JP6216611B2 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

  The present invention does not include an internal electron-donating compound having an aromatic ring such as a phthalate ester, has high polymerization activity and stereoregularity, and is an olefin polymerization using a conventional phthalate ester as an electron donor. The present invention relates to a solid catalyst component for olefin polymerization having a molecular weight distribution and higher hydrogen activity similar to those of a catalyst for olefins, a catalyst for olefin polymerization, and 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 has been used. 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, in Japanese Patent Laid-Open No. 63-3010 (Patent Document 1), a solid catalyst component on which an electron donor, typically a phthalate ester is supported, an organoaluminum compound as a promoter component, and at least one It has been reported that when a silicon compound having Si-OR (wherein R is a hydrocarbon group) is used, excellent polymerization activity and stereospecificity are expressed. Many reports including the above-mentioned patent documents show examples in which it is preferable to use a phthalate ester as an electron donor.

  However, di-n-butyl phthalate and benzyl butyl phthalate, which are phthalate esters, are specified as SVHC (SUBSTANCES OF VERY HIGH CONCERN) in European Regulation, Evaluation, Authorization and Chemicals (REACH) regulations. In Europe, since its use is prohibited in principle after February 21, 2015, the industry is required to switch to a catalyst system that does not use SVHC. A solid catalyst component using diethyl phthalate as an electron donor is known as a phthalate ester that does not correspond to SVHC indicated by REACH regulations (Japanese Patent Laid-Open No. 10-182720 (Patent Document 2). )), However, there is a move to avoid the use of some phthalate esters as electron donors of solid catalyst components, even if the phthalate esters do not fall under SVHC. Regardless of the REACH regulations, it is desired to develop an electron donor that does not contain an aromatic ring in consideration of environmental impact. Therefore, there is currently a need for solid catalyst components and catalysts for olefin polymerization that do not use phthalate esters or compounds containing aromatic rings as electron donors.

  On the other hand, as electron donors that are not subject to SVHC regulation, fatty acid esters such as malonic acid esters and succinic acid esters, diethers such as 1,2-diether, 1,3-diether, and 1,4-diether, phthalic acid, etc. Solid catalyst components prepared without the use of esters are known.

  Examples of solid catalyst components for olefin polymerization using a malonic acid ester include WO2012 / 060361 (Patent Document 3), JP-A 2004-91513 (Patent Document 4), and JP-A-6-122716 (Patent Document 5). ), WO2013 / 005463 (patent document 6) and the like.

  Patent Document 3 includes di-iso-butyl malonate dimethyl, di-iso-propyl malonate dimethyl, di-n-propyl malonate dimethyl, di-n-butyl malonate dimethyl, dineopentyl malonate dimethyl, bis A solid catalyst component using a malonic ester selected from dimethyl (3-chloro-n-propyl) malonate and dimethyl dibromomalonate is disclosed.

Patent Document 4 discloses a solid catalyst component using a malonic acid ester represented by R ¹ R ² C (COOR ³ ) ₂ . Patent Document 5 discloses a solid catalyst component using a cyclic malonate represented by XC (COOR ¹ ) (COOR ² ). Patent Document 6 discloses a solid catalyst component using a malonic acid ester represented by R ¹ R ² C═C (COOR ³ ) (COOR ⁴ ). Japanese Unexamined Patent Publication No. 2002-542347 (Patent Document 7) discloses a solid catalyst component using a succinic acid ester represented by (R ¹ OOC) CR ³ R ⁴ CR ⁵ R ⁶ (COOR ² ). Japanese Patent Laid-Open No. 03-706 (Patent Document 8) discloses a solid catalyst component using a diether represented by ROCH ₂ CR ¹ R ² CH ₂ OR. Patent Document 9 discloses a solid catalyst component using a diether represented by R ²¹ R ²² R ²³ CO (R ¹ R ^{n + 1} C... CR ⁿ R ²ⁿ ) OCR ²⁴ R ²⁵ R ²⁶ . .

  The catalyst system composed of solid catalyst components using malonic acid esters and diethers has a relatively high hydrogen activity, so the polypropylene obtained when used for propylene polymerization is injection molding that requires a high melt flow. Although it is suitable for the body, the stereoregularity is not sufficiently high, and it is difficult to apply to the production of a high-rigidity injection-molded body. In addition, general-purpose grades such as fibers, films, and sheets that are applied to polypropylene produced by a solid catalyst using a conventional phthalate ester as an electron donor are required to have a low melt flow. The catalyst system used as the internal electron donor has a problem of lowering the polymerization activity in the low melt flow region because of its characteristics.

  A catalyst system composed of a solid catalyst component using succinate as an internal electron donor has a very wide molecular weight distribution of the obtained olefin polymer, but the stereoregularity is not at a sufficiently high level. The molecular weight distribution of polypropylene generally used is required to be controllable between, for example, about 4 to 6 in terms of Mw / Mn value, and a solid catalyst that exhibits a certain degree of crystallinity and a certain degree of high polymerization activity in that range. It is said that it is the most practical component. And the catalyst comprised from the solid catalyst component using the conventional phthalate ester is known as what satisfies this.

JP-A 63-3010 Japanese Patent Laid-Open No. 10-182720 WO2012 / 060361 JP 2004-91513 A Japanese Patent Laid-Open No. 06-122716 WO2013 / 005463 publication Japanese translation of PCT publication No. 2002-542347 Japanese Patent Laid-Open No. 03-706 Japanese Patent Laid-Open No. 04-96910

  Therefore, the object of the present invention is not to use a compound having an aromatic ring such as a phthalate ester as an internal electron donor, and has a higher polymerization activity than that using a conventional malonic acid ester, diether or succinic acid ester, Solid for olefin polymerization having stereoregularity and having the same molecular weight distribution as that using a conventional phthalate ester, and suitable for the production of an olefin polymer exhibiting higher antihydrogen activity An object is to provide a catalyst component, a catalyst for olefin polymerization, and a method for olefin polymerization.

  In such a situation, the present inventors have conducted intensive studies, and as a result, have obtained solid catalyst components for olefin polymerization containing titanium, magnesium, halogen and a specific norbornene dicarboxylic acid or a specific norbornane dicarboxylic acid as essential components, and The inventors have found that an olefin polymerization catalyst formed using a solid catalyst component can achieve the above object, and have completed the present invention.

（式中、Ｒ^１〜Ｒ^１０は、水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基若しくは置換炭化水素基またはヘテロ原子含有基を示し、互いに同一であっても異なっていてもよく、隣接する基同士は互いに結合して環を形成してもよい。Ｒ^１１およびＲ^１２は、炭素数１〜２０の炭化水素基を示し、互いに同一であっても異なっていてもよい。）の化合物から選択される１種又は２種以上のエステル化合物を含有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 provides titanium, magnesium, halogen and the following formula (1);

(Wherein R ^{1 to} R ¹⁰ represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted hydrocarbon group, or a heteroatom-containing group, and may be the same or different from each other. The adjacent groups may be bonded to each other to form a ring, and R ¹¹ and R ¹² represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. one or olefin polymerization solid catalyst component containing two or more ester compounds selected of compound et al is intended to provide.

The present invention also provides (I) the solid catalyst component, (II) the following general formula (3);
R ²³ _p AlQ _3-p (3)
(In the formula, R ²³ represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen atom or halogen, and p is a real number of 0 <p ≦ 3, which may be the same or different.) And (III) a catalyst for olefin polymerization obtained by contacting an external electron donating compound as required.

  The solid catalyst component for olefin polymerization of the present invention overcomes the problems of conventional solid catalyst components containing malonic acid diester, succinic acid diester or diether when subjected to olefin polymerization, Even without using a phthalate ester, an olefin polymer having a molecular weight distribution equivalent to that of a solid catalyst component containing a conventional phthalate ester and having a higher hydrogen activity can be obtained in a high yield. .

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

(Description of solid catalyst component for olefin polymerization)
The solid catalyst component for olefin polymerization of the present invention (hereinafter sometimes simply referred to as “component (I)”) includes magnesium, titanium, halogen and an ester compound of the above general formula (1) or general formula (2) ( Hereinafter, it may be simply referred to as “ester compound (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.

  In the above general formula (1) and general formula (2), examples of the halogen include fluorine, chlorine, bromine or iodine atoms. Among them, chlorine, bromine or iodine is preferable, and chlorine or bromine is particularly preferable. Bromine.

  In said general formula (1) and general formula (2), as a C1-C20 hydrocarbon group or a substituted hydrocarbon group, a C1-C20 linear alkyl group, a C3-C20 branch Alkyl group, vinyl group, linear or branched alkenyl group having 3 to 20 carbon atoms, linear or branched halogen-substituted alkyl group having 2 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, carbon A C3-C20 cycloalkenyl group and a C6-C20 aromatic hydrocarbon group are mentioned. Further, examples of the hetero atom-containing group include groups selected from nitrogen-containing groups, oxygen-containing groups, phosphorus-containing groups, and silicon-containing groups.

  Examples of the linear alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. Group, n-nonyl group, n-decyl group and the like. Examples of the branched alkyl group having 3 to 20 carbon atoms include secondary or tertiary carbon groups such as iso-propyl group, iso-butyl group, t-butyl group, iso-pentyl group, and neopentyl group. Can be mentioned. Examples of the linear alkenyl group having 3 to 20 carbon atoms include n-propenyl group, n-butenyl group, n-pentenyl group, n-hexenyl group, n-heptenyl group, n-octenyl group, n-nonenyl group, Examples of the branched alkenyl group having 3 to 20 carbon atoms include, for example, iso-protenyl group, iso-butenyl group, t-butenyl group, iso-pentenyl group, neopentenyl group and the like. Examples include alkenyl groups having secondary or tertiary carbon.

  Examples of the linear or branched halogen-substituted alkyl group having 2 to 20 carbon atoms include a halogenated methyl group, a halogenated ethyl group, a halogenated n-propyl group, a halogenated iso-propyl group, and a halogenated n- Butyl group, halogenated iso-butyl group, halogenated n-pentyl group, halogenated n-hexyl group, halogenated n-heptyl group, halogenated n-octyl group, halogenated n-nonyl group, halogenated n-decyl Groups. In addition, examples of halogen include fluorine, chlorine, bromine, and iodine.

  Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a cyclononenyl group, and a cyclodecenyl group.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, methylphenyl group, dimethylphenyl group, ethylphenyl group, benzyl group, 1-phenylethyl group, 2-phenylethyl group, 2-phenylpropyl group. Group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group and the like.

  Nitrogen-containing groups include amino groups; methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, propylamino groups, dipropylamino groups, butylamino groups, dibutylamino groups, pentylamino groups, dipentylamino groups, hexyls. Alkyl groups such as amino group, dihexylamino group, heptylamino group, diheptylamino group, octylamino group, dioctylamino group, nonylamino group, dinonylamino group, decyl group, didecylamino group, cyclohexylamino group, dicyclohexylamino group; phenyl Aryl group or alkylarylamino group such as amino group, diphenylamino group, ditolylamino group, dinaphthylamino group, methylphenylamino group; polycyclic amino group; acetamide group, N-methylacetamide group, An amide group such as a methylbenzamide group; an imino group such as a methylimino group, an ethylimino group, a propylimino group, a butylimino group, or a phenylimino group; an imide group such as an acetimide group or a benzimide group; a hydrazino group; a hydrazono group; a nitro group; A group; a cyano group; an iso-cyano group; an amidino group; a diazo group; an amino group converted to an ammonium salt.

  Examples of the oxygen-containing group include an oxy group; a peroxy group; a hydroxy group; a hydroperoxy group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an iso-propoxy group, and an iso-butoxy group; Aryloxy groups such as methylphenoxy group, dimethylphenoxy group and naphthoxy group; arylalkoxy groups such as phenylmethoxy group and phenylethoxy group; acetoxy group; carbonyl group; acetacetonato group; ether group; acyl group; oxo group; Group; carboxylic anhydride group and the like.

  Examples of the phosphorus-containing group include dialkylphosphine groups such as dimethylphosphine, dibutylphosphine, and dicyclohexylphosphine; diarylphosphine groups such as diphenylphosphine and ditolylphosphine; Examples include a group (phosphide group); a phosphonic acid group; a phosphinic acid group.

  Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, and specifically include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tripropylsilyl, Hydrocarbon-substituted silyl groups such as cyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether; silicon-substituted alkyl groups such as trimethylsilylmethyl; trimethylsilylphenyl and the like Examples include silicon-substituted aryl groups.

Furthermore, in general formula (1) and general formula (2), R ^{1 to} R ¹⁰ and R ^{13 to} R ²⁰ may be bonded to each other to form a ring. For example, R ³ and R ⁴ may be R ⁴ and R ⁵ , R ⁶ and R ⁷ , R ¹ and R ⁸ , R ¹⁵ and R ¹⁶ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹³ and R ¹⁸ , R Examples of the ring formed by combining ⁹ and R ¹⁰ with R ¹⁹ and R ²⁰ are a saturated monocyclic ring, aromatic ring, condensed polycyclic ring, and heterocyclic ring. Specifically, cycloalkane, fluorene, Examples of the ring structure include indene, imidazole, and pyridine.

In general formula (1) and general formula (2), preferable R ^{1 to} R ¹⁰ and R ^{13 to} R ²⁰ are a hydrogen atom, a linear alkyl group having 1 to 6 hydrocarbons, or a branched chain having 3 to 6 carbon atoms. An alkyl group, a vinyl group, a linear or branched alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkenyl group having 5 to 6 carbon atoms, or a fragrance having 6 to 10 carbon atoms. Group hydrocarbon group. Moreover, preferable R < ¹¹ >, R < ¹² >, R < ²¹ > and R < ²² > are a C1-C10 linear alkyl group or a C3-C8 branched alkyl group, Most preferably, it is C1-C4. Or a branched alkyl group having 3 to 4 carbon atoms.

  Specific examples of the ester compound (A) represented by the general formula (1) include dimethyl norbornane-2,2-dicarboxylate, diethyl norbornane-2,2-dicarboxylate, and norbornane-2,2-dicarboxylic acid di-n. -Propyl, norbornane-2,2-dicarboxylic acid di-n-butyl, norbornane-2,2-dicarboxylic acid di-iso-butyl, norbornane-2,2-dicarboxylic acid ethylmethyl; 3-methyl-norbornane-2, Dimethyl 2-dicarboxylate, diethyl 3-methyl-norbornane-2,2-dicarboxylate, 3-methyl-norbornane-2,2-dicarboxylic acid di-n-propyl, 3-methyl-norbornane-2,2-dicarboxylic acid Di-n-butyl, 3-methyl-norbornane-2,2-dicarboxylic acid di-iso-butyl; -Dimethyl norbornane-2,2-dicarboxylate, diethyl 3-ethyl-norbornane-2,2-dicarboxylate, 3-ethyl-norbornane-2,2-dicarboxylate di-n-propyl, 3-ethyl-norbornane-2 , 2-dicarboxylate di-n-butyl, 3-ethyl-norbornane-2,2-dicarboxylate di-iso-butyl; 5-methyl-norbornane-2,2-dicarboxylate dimethyl, 5-methyl-norbornane-2 , 2-dicarboxylate, 5-methyl-norbornane-2,2-dicarboxylate di-n-propyl, 5-methyl-norbornane-2,2-dicarboxylate di-n-butyl, 5-methyl-norbornane-2 , 2-dicarboxylate di-iso-butyl; 5-t-butyl-norbornane-2,2-dicarboxylate dimethyl, 5-t Diethyl butyl-norbornane-2,2-dicarboxylate, 5-t-butyl-norbornane-2,2-dicarboxylic acid di-n-propyl, 5-t-butyl-norbornane-2,2-dicarboxylic acid di-n- Butyl, 5-tert-butyl-norbornane-2,2-dicarboxylate di-iso-butyl;

Dimethyl 3,3-dimethyl-norbornane-2,2-dicarboxylate, diethyl 3,3-dimethyl-norbornane-2,2-dicarboxylate, di-n-3,3-dimethyl-norbornane-2,2-dicarboxylate Propyl, 3,3-dimethyl-norbornane-2,2-dicarboxylate di-n-butyl, 3,3-dimethyl-norbornane-2,2-dicarboxylate di-iso-butyl; 3,3-diethyl-norbornane- Dimethyl 2,2-dicarboxylate, 3,3-diethyl-norbornane-2,2-dicarboxylate diethyl, 3,3-diethyl-norbornane-2,2-dicarboxylate di-n-propyl, 3,3-diethyl- Norbornane-2,2-dicarboxylic acid di-n-butyl, 3,3-diethyl-norbornane-2,2-dicarboxylic acid di-iso-butyl 3,5-dimethyl-norbornane-2,2-dicarboxylic acid dimethyl, 3,5-dimethyl-norbornane-2,2-dicarboxylic acid diethyl, 3,5-dimethyl-norbornane-2,2-dicarboxylic acid di-n- Propyl, 3,5-dimethyl-norbornane-2,2-dicarboxylate di-n-butyl, 3,5-dimethyl-norbornane-2,2-dicarboxylate di-iso-butyl; 3-methyl-5-t- Dimethyl butyl-norbornane-2,2-dicarboxylate, diethyl 3-methyl-5-tert-butyl-norbornane-2,2-dicarboxylate, 3-methyl-5-tert-butyl-norbornane-2,2-dicarboxylic acid Di-n-propyl, 3-methyl-5-t-butyl-norbornane-2,2-dicarboxylic acid di-n-butyl, 3-methyl-5-t-butyl- Diborno-2,2-dicarboxylate di-iso-butyl; dimethyl 5,6-dimethyl-norbornane-2,2-dicarboxylate, diethyl 5,6-dimethyl-norbornane-2,2-dicarboxylate, 5,6- Di-n-propyl dimethyl-norbornane-2,2-dicarboxylate, di-n-butyl 5,6-dimethyl-norbornane-2,2-dicarboxylate, 5,6-dimethyl-norbornane-2,2-dicarboxylic acid Di-iso-butyl;

Spiro (7,1'-cyclopropane-norbornane) -2,2-dicarboxylate, spiro (7,1'-cyclopropane-norbornane) -2,2-dicarboxylate di-n-butyl; Decahydro-1, 4-Methanonaphthalene-2,2-dicarboxylate dimethyl, decahydro-1,4-methanonaphthalene-2,2-dicarboxylate, decahydro-1,4-methanonaphthalene-2,2-dicarboxylate di-n-propyl , Decahydro-1,4-methanonaphthalene-2,2-dicarboxylate di-n-butyl, decahydro-1,4-methanonaphthalene-2,2-dicarboxylate di-iso-butyl;

Dimethyl 5-norbornene-2,2-dicarboxylate, diethyl 5-norbornene-2,2-dicarboxylate, di-n-propyl 5-norbornene-2,2-dicarboxylate, 5-norbornene-2,2-dicarboxylic acid Di-n-butyl, di-iso-butyl 5-norbornene-2,2-dicarboxylate; dimethyl 3-methyl-5-norbornene-2,2-dicarboxylate, 3-methyl-5-norbornene-2,2- Diethyl dicarboxylate, 3-methyl-5-norbornene-2,2-dicarboxylate di-n-propyl, 3-methyl-5-norbornene-2,2-dicarboxylate di-n-butyl, 3-methyl-5- Norbornene-2,2-dicarboxylate di-iso-butyl; 5-chloro-norbornane-2,2-dicarboxylate dimethyl, 5-chloro-norborna Diethyl 2,2-dicarboxylate, 5-chloro-norbornane-2,2-dicarboxylate di-n-propyl, 5-chloro-norbornane-2,2-dicarboxylate di-n-butyl, 5-chloro-norbornane -2,2-dicarboxylic acid di-iso-butyl. These compounds can be used alone or in combination of two or more.

  The ester compound (A) represented by the general formula (1) is, for example, an intermediate obtained by synthesizing an alkylidene malonic acid diester from an aldehyde and a malonic acid diester, and then reacting the alkylidene malonic acid diester with cyclopentadiene. And hydrogenated in the presence of a palladium carbon catalyst. Such a production method is described in the known document Zhurnal Obshchei Khimii (Russian Journal of General Chemistry), 25, 986-9; 1955.

  In the solid catalyst component (I) in the present invention, an electron donating compound other than the ester compound (A) represented by the general formula (1) (hereinafter sometimes referred to as “electron donating compound (D)”) May be included. Examples of the electron donating compound (D) include acid halides, acid amides, nitriles, acid anhydrides, carbonates, ether compounds, and carboxylic acid esters other than the ester compound (A) of the present invention. Is mentioned. Among the above, the ester compound (A) of the present invention and carboxylic acids such as succinic acid diesters, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, malonic acid diesters, alkyl-substituted malonic acid diesters, maleic acid diesters, etc. The use of a solid catalyst component prepared in combination with a component (D) selected from diesters and carboxylic acid diesters having substituents, compounds having ester groups and ether groups or diether compounds Similar to the case where the electron donor is used in combination, the stereoregularity of the olefin polymer obtained at the time of polymerization can be improved, and the molecular weight distribution and hydrogen responsiveness can be controlled to a desired level. Therefore, this is one of the preferred embodiments of the present invention.

  Particularly preferred components (D) include malonic acid diesters such as dimethyl malonate and diethyl malonate, dialkylmalonic acid diesters such as dimethyl diisobutylmalonate and diethyl diisobutylmalonate, diethyl maleate, and di-n-butyl maleate. It is a cycloalkane dicarboxylic acid diester such as maleic acid diester or dimethyl cyclohexane-1,2-dicarboxylate. Such electron donating compounds (D) may be used in combination of two or more.

The solid catalyst component (I) in the present invention may contain polysiloxane (hereinafter sometimes simply referred to as “polysiloxane (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 0.03 to ⁵ cm ² / s (3 to 500 centistokes), 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 content of titanium, magnesium, halogen, and ester compound (A) in the solid catalyst component (I) in the present invention is 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 8.0 wt%, magnesium is 10 to 70 wt%, more preferably 10 to 50 wt%, particularly preferably 15 to 40 wt% More preferably, it is 15 to 25% by weight, halogen is 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, The total amount of the ester compound (A) is 0.5 to 40% by weight, more preferably 1 to 30% by weight, and particularly preferably 2 to 25% by weight. When the solid catalyst component (I) contains the component (D), the ratio of the component (D) content to the ester compound (A) content is preferably 0.01 to 10 mol, relative to 1 mol of the ester compound (A). Is 0.1-1 mol, more preferably 0.2-0.6 mol.

  In addition to the above components, the solid catalyst component (I) in the present invention may further contain a reaction reagent containing a metal such as silicon, phosphorus or aluminum. These reaction agents include organosilicon compounds having Si—O—C bonds, organosilicon compounds having Si—N—C bonds, phosphate compounds having P—O bonds, trialkylaluminum, dialkoxyaluminum chloride, Examples include organoaluminum compounds such as alkoxyaluminum dihalides and trialkoxyaluminums, and aluminum trihalides. Preferably, organosilicon compounds having Si—O—C bonds, organosilicon compounds having Si—N—C bonds, and organic It is an aluminum compound. The solid catalyst component (I) containing such a reaction reagent is preferable in that the polymerization activity and stereoregularity of the obtained solid catalyst component can be improved.

  Examples of the organosilicon compound having a Si—O—C bond and the organosilicon compound having a Si—N—C bond include exemplified compounds and specific examples of organosilicon compounds represented by the following general formulas (4) and (5). Since the thing similar to a compound is mentioned, the description is abbreviate | omitted. Moreover, since the said organoaluminum compound can mention the thing similar to the organoaluminum compound of General formula (3) mentioned later, the description is abbreviate | omitted. These reaction reagents may contain 1 type (s) or 2 or more types.

Moreover, the solid catalyst component (I) containing the reaction reagent is further represented by the general formula (8);
_{[CH 2 = CH- (CH 2)} u ] ^{_{t SiR 23 4-t (8}} )
Wherein R ²³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, or a halogen atom, and may be the same or different, and u is 0 or 1 to 5 And an organic silicon compound having an unsaturated alkyl group represented by the following formula: t is an integer of 1 to 4. Thereby, the further polymerization activity and hydrogen responsiveness of the obtained solid catalyst component can be improved.

An unsaturated alkyl group is a vinyl group or an alkenyl group. Specifically, a vinyl group-containing alkylsilane, a vinyl group-containing alkoxysilane, a vinyl group-containing cycloalkylsilane, a vinyl group-containing phenylsilane, a vinyl group-containing halogen. Silane, vinyl group-containing alkyl halogenated silane, alkenyl group-containing vinyl silane, alkenyl group-containing alkyl silane, alkenyl group-containing alkoxy silane, alkenyl group-containing cycloalkyl silane, alkenyl group-containing phenyl silane, alkenyl group-containing halogenated silane, alkenyl group Containing alkylhalogenated silanes. The vinyl group is a CH ₂ ═CH— group, and the alkenyl group is a CH ₂ ═CH— (CH ₂ ) _u — group. Among these, vinyltrialkylsilane, allyltrialkylsilane, divinylalkylsilane, diallyldialkylsilane, trivinylalkylsilane and triallylalkylsilane are preferable, and allyldimethylvinylsilane, diallyldimethylsilane and triallylmethylsilane are particularly preferable. Di-3-butenylsilane dimethylsilane, diallyldichlorosilane, allyltriethylsilane. In addition, the organosilicon compound which has said unsaturated alkyl group may contain 1 type, or 2 or more types.

(Description of production method of solid catalyst component (I) for olefin polymerization)
The solid catalyst component (I) for olefin polymerization of the present invention includes 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), And if necessary, the electron donating compound (D) is prepared by bringing them into contact with each other.

  Examples of the magnesium compound (B) (hereinafter sometimes simply referred to as “magnesium compound (B)”) used in the method for producing a solid catalyst component of the present invention include dihalogenated magnesium, dialkylmagnesium, alkylmagnesium halide, One or more selected from dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, fatty acid magnesium and the like can be mentioned. 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 dialkoxymagnesiums can be used in combination.

  Furthermore, in the preparation of the solid catalyst component of the present invention, when dialkoxymagnesium is used, it is preferably in the form of granules or powder, and the shape can 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 operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer powder Problems such as occlusion caused by fine powder contained in the product 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 system 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, and 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 magnesium compound in solution 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 of the magnesium compound (B) to form a magnesium compound in a solution place, or has a solubilizing ability of 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, iso-propyl alcohol, iso Alcohols having 1 to 18 carbon atoms such as propylbenzyl alcohol and ethylene glycol; Halogen-containing alcohols having 1 to 18 carbon atoms such as trichloromethanol, trichloroethanol and trichlorohexanol; methyl ether, ethyl ether and iso-propyl Ether, butyl ether, amyl ether, tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, diphenyl ether Ethers having 2 to 20 carbon atoms such as ter; metals such as tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium, tetraethoxy zirconium Acid ester etc. are mentioned, Above all, alcohol such as ethanol, propanol, butanol and 2-ethylhexanol is 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 have high safety and industrial versatility, and are specifically linear or branched having a boiling point of 50 to 200 ° C. such as hexane, heptane, decane, and methylheptane. Aliphatic hydrocarbon compounds such as aliphatic hydrocarbon compounds, cyclohexane, ethylcyclohexane, decahydronaphthalene, and ethylbenzene having a boiling point of 50 to 200 ° C., and aromatic hydrocarbon compounds having a boiling point of 50 to 200 ° C. such as toluene, xylene, and ethylbenzene. Among them, 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. It is done. Moreover, these may be used independently or may be used in mixture of 2 or more types.

Examples of the titanium compound (hereinafter sometimes referred to as “titanium compound (C)”) used in the preparation of the component (I) in the present invention include the general formula (7);
Ti (OR ²⁴ ) _j X _4-j (7)
(R ²⁷ is a hydrocarbon group having 1 to 10 carbon atoms, and when a plurality of OR ²⁴ groups are present, the plurality of R ²⁴ 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 (7) is one or more compounds selected from the group consisting of alkoxy titanium, titanium halides and alkoxy titanium halides. 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, dialkoxy titanium dihalides such as di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tri Examples include trialkoxy titanium halides such as propoxy titanium chloride and tri-n-butoxy titanium chloride. 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. Furthermore, the tetravalent titanium compound represented by the general formula (7) may be diluted with a hydrocarbon compound or a halogen 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 ester compound (A) used in the preparation of the solid catalyst component (I) of the present invention is the same as the ester compound (A) of the solid catalyst component (I) of the present invention, and the description thereof is omitted. The electron donating compound (D) used as necessary in the preparation of the solid catalyst component (I) of the present invention is the same as the electron donating compound (D) of the solid catalyst component (I) of the present invention. Yes, the description is omitted. Further, the polysiloxane (E) used as necessary in the preparation of the solid catalyst component (I) of the present invention is the same as the polysiloxane (E) of the solid catalyst component (I) of the present invention, and its description Is omitted.

  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, an ester compound (A) and a titanium halide, or an adduct such as alcohol. A halogenated magnesium compound, ester compound (A) and titanium halide in the presence of an inert hydrocarbon solvent, dialkoxymagnesium, ester compound (A) and titanium halide in an inert hydrocarbon solvent Examples thereof include a method in which the solid catalyst is brought into contact, a method in which a reducing magnesium compound, an ester compound (A) and a titanium halide are brought into contact with each other to precipitate a solid catalyst.

  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 ester compound (A), an electron donating compound (D) other than the ester compound (A) may be used in combination. Furthermore, you may perform the said contact in coexistence of other reaction reagents and surfactant, such as a silicon | silicone, phosphorus, and aluminum, 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 the ester compound (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 contacted with the uniform solution, and then the solution is contacted with titanium halide and the ester compound (A) to form a solid. And 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 the solid product is converted into an ester compound (A ) And a titanium halide are contact-reacted to prepare a solid catalyst component (I) for olefin polymerization. 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 the ester compound (A) in the presence of an aromatic hydrocarbon solvent, and then further contacted with titanium tetrachloride to obtain a solid catalyst for olefin polymerization. Method for obtaining component (I).
(5) Magnesium chloride, tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to form a homogeneous solvent, and after contacting the solution and titanium halide, the temperature is raised to precipitate a solid, A method in which an ester compound (A) is brought into contact with the solid and further reacted with titanium halide to obtain a solid catalyst component (I) for olefin polymerization.
(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 obtain a homogeneous solution. After adding titanium tetrachloride, the temperature is raised to precipitate a solid product, the solid product ester compound (A) is contacted, and further reacted with titanium tetrachloride to give a solid catalyst component (I) for olefin polymerization. How to prepare.
(7) After suspending dialkoxymagnesium in a hydrocarbon solvent, the temperature is raised after contact with titanium tetrachloride, and contact with the ester compound (A) to obtain a solid product, and the solid product is carbonized. A method of preparing the solid catalyst component (I) for olefin polymerization by washing with a hydrogen solvent and then again contacting with titanium tetrachloride 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 suspending dialkoxymagnesium in a hydrocarbon solvent, contact reaction with titanium halide and ester compound (A) to obtain a solid product, and washing the solid product with an inert organic solvent And a method of obtaining a solid catalyst component (I) for olefin polymerization by contacting and reacting with 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 ester compound (A). Then, a method for preparing a solid catalyst component (I) for olefin polymerization by further contacting with a titanium halide.
(10) The dialkoxymagnesium and the ester compound (A) are suspended in a hydrocarbon solvent, and the suspension is contacted and reacted with a titanium halide to obtain a solid product. The solid product is obtained with a hydrocarbon solvent. A method of obtaining a solid catalyst component (I) for olefin polymerization by contacting titanium halide in the presence of a hydrocarbon solvent after washing.
(11) Preparation of solid catalyst component (I) for olefin polymerization by contacting aliphatic magnesium such as magnesium stearate with titanium halide and ester compound (A) and then further contacting with titanium halide. how to.
(12) The dialkoxymagnesium is suspended in a hydrocarbon solvent, brought into contact with titanium halide, heated, and contacted with the ester compound (A) to obtain a solid product, which is then converted into a hydrocarbon. A method of preparing a solid catalyst component (I) for polymerization of olefins by washing with a solvent and then again contacting with a titanium halide in the presence of a hydrocarbon solvent, which is one of the above suspension / contact and contact reactions In the step of preparing a solid catalyst component (I) for olefin polymerization by contacting aluminum chloride.
(13) Dialkoxymagnesium, 2-ethylhexyl alcohol and carbon dioxide are contact-reacted in the presence of a hydrocarbon solvent to obtain a homogeneous solution, and this solution is contacted with titanium halide and the ester compound (A) to form a solid product. Further, this solid product is 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 an olefin. 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, the solid compound is brought into contact with the ester compound (A) and reacted, and the resulting reaction product is washed with a hydrocarbon solvent and then contacted again with a titanium halide in the presence of the hydrocarbon solvent. To obtain a solid catalyst component (I) for olefin polymerization.
(15) A dialkoxymagnesium, a titanium compound and an ester compound (A) are contact-reacted in the presence of a hydrocarbon solvent, and the resulting reaction product is contacted with a silicon compound such as polysiloxane, and titanium halide is further reacted. A method for obtaining a solid catalyst component (I) for olefin polymerization by contacting a metal salt of an organic acid and then contacting a titanium halide again.
(16) The dialkoxymagnesium and the ester compound (A) are suspended in a hydrocarbon solvent, and then heated to be brought into contact with the silicon halide, and then brought into contact with the titanium halide to obtain a solid product. A method for preparing the solid catalyst component (I) for olefin polymerization by washing the product with a hydrocarbon solvent and then bringing the product into contact with a titanium halide again 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 the component (I) in the present invention, any of the above methods can be suitably used. Among them, (1), (3), (4), (5), (7) The method of (8) or (10) is preferred, and the method of (3), (4), (7), (8), (10) is a solid catalyst component for olefin polymerization having high stereoregularity. It is particularly preferable in that it is obtained. In the most preferable preparation method, sarcoxymagnesium and ester compound (A) are suspended in a hydrocarbon solvent selected from linear hydrocarbons 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. Thus, the solid catalyst component (I) for olefin polymerization is obtained.

  In addition, from the viewpoint of improving the polymerization activity and hydrogen responsiveness of the solid catalyst component, the solid catalyst component (I) obtained by the above method is converted into an organosilicon compound having the Si—O—C bond, Si—N—. One of the preferred embodiments of the present invention is to contact the organosilicon compound having a C bond, and if necessary, the organoaluminum compound and, if necessary, the organosilicon compound represented by the general formula (8). is there. These compounds are contacted in the presence of a hydrocarbon solvent. Moreover, after making each component contact, in order to remove an unnecessary component, it fully wash | cleans with a hydrocarbon solvent. Further, these compounds may be contacted repeatedly.

  The temperature at which each component is brought into contact is −10 ° C. to 100 ° C., preferably 0 ° C. to 90 ° C., particularly preferably 20 ° C. to 80 ° C. The contact time is 1 minute to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 2 hours. The amount ratio used when contacting each component is arbitrary as long as the effect is not adversely affected, and is not particularly limited. Usually, the organosilicon compound having a Si—O—C bond, the organosilicon compound having a Si—N—C bond, and the organosilicon compound component represented by the general formula (8) are included in the solid catalyst component (I). In the range of 0.2 to 20 mol, preferably in the range of 0.5 to 10 mol, particularly preferably in the range of 1 to 5 per mol of titanium atom, the organoaluminum compound is a titanium atom 1 in the solid catalyst component (I). It is used in the range of 0.5 to 50 mol, preferably 1 to 20 mol, particularly preferably 1.5 to 10 mol per mol.

  The obtained solid catalyst component (I) for olefin polymerization is a powdered solid component by removing the remaining solvent until the weight ratio to the solid component is 1/3 or less, preferably 1/20 to 1/6. It is preferable to remove fine powder having a particle size of 11 μm or less mixed in the powder solid component by means such as air classification.

  The amount of each component used in preparing the solid catalyst component (I) varies depending on the preparation method, and thus cannot be specified 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 the ester compound (A) or the sum of the ester compound (A) and the electron donating compound (D) The amount is 0.01 to 10 mol, preferably 0.01 to 1 mol, more preferably 0.02 to 0.6 mol, and the solvent is 0.001 to 500 mol, preferably 0.001 to 100 mol, More preferably, it is 0.005-10 mol, and polysiloxane (E) is 0.01-100 g, Preferably it is 0.05-80 g, More preferably, it is 1-50 g.

  The olefin polymerization catalyst of the present invention comprises (I) a solid catalyst component, (II) an organoaluminum compound (hereinafter sometimes simply referred to as “organoaluminum compound (F)”), and (III) an external electron donating compound. (Hereinafter, it may be simply referred to as “external electron donating compound (G)”) to form a catalyst for olefin polymerization, and polymerization or copolymerization of olefins in the presence of the catalyst. it can. The solid catalyst component (I) contains the organosilicon compound having the Si—O—C bond, the organosilicon compound having the Si—N—C bond, or the organoaluminum compound (reaction reagent), or the reaction reagent. In the case where the solid catalyst component containing further contains an organosilicon compound represented by the general formula (7), the use of the external electron donating compound (G) can be omitted. This is because the solid catalyst component and the catalyst formed from organoaluminum exhibit excellent performance in polymerization activity and hydrogen responsiveness without using the external electron donating compound (G).

(II) As an organoaluminum compound, the following general formula (3);
R ²³ _p AlQ _3-p (3)
If R ²³ is a straight-chain or branched alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or halogen, and p is a real number of 0 <p ≦ 3, the compound is particularly limited. Although R ²³ is preferably an ethyl group or an iso-butyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, and particularly preferably 3.

  Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, tri-iso-propylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-iso-butylaluminum, and diethylaluminum. Examples include chloride, halogenated alkylaluminum such as diethylaluminum bromide, diethylaluminum hydride, etc. Among them, alkylaluminum halide such as diethylaluminum chloride, or triethylaluminum, tri-n-butylaluminum, tri-iso-butylaluminum, etc. Trialkylaluminum is preferably used, particularly preferably triethylaluminum and tri-iso-butylal It is a bromide. These organoaluminum 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, iso-cyanates, organosilicon compounds, especially organosilicon compounds having Si—O—C bonds or Si—N—C bonds An aminosilane compound having In addition, it is also possible to use the ester compound (A) of this invention as ester.

  Among these, esters such as ethyl benzoate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, 1,3 -Diethers, organosilicon compounds containing Si-O-C bonds, aminosilane compounds containing Si-N-C bonds are preferred, organosilicon compounds having Si-O-C bonds, aminosilanes having Si-N-C bonds Particularly preferred are compounds, 1,3-diethers.

Among the external electron donating compounds of the above (III), as the organosilicon compound having a Si—O—C bond, the following general formula (4);
R ²⁴ _q Si (OR ²⁵ ) _4-q (4)
(In the formula, R ²⁴ represents an alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, or a carbon number. Any one of 1 to 12 dialkylamino groups, which may be the same or different, R ²⁵ represents an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, or an allyl group; And an aralkyl group, which may be the same or different, and q is an integer of 0 ≦ q ≦ 3).

Among the external electron donating compounds of the above (III), as the aminosilane compound having a Si—N—C bond, the following general formula (5):
(R ²⁶ R ²⁷ N) _s SiR ²⁸ _4-s (5)
(Wherein R ²⁶ and R ²⁷ are a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, and a cycloalkyl having 3 to 20 carbon atoms. R ²⁶ and R ²⁷ may be the same or different, and R ²⁶ and R ²⁷ may be bonded to each other to form a ring, and R ²⁸ is a straight chain having 1 to 20 carbon atoms. Chain or branched alkyl group having 3 to 20 carbon atoms, vinyl group, allyl group, aralkyl group, linear or branched alkoxy group having 1 to 20 carbon atoms, vinyloxy group, allyloxy group, cycloalkyl having 3 to 20 carbon atoms group, aryl group, aryloxy group, and shows their derivatives, if R ²⁸ is plural, R ²⁸ is represented by good .s be the same or different is an integer of 1 to 3.) Aminosila Compounds.

  Examples of such organosilicon compounds include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) alkoxysilane, and alkyl (alkylamino). Examples include alkoxysilanes, cycloalkyl (alkylamino) alkoxysilanes, tetraalkoxysilanes, tetrakis (alkylamino) silanes, alkyltris (alkylamino) silanes, dialkylbis (alkylamino) silanes, and trialkyl (alkylamino) silanes. Specifically, phenyltrimethoxysilane, t-butyltrimethoxysilane, di-iso-propyldimethoxysilane, iso-propyl-i o-butyldimethoxysilane, di-iso-pentyldimethoxysilane, bis (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, diethylaminotriethoxysilane, bis (cyclohexyl) Mino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, etc., among which phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-iso-propyldimethoxysilane, iso-propyl-iso-butyldimethoxysilane, di-iso-pentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane , Tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) Silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotriethoxysilane and the like are preferably used.

Among the external electron donating compounds of the above (III), 1,3 diethers include the following general formula (6);
R ²⁹ R ³⁰ R ³¹ COCH ₂ (R ³⁵ R ³⁶ C) CH ₂ OCR ³² R ³³ R ³⁴ (6)
(In the formula, R ^{29 to} R ³⁴ are each a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group. R ³⁵ and R ³⁶ may be either a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a carbon number. Any one of 3 to 6 cycloalkyl groups and phenyl groups, which may be the same or different, and R ³⁵ and R ³⁶ may be bonded to each other to form a ring. , 3-diether compounds.

  Moreover, as such a 1,3-diether compound, specifically, 2-iso-propyl-2-iso-butyl-1,3-dimethoxypropane, 2,2-di-iso-butyl-1, 3-dimethoxypropane, 2-iso-propyl-2-iso-pentyl-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-iso-propyl-2-iso-butyl-1,3-dimethoxypropane, 9.9-bis (methoxymethyl) fluorene Etc. are preferably used.

  In addition, as the external electron donating compound (III), the organosilicon compound represented by the general formula (4), the organosilicon compound represented by the general formula (5), and the diether represented by the general formula (6). One or a combination of two or more of the compounds can also 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. , 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 in the range of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of the organoaluminum compound (F). Used.

  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 components and monomers is arbitrary, but preferably, the organoaluminum compound (F) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, Next, after contacting the solid 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 the external electron donating compound (G), the organoaluminum compound (F) is first charged into the prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then externally. A method in which the electron donating compound (G) is contacted and the solid catalyst component (I) is further contacted, and then an olefin such as propylene, or a mixture of propylene and one or more other olefins is contacted. 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 the α-olefin 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. Preferable polymerization methods are bulk polymerization method and gas phase polymerization method.

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. In this specification, Example 6 is a reference example.

(Production Example 1)
[Synthesis of diethyl norbornane-2,2-dicarboxylate]
To a mixture of 1.2 L toluene containing 4.26 moles of paraformaldehyde and 3.96 moles of acetic acid, 620 mmol of copper (II) acetate is added at 20 ° C. and the reaction is heated to 90 ° C., where 3.36 mol of diethyl malonate were added dropwise. The mixture was stirred under reflux for 5 hours using a Dean-Stark apparatus, cooled to room temperature and filtered. The filtrate was washed with water and then dried over anhydrous sodium sulfate. The mixture was added to 5 g of hydroquinone and 5 g of maleic acid, concentrated under reduced pressure, and the residue was distilled to obtain Intermediate 1 (diethyl 2-methylenemalonate). Next, 1.13 mol of cyclopentadiene was added dropwise at 20 ° C. to a stirred mixture of Intermediate 1 and 1.3 L of acetonitrile, and after stirring for 16 hours, the reaction was poured into 2 L of water, and ethyl acetate was added. The product was extracted. The mixed extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain intermediate 2 (5-norbornene-2,2-dicarboxylic acid Diethyl) was obtained. A palladium-carbon catalyst is added to a stirred solution of Intermediate 2 and 1.2 L of ethanol, the suspension is degassed under vacuum and purged with hydrogen for several minutes, after which the reaction mixture is stirred at 16 ° C. under hydrogen at 50 ° C. Stir for hours. The target product was obtained by removing the catalyst by filtration and concentrating under low pressure. The yield was 84%.

As a result of analyzing the ¹ H-NMR spectrum by the nuclear magnetic resonance apparatus, the chemical shift values are 1.08 to 1.32 (m, 8H), 1.35 to 1.55 (m, 3H), 1 respectively. .59 to 1.65 (m, 1H), 2.20 to 2.30 (m, 2H), 2.83 (d, 1H), 4.00 to 4.30 (m, 4H) ppm, From this, it was confirmed that the obtained product was diethyl norbornane-2,2-dicarboxylate. In addition, as a result of measuring by liquid chromatography, the purity of the obtained diethyl norbornane-2,2-dicarboxylate was 98%.

(Production Example 2)
[Synthesis of dimethyl norbornane-2,2-dicarboxylate]
To a mixture consisting of 1.5 L toluene containing 4.77 mol paraformaldehyde and 4.43 mol acetic acid, 682 mmol of copper (II) acetate is added at 20 ° C. and the reaction is heated to 90 ° C., where 3.79 mol of dimethyl malonate was added dropwise. The mixture was stirred at reflux for 4 hours using a Dean-Stark apparatus and filtered. The filtrate was washed with water and then dried over anhydrous sodium sulfate. The mixture was added to 5 g of hydroquinone and 5 g of maleic acid, concentrated under reduced pressure, and the residue was distilled to obtain Intermediate 1 (dimethyl 2-methylenemalonate). Next, 902 mmol of cyclopentadiene was added dropwise at 20 ° C. to a stirred mixture of Intermediate 1 and 1.3 L of acetonitrile, and after stirring for 16 hours, the reaction was poured into 2 L of water and the product was added with ethyl acetate. Extracted. The mixed extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain intermediate 2 (5-norbornene-2,2-dicarboxylic acid Dimethyl) was obtained. A palladium-carbon catalyst is added to a stirred solution of Intermediate 2 and 1.2 L of ethanol, the suspension is degassed under vacuum and purged with hydrogen for several minutes, after which the reaction mixture is stirred at 16 ° C. under hydrogen at 50 ° C. Stir for hours. The target product was obtained by removing the catalyst by filtration and concentrating under low pressure. The yield was 96%.

As a result of analyzing the ¹ H-NMR spectrum by the nuclear magnetic resonance apparatus, the chemical shift values are 1.04 to 1.14 (m, 1H), 1.19 to 1.27 (m, 1H), 1 respectively. .31 to 1.40 (m, 1H), 1.41 to 1.59 (m, 2H), 1.60 to 1.68 (m, 1H), 1.71 to 1.80 (m, 1H) , 2.21 to 2.27 (m, 2H), 2.83 to 2.85 (m, 1H), 3.65 to 3.70 (m, 6H) ppm. It was confirmed that the product was dimethyl norbornane-2,2-dicarboxylate. In addition, as a result of measuring by liquid chromatography, the purity of the obtained dimethyl norbornane-2,2-dicarboxylate was 99%.

(Production Example 3)
[Synthesis of norbornane-2,2-dicarboxylate dibutyl]
A mixture of 720 mL of toluene containing 1.92 mol of malonic acid, 11.5 mol of 1-butanol and 22.0 mol of 4-methylbenzene sulfonic acid was refluxed using a Dean-Stark apparatus at reflux. The mixture was stirred for an hour, cooled to room temperature, washed with 500 mL of a saturated aqueous solution of sodium bicarbonate, and dried over anhydrous sodium sulfate. The mixture was concentrated under low pressure to obtain Intermediate 1 (dibutyl malonate). To a stirred mixed solution consisting of 500 mL of toluene and 550 mmol of acetic acid containing 600 mmol of paraformaldehyde, 80 mmol of copper (II) sulfate was added at 20 ° C., heated to 90 ° C., and 460 mmol of intermediate 1 was added dropwise. did. The mixture was stirred at reflux using a Dean-Stark apparatus for 5 hours, cooled to room temperature and filtered. The filtrate was washed with water and dried over anhydrous sodium sulfate. Thereto, 0.5 g of hydroquinone and 0.5 g of maleic acid were added, concentrated under low pressure, and the residue was distilled to obtain Intermediate 2 (dibutyl 2-methylenemalonate). Next, 0.293 mol of cyclopentadiene was added dropwise to a stirred mixture of Intermediate 2 and 200 mL of acetonitrile at 20 ° C. and stirred for 16 hours, and then the reaction was poured into 2 L of water, and the product was diluted with ethyl acetate. Extracted. The combined extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain intermediate 3 (dibutyl 5-norbornene-2,2-dicarboxylate). ) The palladium-carbon catalyst was added to a stirred solution of Intermediate 3 and 500 mL of ethanol, the suspension was degassed under vacuum, purged with hydrogen for several minutes, and then the reaction mixture was stirred at 40 ° C. under hydrogen for 16 hours. . The target product was obtained by removing the catalyst by filtration and concentrating under low pressure. The yield was 75%.

As a result of analyzing the ¹ H-NMR spectrum by a nuclear magnetic resonance apparatus, the chemical shift values are 0.92 to 0.96 (m, 6H), 1.14 to 1.19 (m, 1H), 1 respectively. .27 to 1.41 (m, 6H), 1.46 to 1.55 (m, 2H), 1.60 to 1.66 (m, 5H), 1.76 to 1.78 (m, 1H) 2.26-2.30 (m, 2H), 2.88 (br, 1H), 4.07-4.15 (m, 4H) ppm, from which the product obtained was norbornane It was confirmed that it was dibutyl-2,2-dicarboxylate. In addition, as a result of measuring by liquid chromatography, the purity of the obtained norbornane-2,2-dicarboxylate dibutyl was 98%.

(Production Example 4)
[Synthesis of dimethyl 3-methyl-norbornane-2,2-dicarboxylate]
To a stirred solution of 2 L anhydrous tetrahydrofuran containing 908 mmol titanium tetrachloride and 200 mL carbon tetrachloride, 50 mL carbon tetrachloride containing 682 mmol anhydrous acetaldehyde and 454 mmol dimethyl malonate was added at 0 ° C. After stirring for 1 min, 1.82 mol of pyridine was added dropwise. After stirring the reaction mixture at 20 ° C. for 16 hours, the reaction was poured into 2 L of cold water and extracted with ethyl acetate. The mixed extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain Intermediate 1 (dimethylidene malonate). To a stirred mixture of intermediate 12 and 500 mL of toluene containing 510 mmol of cyclopentadiene, 51 mmol of titanium tetrachloride was added dropwise at 0 ° C. and the reaction mixture was stirred at 20 ° C. for 16 hours, after which the reaction was added to 800 mL of Poured into water and extracted with ethyl acetate. The combined extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain Intermediate 2. A palladium carbon catalyst was added to a stirred solution of Intermediate 2 and 1.2 L of ethanol, degassed under vacuum and purged with hydrogen for several minutes, and then the reaction mixture was stirred under hydrogen at 25 ° C. for 16 hours. After removing the catalyst by filtration and concentrating under low pressure, the residue was purified by silica gel column chromatography to obtain the desired product. The yield was 76%.

As a result of analyzing the ¹ H-NMR spectrum by a nuclear magnetic resonance apparatus, the chemical shift values were 0.88 (d, 2.4 H), 0.9 to 1.1 (m, 1 H), and 1.13, respectively. (D, 0.6H), 1.25 to 1.35 (m, 2H), 1.40 to 1.65 (m, 3H), 1.71 to 1.80 (m, 0.2H), 1 .90 (d, 0.8H), 0.95 to 2.05 (m, 0.8H), 2.13 (s, 0.2H), 2.45 to 2.56 (m, 0.2H) , 2.60-2.70 (m, 0.8H), 2.72-2.85 (m, 1H), 3.64-3.68 (m, 3H), 3.69-3.72 ( m, 3H) ppm. From this, it was confirmed that the obtained product was dimethyl 3-methyl-norbornane-2,2-dicarboxylate. As a result of measurement by gas chromatography, the purity of the obtained dimethyl 3-methyl-norbornane-2,2-dicarboxylate was 98%.

(Production Example 5)
[Synthesis of diethyl 5-norbornene-2,2-dicarboxylate]
To a mixture of 1.2 L toluene containing 4.15 mol of paraformaldehyde and 4.25 mol acetic acid, 450 mmol of copper (II) acetate was added at 20 ° C. and the reaction was heated to 90 ° C., where 2.50 mol of diethyl malonate was added dropwise. The mixture was stirred under reflux for 6 hours using a Dean-Stark apparatus, cooled to room temperature and filtered. The filtrate was washed with water and then dried over anhydrous sodium sulfate. The mixture was added to 5 g of hydroquinone and 5 g of maleic acid, concentrated under reduced pressure, and the residue was distilled to obtain Intermediate 1 (diethyl 2-methylenemalonate). Next, 930 mmol of cyclopentadiene was added dropwise at 20 ° C. to a stirred mixture of Intermediate 1 and 1.0 L of acetonitrile, and after stirring for 16 hours, the reaction was poured into 2 L of water and the product was added with ethyl acetate. Extracted. The mixed extract was washed with brine, dried over anhydrous sodium sulfate, concentrated under low pressure, and the residue was purified by silica gel column chromatography to obtain the desired product. The yield was 5.2%.

As a result of analyzing the ¹ H-NMR spectrum by the nuclear magnetic resonance apparatus, the chemical shift values are 1.15 to 1.28 (m, 6H), 1.45 to 1.55 (m, 1H), 1 respectively. .60 to 1.70 (d, 1H), 1.92 to 2.15 (m, 2H), 2.88 (brs, 1H), 4.05 to 4.30 (m, 4H), 5.90 ˜6.05 (m, 1H), 6.20 to 6.30 (m, 1H) ppm, and from this, the product obtained is diethyl 5-norbornene-2,2-dicarboxylate It was confirmed. In addition, as a result of measuring by gas chromatography, the purity of the obtained diethyl 2,2-norbornane dicarboxylate was 99%.

Example 1
[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 The temperature was raised by adding 20 ml of titanium tetrachloride, and when the temperature reached 60 ° C., 15.3 mmol of diethyl norbornane-2,2-dicarboxylate was added to reach 100 ° C. Then, it was made to react for 90 minutes in the state holding the temperature of 100 degreeC. After completion of the reaction, the supernatant was extracted, and the reaction product was washed 6 times with 75 ml of toluene at 100 ° C. 50 ml of toluene and 10 ml of titanium tetrachloride were newly added and the temperature was raised, and the reaction was carried out with stirring for 15 minutes. After completion of the reaction, the supernatant was extracted and the same reaction was performed twice more. Subsequently, it was washed 6 times with 75 ml of n-heptane at 40 ° C. to obtain a solid catalyst component A.
The solid solution of the solid catalyst component A was separated, and the titanium content in the solid content and the content of diethyl norbornane-2,2-dicarboxylate as an electron donating compound were measured. The titanium content was 2.6. % By weight and the content of diethyl norbornane-2,2-dicarboxylate was 15.6% by weight.
In Examples and Comparative Examples, the titanium content in the solid content and the content of the internal electron donating compound were measured as follows.

[Titanium content in solids]
The titanium content in the solid content was measured according to the method of JIS M 8301.

[Content of internal electron donating compound in solid content]
The content of the internal electron donating compound in the solid is determined by hydrolyzing the solid with a certain amount of toluene and distilled water, and extracting the internal electron donating compound extracted in toluene with a gas chromatograph (Shimadzu Corporation). Using a calibration curve measured in advance at a known concentration from the measurement result of gas chromatography for the number of moles of each component (each internal electron donating compound). Asked.
(Measurement condition)
Column: packed column (φ 2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAW DMCS 80/100, manufactured by GL Sciences Inc.)
・ Detector: FID (Frame Ionization Detector, hydrogen flame ionization detector)
Carrier gas: helium, flow rate 40 ml / min Measurement temperature: vaporization chamber 280 ° C, column 225 ° C, detector 280 ° C

[Formation and polymerization of polymerization catalyst]
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. The polymerization activity per gram of the solid catalyst component at this time, the ratio of p-xylene solubles in the produced polymer (XS), the melt flow rate value (MFR) of the produced polymer, and the molecular weight distribution of the produced polymer are shown. It was shown in 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) = mass of polymer (g) / mass of solid catalyst component (g)

(Measurement of xylene solubles (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.). -The polymer was dissolved over 2 hours while maintaining the temperature of xylene at the boiling point (137-138 ° C). 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.

(Molecular weight distribution of polymer)
The molecular weight distribution of the polymer was evaluated by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained by measurement under the following conditions using a gel permeation chromatograph (GPC) (GPCV2000 manufactured by Waters).
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: 1.0ml / min

(Example 2)
[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that 6.0 liter of hydrogen gas was used instead of 1.5 liter of hydrogen gas. The polymerization results are shown in Table 1.

(Example 3)
[Synthesis of Solid Catalyst Component B]
A solid catalyst component B was prepared in the same manner as in Example 1, except that 15.3 mmol of norbornane-2,2-dicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. . As a result, the titanium content in the obtained solid catalyst component was 2.6% by weight, and the content of dimethyl norbornane-2,2-dicarboxylate was 12.9% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component B was used in place of the solid catalyst component A. The polymerization results are shown in Table 1.

Example 4
[Synthesis of Solid Catalyst Component C]
A solid catalyst component C was prepared in the same manner as in Example 1 except that 15.3 mmol of norbornane-2,2-dicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. . As a result, the titanium content in the obtained solid catalyst component was 2.7% by weight, the content of dibutyl norbornane-2,2-dicarboxylate was 16.6% by weight, and ethylbutyl norbornane-2,2-carboxylate. The content was 0.63% by weight, and the content of diethyl norbornane-2,2-dicarboxylate was 0.18% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized 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.

(Example 5)
[Synthesis of solid catalyst component D]
The solid catalyst component was the same as in Example 1, except that 15.3 mmol of dimethyl 3-methyl-norbornane-2,2-dicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. D was prepared. As a result, the titanium content in the obtained solid catalyst component was 1.9% by weight, and the content of dimethyl 3-methyl-norbornane-2,2-dicarboxylate was 6.85% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component D was used instead of the solid catalyst component A. The polymerization results are shown in Table 1.

(Example 6)
[Synthesis 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 diethyl 5-norbornene-2,2-dicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. Prepared. As a result, the titanium content in the obtained solid catalyst component was 4.2% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized 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 1)
[Synthesis of solid catalyst component F]
A solid catalyst component F was prepared in the same manner as in Example 1, except that 15.3 mmol of dimethyl diisobutylmalonate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. As a result, the titanium content in the obtained solid catalyst component was 3.6% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component F was used instead of the solid catalyst component A. The polymerization results are shown in Table 1. However, the molecular weight distribution of the polymer was not evaluated.

(Comparative Example 2)
[Formation and polymerization of polymerization catalyst]
Polymerization was carried out in the same manner as in Comparative Example 1 except that 6.0 liter of hydrogen gas was used instead of 1.5 liter of hydrogen gas. The polymerization results are shown in Table 1.

(Comparative Example 3)
[Synthesis of Solid Catalyst Component G]
A solid catalyst component G was prepared in the same manner as in Example 1 except that 15.3 mmol of diethyl 1,1-cyclobutanedicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. As a result, the titanium content in the obtained solid catalyst component was 3.0% by weight, and the content of diethyl 1,1-cyclobutanedicarboxylate was 11.7% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component G was used instead of the solid catalyst component A. The polymerization results are shown in Table 1.

(Comparative Example 4)
[Synthesis of solid catalyst component H]
Solid catalyst component H was prepared in the same manner as in Example 1 except that 15.3 mmol of diethyl 1,1-cyclohexanedicarboxylate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. As a result, the titanium content in the obtained solid catalyst component was 2.2% by weight, and the content of diethyl 1,1-cyclohexanedicarboxylate was 11.4% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component H was used instead of the solid catalyst component A. The polymerization results are shown in Table 1.

(Reference Example 1)
[Synthesis of Solid Catalyst Component I]
A solid catalyst component I was prepared in the same manner as in Example 1 except that 15.3 mmol of di-n-butyl phthalate was used instead of 15.3 mmol of diethyl norbornane-2,2-dicarboxylate. The content of di-n-butyl phthalate in the obtained solid catalyst component was 14.5% by weight.

[Formation and polymerization of polymerization catalyst]
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component I was used in place of the solid catalyst component A. The polymerization results are shown in Table 1.

(Reference Example 2)
[Formation and polymerization of polymerization catalyst]
Polymerization was carried out in the same manner as in Reference Example 1 except that 6.0 liters of hydrogen gas was used instead of 1.5 liters of hydrogen gas. The polymerization results are shown in Table 1. However, the molecular weight distribution of the polymer was not evaluated.

  The catalyst for olefin polymerization obtained by the present invention has a higher polymerization activity and stereoregularity than the conventional olefin polymer obtained from a solid catalyst component containing a conventional malonic acid ester, and a conventional solid catalyst containing a phthalic acid ester. An olefin polymer having a molecular weight distribution similar to that of the olefin polymer obtained from the components and having a higher hydrogen activity can be obtained in a high yield. A catalyst component and a catalyst for olefin polymerization can be provided.

Claims (10)

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

(Wherein R ^{1 to} R ¹⁰ represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a substituted hydrocarbon group, or a heteroatom-containing group, and may be the same or different from each other. The adjacent groups may be bonded to each other to form a ring, and R ¹¹ and R ¹² represent a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different from each other. one or olefin polymerization solid catalyst component containing two or more ester compounds in selected compounds represented by either et al. R ^{1 to} R ¹⁰ are a hydrogen atom, a linear alkyl group having 1 to 6 hydrocarbons, a branched alkyl group having 3 to 6 carbon atoms, a vinyl group, a linear alkenyl group having 3 to 6 carbon atoms, or branched. The olefin polymerization according to claim 1, which is a alkenyl group, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkenyl group having 5 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. Solid catalyst component. 3. The solid for olefin polymerization according to claim 1, wherein R ¹¹ or R ¹² is a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms. Catalyst component. (I) The solid catalyst component for olefin polymerization according to any one of claims 1 to 3 and (II) the following general formula (3); R ²³ _p AlQ _3-p (3)
(In the formula, R ²³ represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen atom or halogen, and p is a real number of 0 <p ≦ 3, which may be the same or different.) A catalyst for olefin polymerization, which is obtained by contacting an organoaluminum compound represented by the formula:   The catalyst for olefin polymerization according to claim 4, which is obtained by further contacting (III) an external electron donating compound. The external electron donating compound (III) is represented by the following general formula (4):
R ²⁴ _q Si (OR ²⁵ ) _4-q (4)
(In the formula, R ²⁴ represents an alkyl group having 1 to 12 carbon atoms, a vinyl group, an allyl group, an aralkyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, an alkylamino group having 1 to 12 carbon atoms, or a carbon number. is any of 1-12 dialkylamino group, q is 0 <an integer q ≦ 3, when q is 2 or more, plural R ²⁴ may optionally be the same or different .R ²⁵ is alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, a plurality of R ²⁵ may be different even in the same.) And the following general formula (5);
(R ²⁶ R ²⁷ N) _s SiR ²⁸ _4-s (5)
(Wherein R ²⁶ and R ²⁷ are a hydrogen atom, a straight chain having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, an allyl group, an aralkyl group, and a cycloalkyl having 3 to 20 carbon atoms. group, an aryl ^{group, R 26} and ^{R 27} also may, be different even if the same is ^{R 26} and ^{R 27} good ^{.R 28} be bonded to each other to form a ring is 1 carbon atoms 20 straight chain or branched alkyl group having 3 to 20 carbon atoms, vinyl group, allyl group, aralkyl group, straight chain or branched alkoxy group having 1 to 20 carbon atoms, vinyloxy group, allyloxy group, 3 to 20 carbon atoms cycloalkyl group, an aryl group, an aryl group, if R ²⁸ is plural, R ²⁸ is an integer of good .s be different even in the same 1 3.) selected from 1 type or 2 types or more Claim 5, wherein the catalyst for polymerization of olefins, characterized in that the organic silicon compound. The external electron donating compound (III) is represented by the following general formula (6):
_{^{R 29 R 30 R 31 COCH 2}} (R 35 R 36 C) CH 2 OCR 32 R 33 R 34
(6)
(In the formula, R ^{29 to} R ³⁴ are each a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a phenyl group. R ³⁵ and R ³⁶ may be either a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, or a carbon number. Any one of 3 to 6 cycloalkyl groups and phenyl groups, which may be the same or different, and R ³⁵ and R ³⁶ may be bonded to each other to form a ring. The olefin polymerization catalyst according to claim 5, wherein The organosilicon compound is phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, di-iso-propyldimethoxysilane, iso-propyl-iso-butyldimethoxysilane, di-iso-pentyldimethoxysilane. , Diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane , bis (perhydroisoquinolino) dimethoxysilane, claim 6 Symbol, characterized in that one or more compounds selected from diethylamino triethoxy silane The catalyst for polymerization of olefins.   The diether may be 2-iso-propyl-2-iso-pentyl-1,3-dimethoxypropane, 2-iso-propyl-2-iso-butyl-1,3-dimethoxypropane or 9,9-bis (methoxy The catalyst for olefin polymerization according to claim 7, which is methyl) fluorene.   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 9.

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