimethylindene-1,2-dicarboxylate, diethyl 3,4,7-trimethylindene-1,2-dicarboxylate 3,5,6-trimethylindene-1,2-dicarboxylic acid diethyl, 3,5,7-trimethylindene-1,2-dicarboxylic acid diethyl, 3,6,7-trimethylindene-1,2-dicarboxylic acid Diethyl,

  Diethyl 4,5,6-trimethylindene-1,2-dicarboxylate, diethyl 4,5,7-trimethylindene-1,2-dicarboxylate, diethyl 4,6,7-trimethylindene-1,2-dicarboxylate , Diethyl 5,6,7-trimethylindene-1,2-dicarboxylate,

  Diethyl 3,4,5,6-tetramethylindene-1,2-dicarboxylate, diethyl 3,4,5,7-tetramethylindene-1,2-dicarboxylate, 4,5,6,7-tetramethyl Examples include diethyl indene-1,2-dicarboxylate, diethyl 3,4,5,6,7-pentamethylindene-1,2-dicarboxylate, and the like. In addition, the compound represented by General formula (1) can also be used individually or in combination of 2 or more types.

  Among the compounds of the general formula (1), particularly preferred are dimethyl indene-1,2-dicarboxylate, diethyl indene-1,2-dicarboxylate, di-n-propyl indene-1,2-dicarboxylate, and indene. Di-n-butyl-1,2-dicarboxylate, diisobutyl indene-1,2-dicarboxylate, dimethyl 4-methylindene-1,2-dicarboxylate, diethyl 4-methylindene-1,2-dicarboxylate, 4 -Methylindene-1,2-dicarboxylic acid di-n-propyl, 4-methylindene-1,2-dicarboxylic acid di-n-butyl, 4-methylindene-1,2-dicarboxylic acid diisobutyl, 5-methylindene Dimethyl-1,2-dicarboxylate, diethyl 5-methylindene-1,2-dicarboxylate, 5-methylindene-1,2- Di-n-propyl carboxylate, di-n-butyl 5-methylindene-1,2-dicarboxylate, diisobutyl 5-methylindene-1,2-dicarboxylate, dimethyl 6-methylindene-1,2-dicarboxylate 6-methylindene-1,2-dicarboxylate, 6-methylindene-1,2-dicarboxylate di-n-propyl, 6-methylindene-1,2-dicarboxylate di-n-butyl, Methylindene-1,2-dicarboxylate diisobutyl, 7-methylindene-1,2-dicarboxylate dimethyl, 7-methylindene-1,2-dicarboxylate diethyl, 7-methylindene-1,2-dicarboxylate di- n-propyl, 7-methylindene-1,2-dicarboxylic acid di-n-butyl, 7-methylindene-1,2-dicarboxylic acid dii Butyl, dimethyl 4-ethylindene-1,2-dicarboxylate, dimethyl 4-n-propylindene-1,2-dicarboxylate, dimethyl 4-isopropylindene-1,2-dicarboxylate, 4-n-butylindene Dimethyl 1,2-dicarboxylate, dimethyl 4-isobutylindene-1,2-dicarboxylate, dimethyl 4-t-butylindene-1,2-dicarboxylate, dimethyl 4-phenylindene-1,2-dicarboxylate, 4 -Dimethyl cyclohexylindene-1,2-dicarboxylate, diethyl 4-ethylindene-1,2-dicarboxylate, diethyl 4-n-propylindene-1,2-dicarboxylate, 4-isopropylindene-1,2-dicarboxylic acid Diethyl acetate, diethyl 4-n-butylindene-1,2-dicarboxylate, 4-iso Diethyl butylindene-1,2-dicarboxylate, diethyl 4-t-butylindene-1,2-dicarboxylate, diethyl 4-phenylindene-1,2-dicarboxylate, 4-cyclohexylindene-1,2-dicarboxylic acid Examples include diethyl.

  The feature of the compound of the general formula (1) is that the aromatic ring has a conjugated structure with one carbonyl group through the cycloalkene structure, and this feature makes it possible to use conventional succinic acid esters and cycloalkanedicarboxylic acid esters. It is inferred that a behavior different from the molecular weight distribution of the polymer obtained by using is expressed.

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

  The solid catalyst component (I) in the present invention may contain an electron donating compound (hereinafter also referred to as component (D)) other than the component (A) represented by the general formula (1). . Examples of the electron donating compound (D) include acid halides, acid amides, nitriles, acid anhydrides, diether compounds, dicarbonate compounds, carbonate compounds containing an ether group, and components (A). Examples include organic acid esters. Two or more of these electron donating compounds (D) can be used in combination.

  The solid catalyst component (I) 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— 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, it is a chain, partially hydrogenated, cyclic or modified polysiloxane which is liquid or viscous at room temperature and has 0.03 to 5 cm 2 / s (3 to 500 centistokes).

  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 content of titanium, magnesium, halogen atom and ester compound (A) in the solid catalyst component (I) in the present invention is not particularly specified, but preferably 0.1 to 10% by weight of titanium, preferably 0 0.5 to 8.0 wt%, more preferably 1.0 to 8.0 wt%, magnesium is 10 to 40 wt%, more preferably 10 to 30 wt%, particularly preferably 13 to 25 wt%, The halogen atom is 20 to 89% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 75% by weight, and the ester compound (A) is 0.5 to 40% by weight in total, more preferably 1 to 30% in total. % By weight, particularly preferably 2 to 25% by weight in total.

(Description of production method of solid catalyst component (I) for olefin polymerization)
The solid catalyst component (I) for olefin polymerization of the present invention comprises the following magnesium compound, titanium compound, and if necessary, a halogen compound other than the titanium compound and the ester compound (A) of the general formula (1). Prepared by bringing them into contact with each other.

  Examples of the magnesium compound (B) (hereinafter also simply referred to as “component (B)”) used in the method for producing a solid catalyst component of the present invention include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium. , One or more selected from diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium and the like. Among these magnesium compounds, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, and dialkoxymagnesium are preferable, and dialkoxymagnesium is particularly preferable.

  Examples of dialkoxymagnesium include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. These dialkoxymagnesiums may be prepared by reacting metal magnesium with alcohol in the presence of halogen or a halogen-containing metal compound. One or more of the above dialkoxymagnesium can be used in combination.

  Furthermore, in the solid catalyst component of the present invention, dialkoxymagnesium is preferably in the form of granules or powders, and the shape 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 at the time of polymerization, and the handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer Problems such as blockage caused by fine powder contained in the powder are solved.

  The spherical dialkoxymagnesium does not necessarily have a true spherical shape, and an elliptical shape or a potato shape can also be used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter w is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. .

  The average particle diameter of the dialkoxymagnesium is 1 to 1 in terms of an average particle diameter D50 (50% in the cumulative particle size distribution) when measured using a laser light scattering diffraction particle size analyzer. The thing of 200 micrometers is preferable and the thing of 5-150 micrometers is more preferable. In the case of spherical dialkoxymagnesium, the average particle size is preferably 1 to 100 μm, more preferably 5 to 50 μm, and even more preferably 10 to 40 μm. Further, as for the particle size, those having a small particle size distribution with less fine powder and coarse powder are desirable. Specifically, the particle size of 5 μm or less is preferably 20% or less, more preferably 10% or less when measured using a laser light scattering diffraction particle size measuring instrument. On the other hand, particles having a particle size of 100 μm or more are preferably 10% or less, more preferably 5% or less.

  Furthermore, the particle size distribution is ln (D90 / D10) (where D90 is the cumulative particle size in the volume cumulative particle size distribution and 90% of the particle size, and D10 is the cumulative particle size in the volume cumulative particle size distribution of 10%). Is preferably 3 or less, more preferably 2 or less. For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388 can be used to produce spherical dialkoxymagnesium as described above. It is exemplified in the publication.

  In the present invention, as the magnesium compound (B), either a solution-like magnesium compound or a magnesium compound suspension can be used. When the magnesium compound (B) is a solid, it is dissolved in a solvent having a solubilizing ability for the magnesium compound (B) to form a solution-like magnesium compound, or has a solubilizing ability for the magnesium compound (B). Suspend in a non-solvent and use as a magnesium compound suspension. When the magnesium compound (B) is a liquid, it can be used as it is as a solution-like magnesium compound, or it can be dissolved in a solvent capable of solubilizing the magnesium compound and used as a solution-like magnesium compound. .

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

  On the other hand, as a medium that does not have the solubilizing ability of the magnesium compound (B), a saturated hydrocarbon solvent or an unsaturated hydrocarbon solvent that does not dissolve the magnesium compound is used. Saturated hydrocarbon solvents or unsaturated hydrocarbon solvents are high in safety and industrial versatility, and are specifically linear or branched with a boiling point of 50 to 200 ° C. such as hexane, heptane, decane, and methylheptane. Alicyclic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as cycloaliphatic hydrocarbon compounds, cyclohexane, ethylcyclohexane and decahydronaphthalene, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene and ethylbenzene. Of these, linear aliphatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as hexane, heptane and decane, and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene and ethylbenzene are preferably used. . Moreover, these may be used independently or may be used in mixture of 2 or more types.

Examples of the titanium compound (C) (hereinafter sometimes referred to as “component (C)”) used in the preparation of the component (I) in the present invention include the general formula (6);
Ti (OR ¹⁸ ) _j X _4-j (6)
(R ¹⁸ is a hydrocarbon group having 1 to 10 carbon atoms, and when a plurality of OR ¹⁸ groups are present, the plurality of R ¹⁸ may be the same or different, X is a halogen group, In the case where a plurality of are present, each X may be the same or different, and j is 0 or an integer of 1 to 4.).

  The tetravalent titanium compound represented by the general formula (6) is one or more compounds selected from the group consisting of an alkoxy titanium, a titanium halide, and an alkoxy titanium halide group. Specifically, titanium tetrahalide, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other titanium tetrahalides, alkoxy titanium halides such as methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxy Alkoxy titanium trihalides such as titanium trichloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, dialkoxy titanium dihalide, trimethoxy titanium chloride, triethoxy titanium chloride, Trialkoxy titanium halides such as tripropoxy titanium chloride and tri-n-butoxy titanium chloride are exemplified. Among these, halogen-containing titanium compounds are preferably used, and titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, the tetravalent titanium compound represented by the general formula (6) may be used after diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

  In the preparation of the solid catalyst component (I) of the present invention, a halogen compound other than the titanium compound (C) may be used as necessary. Examples of the halogen compound include tetravalent halogen-containing silicon compounds. More specifically, tetrachlorosilane (silicon tetrachloride), silane tetrahalides such as tetrabromosilane, methoxytrichlorosilane, ethoxytrichlorosilane, propoxytrichlorosilane, n-butoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, Examples include alkoxy group-containing halogenated silanes such as dipropoxydichlorosilane, di-n-butoxydichlorosilane, trimethoxychlorosilane, triethoxychlorosilane, tripropoxychlorosilane, and tri-n-butoxychlorosilane.

  The component (A) used in the preparation of the solid catalyst component (I) of the present invention is the same as the component (A) of the solid catalyst component (I) of the present invention, and the description thereof is omitted. The electron donating compound (D) other than the component (A) used as necessary in the preparation of the solid catalyst component (I) of the present invention is the electron donating property of the solid catalyst component (I) of the present invention. This is the same as compound (D), and its description is omitted. In addition, the component (E) used as necessary in the preparation of the solid catalyst component (I) of the present invention is the same as the component (E) of the solid catalyst component (I) of the present invention, and the description thereof is omitted. To do.

  In the present invention, suitable methods for preparing the solid catalyst component (I) include, for example, a method of co-grinding a solid magnesium compound having no reducing property, component (A) and titanium halide, and an adduct such as alcohol. Contacting magnesium halide compound, component (A) and titanium halide in the presence of inert hydrocarbon solvent, dialkoxymagnesium, component (A) and titanium halide in the presence of inert hydrocarbon solvent And a method in which a solid catalyst is deposited by bringing the reducing magnesium compound, component (A) and titanium halide into contact with each other.

  Below, the specific preparation method of the solid catalyst component (I) for olefin polymerization is illustrated. In the following methods (1) to (16), in addition to the component (A), an electron donating compound (D) other than the component (A) may be used in combination. Furthermore, you may perform the said contact in coexistence of other reaction reagents, such as silicon, phosphorus, aluminum, and surfactant, for example.

(1) After dissolving magnesium halide in an alkoxytitanium compound, the organosilicon compound is contacted to obtain a solid product, the solid product is reacted with titanium halide, and then component (A) is contacted. To prepare a solid catalyst component (I) for olefin polymerization. At this time, the component (I) can be further subjected to preliminary polymerization treatment with an organoaluminum compound, an organosilicon compound and olefins.
(2) After reacting magnesium halide and alcohol to make a uniform solution, the carboxylic acid anhydride is brought into contact with the homogeneous solution, and then the titanium halide and component (A) are contacted with the solution to obtain a solid product. A solid catalyst component (I) for olefin polymerization is prepared by further contacting a titanium halide with the solid product.
(3) An organomagnesium compound is synthesized by reacting magnesium metal, butyl chloride, and dialkyl ether, and the organomagnesium compound is contacted with alkoxytitanium to obtain a solid product. And a method of preparing a solid catalyst component (I) for olefin polymerization by catalytically reacting titanium halide. At this time, the solid component can be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin to prepare a solid catalyst component (I) for olefin polymerization.
(4) An organomagnesium compound such as dialkylmagnesium and an organoaluminum compound are brought into contact with alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution, and a silicon compound such as silicon tetrachloride is brought into contact with this solution to form a solid. Then, the solid product is contacted with titanium halide and component (A) in the presence of an aromatic hydrocarbon solvent, and further contacted with titanium tetrachloride to solid catalyst component for olefin polymerization. A method of obtaining (I).
(5) Magnesium chloride, tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to obtain a homogeneous solution, and after contacting the solution and titanium halide, the temperature is raised to precipitate a solid, A method of obtaining the solid catalyst component (I) for olefin polymerization by bringing the solid (B) into contact with the component and further reacting with titanium halide.
(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 a hydrocarbon solvent to form a homogeneous solution, and the solution After adding titanium tetrachloride to the mixture, the temperature is raised to precipitate a solid product. The solid product is contacted with component (A) and further reacted with titanium tetrachloride to solidify the solid catalyst component (I) for olefin polymerization. How to prepare.
(7) Suspend dialkoxymagnesium in a hydrocarbon solvent, then contact with titanium tetrachloride, raise the temperature, contact with component (A) to obtain a solid product, and convert the solid product to hydrocarbon A method of preparing a solid catalyst component (I) for olefin polymerization by washing with a solvent and then contacting with titanium tetrachloride again in the presence of a hydrocarbon solvent. At this time, the solid component can be heat-treated in the presence or absence of a hydrocarbon solvent.
(8) After dialkoxymagnesium is suspended in a hydrocarbon solvent, it is contacted with titanium halide and component (A) to obtain a solid product. After washing the solid product with an inert organic solvent, A method for obtaining a solid catalyst component (I) for olefin polymerization by contacting and reacting with a titanium halide again in the presence of a hydrocarbon solvent. At this time, the solid component and the titanium halide can be contacted twice or more.
(9) dialkoxymagnesium, calcium chloride and alkoxy group-containing silicon compound are co-ground, and the obtained pulverized solid is suspended in a hydrocarbon solvent, and then contacted with titanium halide and component (A), Next, a method for preparing a solid catalyst component (I) for olefin polymerization by further contacting a titanium halide.
(10) The dialkoxymagnesium and component (A) are suspended in a hydrocarbon solvent, the suspension is contacted with titanium halide and reacted to obtain a solid product, and the solid product is washed with a hydrocarbon solvent. Thereafter, the method further comprises contacting a titanium halide in the presence of a hydrocarbon solvent to obtain a solid catalyst component (I) for olefin polymerization.
(11) A solid catalyst component (I) for olefin polymerization is prepared by contacting aliphatic magnesium such as magnesium stearate with titanium halide and component (A), and then further contacting with titanium halide. Method.
(12) The dialkoxymagnesium is suspended in a hydrocarbon solvent, brought into contact with the titanium halide, heated, and contacted with the component (A) to obtain a solid product. The solid product is treated with a hydrocarbon solvent. In the presence of a hydrocarbon solvent and again contacting with a titanium halide to prepare the solid catalyst component (I) for olefin polymerization, which is one of the above suspension / contact and catalytic reaction In the step, the solid catalyst component (I) for olefin polymerization is prepared by contacting aluminum chloride.
(13) Dialkoxymagnesium, 2-ethylhexyl alcohol, and carbon dioxide are contact-reacted in the presence of a hydrocarbon solvent to form a homogeneous solution, and this solution is contacted with titanium halide and component (A) to form a solid product. The solid product is further dissolved in tetrahydrofuran, and then a solid product is further precipitated. The solid product is contacted with titanium halide, and if necessary, contact reaction with titanium halide is repeated to obtain olefins. A method for preparing a solid catalyst component (I) for polymerization. In this case, for example, a silicon compound such as tetrabutoxysilane may be used in any of the contact, contact reaction, and dissolution steps.
(14) After suspending magnesium chloride, an organic epoxy compound and a phosphoric acid compound in a hydrocarbon solvent, the mixture is heated to obtain a homogeneous solution, and this solution is contacted with a carboxylic acid anhydride and a titanium halide to form a solid. A product is obtained, and the solid product is allowed to react with the component (A). The obtained reaction product is washed with a hydrocarbon solvent, and then again contacted with a titanium halide in the presence of the hydrocarbon solvent. To obtain a solid catalyst component (I) for olefin polymerization.
(15) Contact reaction of dialkoxymagnesium, titanium compound and component (A) in the presence of a hydrocarbon solvent, contact reaction of the resulting reaction product with a silicon compound such as polysiloxane, and further contact with a titanium halide A method of obtaining a solid catalyst component (I) for olefin polymerization by reacting, then contacting a metal salt of an organic acid, and then contacting a titanium halide again. (16) After dialkoxymagnesium and component (A) are suspended in a hydrocarbon solvent, the temperature is raised and brought into contact with the silicon halide, and then brought into contact with the titanium halide to obtain a solid product. A method of preparing a solid catalyst component (I) for polymerizing olefins by washing the product with a hydrocarbon solvent and then again contacting with a titanium halide in the presence of the hydrocarbon solvent. At this time, the solid component may be heat-treated in the presence or absence of a hydrocarbon solvent.

  In addition, in order to further improve the polymerization activity at the time of olefin polymerization and the stereoregularity of the produced polymer, a titanium halide is newly added to the solid catalyst component (I) after washing in the methods (1) to (16). And a hydrocarbon solvent are contacted at 20 to 100 ° C., the temperature is raised, a reaction treatment (secondary reaction treatment) is performed, and then an operation of washing with a liquid inert organic solvent at room temperature is repeated 1 to 10 times. May be.

  As a method for preparing component (I) in the present invention, any of the above methods can be suitably used. Among them, (1), (3), (4), (5), (7), The method (8) or (10) is preferred, and the method (3), (4), (7), (8), (10) provides a solid catalyst component for olefin polymerization having high stereoregularity. Are particularly preferable. The most preferred method of preparation is to suspend dialkoxymagnesium and component (A) in a hydrocarbon solvent selected from linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. The suspension is added to titanium halide and reacted to obtain a solid product. The solid product is washed with a hydrocarbon solvent, and further contacted with titanium halide in the presence of a hydrocarbon solvent. This is a method for obtaining a solid catalyst component (I) for olefin polymerization.

  The amount of each component used in preparing the solid catalyst component (I) varies depending on the preparation method and cannot be defined unconditionally. For example, a tetravalent titanium halogen compound (C) per mole of the magnesium compound (B) can be used. ) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and component (A) (when component (I) does not contain an electron-donating compound (D)) Body, or the total amount of component (A) and electron donating compound (D) (when component (I) contains electron donating compound (D)) is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol, the solvent is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol, and polysiloxane ( E) 0.01-100 , Preferably 0.05～80G, more preferably 1 to 50 g.

(Description of olefin polymerization catalyst)
The olefin polymerization catalyst of the present invention comprises (I) a solid catalyst component, (II) an organoaluminum compound (hereinafter sometimes simply referred to as “component (F)”), and (III) an external electron donating compound (hereinafter referred to as “component”). , Simply referred to as “component (G)”) to form a catalyst for olefin polymerization, and polymerization or copolymerization of olefins can be carried out in the presence of the catalyst.

(II) If a compound represented by organic aluminum compounds represented by the general formula (2) is not particularly limited, examples of R ^8, an ethyl group, an isobutyl group are preferable, as the Q, hydrogen atom, A chlorine atom, a bromine atom, an ethoxy group, or a phenoxy group is preferable, and p is preferably 2, 2.5 or 3, and particularly preferably 3.

  Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diethylaluminum bromide, etc. Alkyl aluminum halides such as alkyl aluminum hydride such as diethyl aluminum hydride and diisobutyl aluminum hydride, and alkyl aluminum alkoxides such as diethyl aluminum ethoxide and diethyl aluminum phenoxide. Tri-n-butylaluminum, Trialkylaluminum such as Li isobutyl aluminum are preferably used, particularly preferably triethyl aluminum and triisobutyl aluminum. These aluminum compounds can be used alone or in combination of two or more.

  Examples of the (III) external electron donating compound used in forming the olefin polymerization catalyst of the present invention include organic compounds containing oxygen atoms or nitrogen atoms, such as alcohols, phenols, ethers, Esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds, especially organosilicon compounds having Si—O—C bonds, or Si—N—C bonds Examples thereof include aminosilane compounds.

  Among the above, in particular, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, diethers, An organosilicon compound containing a Si—O—C bond and an aminosilane compound containing a Si—N—C bond are preferred, an organosilicon compound having a Si—O—C bond, an aminosilane compound having a Si—N—C bond, 2 1,3-diethers having a substituent at the position are particularly preferred.

Among the external electron donating compounds of the above (III), as the organosilicon compound having a Si—O—C bond, the following general formula (3); R ⁹ _q Si (OR ¹⁰ ) _4-q (3)
(In the formula, R ⁹ is 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. Either a hydrocarbon group or an aromatic hydrocarbon group having a substituent, which may be the same or different, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, or an alkenyl group having 3 to 12 carbon atoms. , A cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, which may be the same or different. q is an integer of 0 ≦ q ≦ 3)).

Among the external electron donating compounds of the above (III), the aminosilane compound having a Si—N—C bond is represented by the following general formula (4): (R ¹¹ R ¹² N) _s SiR ¹³ _4-s (4)
Wherein R ¹¹ and R ¹² 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 or a cycloalkenyl group, R ¹¹ and R ¹² may be the same or different and may be bonded to each other to form a ring, and R ¹³ 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, and C6-C6 an aryl group or an aryloxy group of 20, amino R ¹³ can be more than one, a plurality of R ¹³ is represented by from the same or different .s is an integer from 1 to 3.) A silane compound is mentioned.

  Examples of these organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) alkoxysilane, and alkyl (alkylamino) alkoxysilane. , Cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, etc. Specifically, phenyltrimethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, diisopentyldimethoxysilane, (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis (Ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (methylamino) (methylcyclopentylamino) methylsilane, diethylaminotri Ethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysila Bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, trimethylsilyltrimethoxysilane, or trimethylsilyltriethoxysilane, among others, phenyltrimethoxysilane, t -Butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) Silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (par Hydroisoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane or the like is preferably used. In addition, the organosilicon compound may be used alone or in combination of two or more selected from the organosilicon compound represented by the general formula (3) and the aminosilane compound represented by the general formula (4).

Moreover, as a 1, 3- diether compound which has a substituent in 2-position, following General formula (5);
R ¹⁴ OCH ₂ CR ¹⁵ R ¹⁶ CH ₂ OR ¹⁷ (5)
(In the formula, R ¹⁵ and R ¹⁶ 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 ¹⁴ and R ¹⁷ 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 And may be the same or different from each other).

  Specifically, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-di-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene and the like, among others, 2-isopropyl- 2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene and the like are preferably used, and at least one of these compounds is used. Two or more kinds can be used.

(Olefin polymerization method)
In the present invention, olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst. Examples of olefins include ethylene, propylene, 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. Ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene.

  When propylene is polymerized, it can be copolymerized with other olefins. 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.

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (F) is titanium in the solid catalyst component (I). It is used in the range of 1 to 2000 mol, preferably 50 to 1000 mol, per mol of atoms. The external electron donating compound (G) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per 1 mol of the component (F). .

  The order of contacting the components is arbitrary, but the organoaluminum compound (F) is first charged into the polymerization system, and then the external electron donating compound (G) is contacted and then the component (I) is contacted. desirable. The polymerization of olefin 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.

  Furthermore, in the present invention, when polymerizing an olefin using a catalyst containing a solid catalyst component for olefin polymerization, an organoaluminum compound, and an external electron donating compound (also referred to as main polymerization), catalytic activity, stereoregularity and In order to further improve the particle properties and the like of the polymer produced, it is desirable to carry out 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. Preferably, the component (F) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the solid After contacting the catalyst component (I), an olefin such as propylene, or a mixture of propylene and one or more other olefins is contacted.

  When prepolymerization is performed by combining component (G), component (F) is first charged in a prepolymerization system set to an inert gas atmosphere or olefin gas atmosphere, and then component (G) is contacted. Further, after contacting the solid catalyst component (I) further, a method of contacting an olefin such as propylene or a mixture of propylene and one or more other olefins is desirable.

  When producing a propylene block copolymer, it is performed by multistage polymerization of two or more stages, usually propylene is polymerized in the presence of a polymerization catalyst in the first stage, and ethylene and propylene are copolymerized in the second stage. Can be obtained. An α-olefin other than propylene can be coexisted or polymerized alone during the second stage or subsequent polymerization. Examples of α-olefins include ethylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, 1-octene and the like. Specifically, polymerization is carried out by adjusting the polymerization temperature and time so that the proportion of the polypropylene part is 20 to 80% by weight in the first stage, and then in the second stage, ethylene and propylene or other α -Olefin is introduced and polymerized so that the proportion of rubber part such as ethylene-propylene rubber (EPR) is 20 to 80% by weight. The polymerization temperatures in the first and second stages are both 200 ° C. or less, preferably 100 ° C. or less, and the polymerization pressure is 10 MPa or less, preferably 5 MPa or less. In the case of polymerization time in each polymerization stage or continuous polymerization, the residence time is usually 1 minute to 5 hours.

  Examples of the polymerization method include a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane, a bulk polymerization method using a solvent such as liquefied propylene, and a gas phase polymerization method using substantially no solvent. It is done. Preferred polymerization methods are bulk polymerization and gas phase polymerization.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

(Production Example 1)
<Synthesis of dimethyl indene-1,2-dicarboxylate>
To sodium hydride (244 mmol) dispersed in 100 ml of anhydrous toluene was added equimolar dimethyl oxalate at 25 ° C., followed by methyl 3-phenylpropionate (122 mmol). The reaction solution was stirred at 60 ° C. for 1 hour, returned to room temperature, poured into ice water, and the organic layer was extracted with ethyl acetate. The extract was dehydrated with sodium sulfate and concentrated to obtain 20 g of dimethyl 2-oxo-3-phenylmethyl-butanedioate as an intermediate. The above operation was further repeated 4 times to obtain a total of 100 g of intermediate (dimethyl 2-oxo-3-phenylmethyl-butanedioate). Next, 100 g of dimethyl 2-oxo-3-phenylmethyl-butanedioate was added dropwise to 1 L of concentrated sulfuric acid at 0 ° C. over 1 hour. After dropping, the mixture was stirred at 25 ° C. for 2 hours, returned to room temperature, poured into ice water, and the organic layer was extracted with ethyl acetate. The extract was washed with brine, dehydrated with sodium sulfate, and concentrated. Finally, the residue was purified by a silica gel column to obtain 70 g of the target compound.

  As a result of analysis by 1H-NMR, the 1H-NMR chemical shift values were 3.64 (s, 3H), 3.77 (s, 3H), 4.83 (s, 1H), 7.40- 7.45 (m, 2H), 7.51 to 7.55 (m, 1H), 7.61 to 7.65 (m, 1H), 7.87 (d, 1H). The product obtained was confirmed to be dimethyl indene-1,2-dicarboxylate. In addition, when the measurement by LC was performed, the purity of the obtained dimethyl indene-1,2-dicarboxylate was 98.0%.

(Production Example 2)
<Synthesis of indene-1,2-dicarboxylate>
To sodium hydride (244 mmol) dispersed in 100 ml of anhydrous toluene was added equimolar dimethyl oxalate at 25 ° C., followed by ethyl 3-phenylpropionate (122 mmol). The reaction solution was stirred at 60 ° C. for 1 hour, returned to room temperature, poured into ice water, and the organic layer was extracted with ethyl acetate. The extract was dehydrated with sodium sulfate and then concentrated to obtain 22 g of an intermediate diethyl 2-oxo-3-phenylmethyl-butanedioate. The above operation was further performed 4 times to obtain a total of 110 g of an intermediate (diethyl 2-oxo-3-phenylmethyl-butanedioate). Next, 100 g of diethyl 2-oxo-3-phenylmethyl-butanedioate was added dropwise to 1 L of concentrated sulfuric acid at 0 ° C. over 1 hour. After dropping, the mixture was stirred at 25 ° C. for 2 hours, returned to room temperature, poured into ice water, and the organic layer was extracted with ethyl acetate. The extract was washed with brine, dehydrated with sodium sulfate, and concentrated. Finally, the residue was purified by a silica gel column to obtain 75 g of the desired compound.

  As a result of analysis by 1H-NMR, 1H-NMR chemical shift values were 1.17 (t, 3H), 1.27 (t, 3H), 4.02 (m, 2H), and 4.27 (respectively). m, 2H), 4.83 (s, 1H), 7.40-7.45 (m, 2H), 7.51-7.55 (m, 1H), 7.61-7.65 (m, 1H), 7.87 (d, 1H), it was confirmed that the obtained product was diethyl indene-1,2-dicarboxylate. As a result of measurement by LC, the purity of the obtained diethyl indene-1,2-dicarboxylate was 98.2%.

<Synthesis of Solid Catalyst Component A>
10 g (87.4 mmol) of diethoxymagnesium was taken into a 500 ml flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and 55 ml of toluene was added to make a suspension, and then the suspension 30 ml of titanium tetrachloride and 15.3 mmol (3.21 g) of dimethyl indene-1,2-dicarboxylate obtained in Production Example 1 were added, and the temperature was further raised to 90 ° C. Then, it was made to react for 90 minutes in the state holding 90 degreeC temperature. After completion of the reaction, the supernatant was extracted, 20 ml of titanium tetrachloride was added, and the mixture was further reacted at 100 ° C. for 2 hours. After completion of the reaction, the reaction product was washed 4 times with 75 ml of 100 ° C. toluene. Subsequently, it was washed 6 times with 75 ml of n-heptane at 40 ° C. to obtain a solid catalyst component A. After solid-liquid separation, the titanium content in the solid catalyst component A was measured and found to be 2.7% by weight.

<Formation of polymerization catalyst and evaluation of polymerization>
In an autoclave with a stirrer having an internal volume of 2.0 liters that was completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS), and 0.1 wt. 0026 mmol was charged to form a polymerization catalyst. 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. At this time, the polymerization activity per 1 g of the solid catalyst component, the ratio (XS) of p-xylene solubles in the produced polymer, the melt flow rate value (MFR) of the produced polymer, and the molecular weight distribution of the produced polymer Are shown in Table 1.

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

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

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

(Measurement of molecular weight distribution of polymer)
The molecular weight distribution of the polymer is determined by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn determined by gel permeation chromatography (GPC) (Alliance GPC / V2000, manufactured by Waters) under the following conditions. evaluated.
Solvent: o-dichlorobenzene (ODCB)
Measurement temperature: 140 ° C
Column: Showa Denko UT-806 × 3, HT-803 × 1 Sample concentration: 1 mg / mL-ODCB (10 mg / 10 ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0ml / min

  Formation of a polymerization catalyst and evaluation of polymerization were carried out in the same manner as in Example 1 except that 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) was used instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS). The polymerization results are shown in Table 1.

<Preparation of solid catalyst component B>
A solid catalyst was prepared in the same manner as in Example 1 except that 15.3 mmol of indene-1,2-dicarboxylate obtained in Production Example 2 was used instead of 15.3 mmol of dimethyl indene-1,2-dicarboxylate. Component B was obtained. The titanium content in the solid catalyst component B was measured and found to be 2.8% by weight.
<Formation of polymerization catalyst and evaluation of polymerization>
A polymerization catalyst was formed and evaluated for polymerization in the same manner as in Example 1 except that the solid catalyst component B was used instead of the solid catalyst component A. The polymerization results are shown in Table 1.

  Formation of a polymerization catalyst and evaluation of polymerization were carried out in the same manner as in Example 3 except that 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) was used instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS). The polymerization results are shown in Table 1.

Comparative Example 1
<Preparation of solid catalyst component C>
A solid catalyst was prepared in the same manner as in Example 2 except that 15.3 mmol of 3,6-dimethylcyclohexane-1,2-dicarboxylate diisobutyl was used instead of 15.3 mmol of dimethyl indene-1,2-dicarboxylate. Component C was prepared. The titanium content in the obtained solid catalyst component was 3.0% by weight.
<Formation of polymerization catalyst and evaluation of polymerization>
A polymerization catalyst was formed and evaluated in the same manner as in Example 1 except that the solid catalyst component C was used in place of the solid catalyst component A. The polymerization results are shown in Table 1.

Comparative Example 2
<Preparation of solid catalyst component D>
Solid catalyst component D was prepared in the same manner as in Example 1, except that 15.3 mmol of diethyl diisopropyl succinate was used instead of 15.3 mmol of dimethyl indene-1,2-dicarboxylate. The titanium content in the obtained solid catalyst component was 3.6% by weight.
<Formation of polymerization catalyst and evaluation of polymerization>
A polymerization catalyst was formed and evaluated for polymerization in the same manner as in Example 1 except that the solid catalyst component D was used in place of the solid catalyst component A. The polymerization results are shown in Table 1.

Comparative Example 3
A polymerization catalyst was formed and polymerized in the same manner as in Comparative Example 2 except that 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS) was used instead of 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS). The polymerization results are shown in Table 1.

Comparative Example 4
<Preparation of solid catalyst component E>
The solid catalyst component E was prepared in the same manner as in Example 1 except that 15.3 mmol of octahydroindene-1,2-dicarboxylate was used instead of 15.3 mmol of dimethyl indene-1,2-dicarboxylate. Prepared. The titanium content in the obtained solid catalyst component was 2.6% by weight.
<Formation of polymerization catalyst and evaluation of polymerization>
A polymerization catalyst was formed and evaluated for polymerization in the same manner as in Example 1 except that the solid catalyst component E was used instead of the solid catalyst component A. The polymerization results are shown in Table 1.

Comparative Example 5
<Preparation of solid catalyst component F>
A solid was obtained in the same manner as in Example 1 except that 15.3 mmol of diethyl 1,2-dihydronaphthalene-2,3-dicarboxylate was used instead of 15.3 mmol of dimethyl indene-1,2-dicarboxylate. Catalyst component F was prepared. The titanium content in the obtained solid catalyst component was 2.8% by weight.
<Formation of polymerization catalyst and evaluation of polymerization>
A polymerization catalyst was formed and evaluated in the same manner as in Example 1 except that the solid catalyst component F was used in place of the solid catalyst component A. The polymerization results are shown in Table 1.

  The catalyst for olefin polymerization of the present invention can obtain an olefin polymer having an appropriate molecular weight distribution that is neither wide nor narrow in high yield while maintaining high stereoregularity. Therefore, it is possible to provide a general-purpose polyolefin that can utilize an existing molding machine at a low cost, and is expected to be useful in the production of a copolymer of olefins having high functionality.

Claims (8)

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

(In the formula, R ¹ and R ² are 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 12 carbon atoms, or a branched alkenyl group. group, a cycloalkyl group having a carbon number of 3-12, a cycloalkenyl group having a carbon number of 3-12, halogen substituted cycloalkyl group having a carbon number of 3-12, halogen-substituted cycloalkenyl groups 3-12 carbon atoms or carbon atoms, 6 shows the 24 aromatic hydrocarbon group and may be the same or different, R ³ to R ⁷ is polymerization of olefins which is characterized by containing a compound represented by the hydrogen atom in shown to.) Solid catalyst component. R ¹ and R ² are each 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 having 3 to 12 carbon atoms or a branched alkenyl group, carbon A cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms, and R ^{3 to} R ⁷ are hydrogen atoms. The solid catalyst component for olefin polymerization according to 1. (I) The solid catalyst component for olefin polymerization according to claim 1 or 2 ,
(II) The following general formula (2); R ⁸ _p AlQ _3-p (2)
(In the formula, R ⁸ 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.) And (III) an olefin polymerization catalyst characterized by being formed from an external electron donating compound. The (III) external electron donating compound is represented by the following general formula (3);
R ⁹ _q Si (OR ¹⁰ ) _4-q (3)
(In the formula, R ⁹ is 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 ¹⁰ 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.) An organosilicon compound represented by the general formula (4);
(R ¹¹ R ¹² N) _s SiR ¹³ _4-s (4)
(Wherein R ¹¹ and R ¹² 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 ¹¹ and R ¹² may be the same or different, and may be bonded to each other to form a ring, and R ¹³ represents 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 ¹³ is plural, R ¹³ is represented by from the same or different .s is an integer from 1 to 3.) The olefin polymerization catalyst according to claim 3 , wherein the catalyst is one or more selected from aminosilane compounds. The (III) external electron donating compound is phenyltrimethoxysilane, n-butyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltriethoxysilane, n-butyltriethoxysilane, cyclopentyltriethoxysilane, Cyclohexyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylcyclopentyldimethoxy Silane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (d Arylamino) silane, dicyclohexyl-bis (ethylamino) silane, dicyclopentyl bis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, claims, characterized in that a diethylamino trimethoxysilane or diethylamino triethoxy silane 3. The catalyst for olefin polymerization according to 3 . The (III) external electron donating compound is represented by the following general formula (5):
R ¹⁴ OCH ₂ CR ¹⁵ R ¹⁶ CH ₂ OR ¹⁷ (5)
(In the formula, R ¹⁵ and R ¹⁶ 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 ¹⁴ and R ¹⁷ 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 The catalyst for olefin polymerization according to claim 3 , which is a diether compound represented by the following formula: The diether compound is 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane or 9,9-bis (methoxymethyl) fluorene. The olefin polymerization catalyst according to claim 6 . A method for producing an olefin polymer, wherein olefins are polymerized in the presence of the olefin polymerization catalyst according to any one of claims 3 to 7 .

Images