JP5745980B2 - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer - Google Patents

Description

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

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

  For example, Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) discloses a solid titanium catalyst component on which a specific electron donor is supported, an organoaluminum compound as a promoter component, and at least one Si-OR ( In the formula, it is described that when a silicon compound having R is a hydrocarbon group, excellent polymerization activity and stereospecificity are expressed.

  As the specific electron donating component, phthalate ester is used in Patent Document 2 (Japanese Patent Laid-Open No. 58-83006), and cellosolve ester is used in Patent Document 3 (Japanese Patent Laid-Open No. 60-130607). Each is disclosed. However, the solid catalyst component carrying these electron donors has room for improvement in both polymerization activity and stereoregularity.

  On the other hand, as another attempt, Patent Document 4 (Japanese Patent Application Laid-Open No. 2004-91513) discloses a solid catalyst component using a malonic acid diester.

  However, when such a catalyst system composed of a solid catalyst component using a malonic acid ester is used for propylene polymerization, the stereoregularity of the resulting polypropylene is generally not sufficiently high and requires high rigidity. It is difficult to apply to injection molded articles and the like, and it has been mainly used for general-purpose resins whose required level of mechanical strength is not so high. In addition, since the activity against hydrogen is relatively high, when producing a grade such as a sheet that requires a low melt flow, propylene polymerization is carried out in a state where the amount of hydrogenation is small, so that the polymerization activity decreases. There was a problem such as, and further improvement was needed.

Patent Document 5 (Japanese Patent Laid-Open No. 3-706) discloses RO—CH ₂ (CR ¹ R ² ) CH ₂ —OR wherein R, R ¹ and R ² are each 1 to 18 carbon atoms. A solid catalyst component using a diether represented by a linear or branched alkyl, alicyclic, aryl, alkylaryl or arylalkyl group having an atom, and R ¹ or R ² may be hydrogen; (Japanese Patent Laid-Open No. 03-62805) includes R ¹ R ² C (CH ₂ OR ³ ) (CH ₂ OR ⁴ ) (wherein R ¹ and R ² are alkyl having 1 to 18 carbon atoms, Solid catalyst components using a diether compound represented by a cycloalkyl or aryl group, wherein R ³ and R ⁴ are alkyl groups having 1 to 4 carbon atoms are disclosed.

Furthermore, Patent Document 7 (Japanese Patent Laid-Open No. 10-298224) discloses (R ¹ OCH ₂ ) R ³ R ⁴ C (COOR ² ) (wherein R ¹ and R ² are each 1 to 20 carbon atoms. A straight-chain hydrocarbon group or a branched hydrocarbon group having 3 to 20 carbon atoms, wherein R ³ and R ⁴ are linear hydrocarbon groups having 1 to 20 carbon atoms, 3 to 20 A solid catalyst component using an alkoxyester compound represented by a branched hydrocarbon group having 1 carbon atom or a hydrogen atom is disclosed.

  However, when a solid catalyst component using the above diether compound or alkoxy ester compound as an internal electron donor is used for propylene polymerization, the stereoregularity of the resulting olefin polymer is increased, but the polymerization activity is decreased. It had the problem that

  In addition, when a solid catalyst component using the above diether compound as an internal electron donor is used for propylene polymerization, the molecular weight distribution of the resulting olefin polymer is narrowed, and the molecular weight distribution of the resulting olefin polymer is moderate. However, there was a problem that it was difficult to control within a certain range.

JP 57-63310 A JP 58-83006 A JP-A-60-130607 JP 2004-91513 A Japanese Unexamined Patent Publication No. 3-706 Japanese Patent Laid-Open No. 03-62805 JP-A-10-298224

  By the way, as a catalyst to be used for stereoregular polymerization of olefins, various polymerization performances such as activity, stereoregularity, molecular weight distribution, sustainability of activity, MFR controllability (hydrogen responsiveness), and bulk density are required. Because the required performance varies depending on the application, various solid catalyst components having different characteristics and catalysts are required. The molecular weight distribution of a polymer used for general purposes is required to be controllable, for example, in the range of about 4 to 6 in terms of Mw / Mn value, and other performance is excellent in that range, that is, crystallinity of a certain degree or more. It is said that a solid catalyst component exhibiting a high polymerization activity to some extent is most practical.

  Therefore, in order to meet various needs, the object of the present invention is to have a high stereoregularity and a high polymerization activity, and the molecular weight distribution of the polymer within an appropriate Mw / Mn value range that does not impair the moldability. An object of the present invention is to provide a novel controllable solid catalyst component for olefin polymerization and a catalyst for olefin polymerization.

  Under such circumstances, the present inventors have conducted intensive studies and found that an olefin polymerization catalyst containing titanium, magnesium, halogen and an ether-ester compound having a specific structure can solve the above problems. The present invention has been completed.

That is, the present invention relates to titanium, magnesium, halogen and the following general formula (1);

(1)
(In the formula, R ¹ and R ² are a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, and a linear chain having 3 to 20 carbon atoms. Alkenyl group or branched alkenyl group, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, branched halogen-substituted alkyl group having 3 to 20 carbon atoms, linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, carbon number Branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, halogen substitution having 3 to 20 carbon atoms Including a cycloalkenyl group, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and a nitrogen atom having 2 to 24 carbon atoms whose bond ends are carbon atoms. A hydrocarbon group, a C2-C24 oxygen atom-containing hydrocarbon group whose bond terminal is a carbon atom, a C2-C24 phosphorus-containing hydrocarbon group whose bond terminal is a carbon atom, or C1-C24 A silicon-containing hydrocarbon group, wherein R ¹ and R ² may be the same or different, and may be bonded to each other to form a cyclic group, provided that R ¹ is hydrogen or methyl; When it is a group, the carbon number of R ² is 2 or more, and R ³ and R ⁴ are a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, and a carbon number. 3-20 linear alkenyl group or branched alkenyl group, C1-C20 linear halogen-substituted alkyl group, C3-C20 branched halogen-substituted alkyl group, C2-C20 linear halogen Substituted alkenyl group, C3-C20 branch Halogen-substituted alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, carbon A C6-C24 aromatic hydrocarbon group, a C6-C24 halogen-substituted aromatic hydrocarbon group, a C2-C24 nitrogen atom-containing hydrocarbon group in which the bond terminal is a carbon atom, and a bond terminal in the carbon atom An oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms, a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms whose bond ends are carbon atoms, or a silicon-containing hydrocarbon group having 1 to 24 carbon atoms; ³ and R ⁴ may be the same or different, provided that the nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms in R ^{1 to} R ⁴ is a group in which the bond terminal is a C═N group. , The carbon number 2 Oxygen atom-containing hydrocarbon group of 24, those coupling terminal is a carbonyl group, a phosphorus-containing hydrocarbon group of carbon number 2 to 24 are excluded respectively those bond terminus is C = P group. It is intended to provide a solid catalyst component for olefin polymerization containing a compound represented by

The present invention also provides (I) the solid catalyst component,
(II) the following general formula (2);
R ⁵ _p AlQ _3-p (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen atom, a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom, p is a real number of 0 <p ≦ 3, and R ⁵ may be the same or different.)
And (III) a catalyst for polymerization of olefins formed by an external electron donating compound.

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

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

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

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

  The halogen contained as an essential component in component (I) includes, for example, each atom of fluorine, chlorine, bromine or iodine. Among them, chlorine, bromine or iodine is preferable, and chlorine or iodine is particularly preferable. .

In R ¹ and R ² in the above general formula (1), examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms. Among them, chlorine, bromine, and iodine are preferable, and particularly preferable. Chlorine or bromine.

In R ^{1 to} R ⁴ in the general formula (1), examples of the linear alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and the like. Preferably, it is a C1-C12 linear alkyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as C3-C20 branched alkyl group, secondary, such as isopropyl group, isobutyl group, t-butyl group, isopentyl group, neopentyl group etc., for example Examples include alkyl groups having carbon or tertiary carbon. Preferably, it is a C3-C12 branched alkyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 linear alkenyl group, an allyl group, 3-butenyl group, 4-hexenyl group, 5-hexenyl group, 7 -Octenyl group, 10-dodecenyl group etc. are mentioned, Preferably it is a C3-C12 linear alkenyl group.

In R ^{1 to} R ⁴ in the general formula (1), examples of the branched alkenyl group having 3 to 20 carbon atoms include isopropenyl group, isobutenyl group, isopentenyl group, and 2-ethyl-3-hexenyl group. Can be mentioned. Preferably, it is a C3-C12 branched alkenyl group.

In R ^{1 to} R ⁴ in the general formula (1), examples of the linear halogen-substituted alkyl group having 1 to 20 carbon atoms include a halogenated methyl group, a halogenated ethyl group, a halogenated n-propyl group, Examples thereof include a halogenated n-butyl group, a halogenated n-pentyl group, a halogenated n-hexyl group, a halogenated n-pentyl group, a halogenated n-octyl group, a halogenated nonyl group, and a halogenated decyl group. Preferably, it is a C1-C12 linear halogen-substituted alkyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 branched halogen-substituted alkyl group, halogenated isopropyl group, halogenated isobutyl group, halogenated 2-ethylhexyl group, halogenated And neopentyl group. Preferably, it is a branched halogen-substituted alkyl group having 3 to 12 carbon atoms.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), C2-C20 linear halogen-substituted alkenyl group is 2-halogenated vinyl group, 3-halogenated allyl group, 3-halogen. 2-butenyl group, 4-halogenated-3-butenyl group, perhalogenated-2-butenyl group, 6-halogenated-4-hexenyl group, 3-trihalogenated methyl-2-propenyl group, etc. It is done. A halogen-substituted alkenyl group having 2 to 12 carbon atoms is preferred.

In R ^{1 to} R ⁴ in the general formula (1), examples of the branched halogen-substituted alkenyl group having 3 to 20 carbon atoms include 3-trihalogenated-2-butenyl group and 2-pentahalogenated ethyl-3. -Hexenyl group, 6-halogenated-3-ethyl-4-hexenyl group, 3-halogenated isobutenyl group and the like can be mentioned. A branched halogen-substituted alkenyl group having 3 to 12 carbon atoms is preferred.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, A cyclononyl group, a cyclodecyl group, etc. are mentioned. Preferably it is a C1-C12 cycloalkyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 cycloalkenyl group, a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, a norbornene group, etc. are mentioned. It is done. Preferably it is a C3-C12 cycloalkenyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 halogen-substituted cycloalkyl group, a halogen-substituted cyclopropyl group, a halogen-substituted cyclobutyl group, a halogen-substituted cyclopentyl group, a halogen-substituted trimethyl Examples thereof include a cyclopentyl group, a halogen-substituted cyclohexyl group, a halogen-substituted methylcyclohexyl group, a halogen-substituted cycloheptyl group, a halogen-substituted cyclooctyl group, a halogen-substituted cyclononyl group, a halogen-substituted cyclodecyl group, and a halogen-substituted butylcyclopentyl. Preferably it is a C1-C12 halogen substituted cycloalkyl group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C3-C20 halogen-substituted cycloalkenyl group, a halogen-substituted cyclopropenyl group, a halogen-substituted cyclobutenyl group, a halogen-substituted cyclopentenyl group, a halogen-substituted Examples include trimethylcyclopentenyl group, halogen-substituted cyclohexenyl group, halogen-substituted methylcyclohexenyl group, halogen-substituted cycloheptenyl group, halogen-substituted cyclooctenyl group, halogen-substituted cyclononenyl group, halogen-substituted cyclodecenyl group, and halogen-substituted butylcyclopentenyl. Preferably it is a C1-C12 halogen-substituted cycloalkenyl group.

In R ^{1 to} R ⁴ in the general formula (1), a linear halogen-substituted alkyl group, a branched halogen-substituted alkyl group, a linear halogen-substituted alkenyl group, a branched halogen-substituted alkenyl group, a halogen-substituted cycloalkyl group The halogen species of the halogen-substituted cycloalkenyl group and the halogen-substituted aromatic hydrocarbon group include fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, particularly preferably fluorine or chlorine.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a C6-C24 aromatic hydrocarbon group, a phenyl group, a methylphenyl group, a dimethylphenyl group, an ethylphenyl group, a benzyl group, 1 -Phenylethyl group, 2-phenylethyl group, 2-phenylpropyl group, 1-phenylbutyl group, 4-phenylbutyl group, 2-phenylheptyl group, tolyl group, xylyl group, naphthyl group, 1,8-dimethylnaphthyl Groups and the like. Preferably it is a C6-C12 aromatic hydrocarbon group.

In R ^{1 to} R ⁴ in the general formula (1), the halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms includes a halogenated phenyl group, a halogenated methylphenyl group, and a trihalogenated methylphenyl group. Perhalogenated benzyl group, perhalogenated phenyl group, 2-phenyl, 2-halogenated ethyl group, perhalogenated naphthyl group, 4-phenyl, 2,3-dihalogenated butyl group and the like. Preferably it is a 6-12 halogen-containing aromatic hydrocarbon group.

In addition, in R ^{1 to} R ⁴ in the above general formula (1), as the nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms, excluding those in which the bond terminal is a C═N group, the bond terminal is a carbon atom. For example, methylaminomethyl group, dimethylaminomethyl group, ethylaminomethyl group, diethylaminomethyl group, propylaminomethyl group, dipropylaminomethyl group, methylaminoethyl group, dimethylaminoethyl group, ethylaminoethyl Group, diethylaminoethyl group, propylaminoethyl group, dipropylaminoethyl group, butylaminoethyl group, dibutylaminoethyl group, pentylaminoethyl group, dipentylaminoethyl group, hexylaminoethyl group, hexylmethylaminoethyl group, heptylmethyl Aminoethyl, diheptylaminomethyl, oct Alkylaminoalkyl groups such as rumethylaminomethyl group, dioctylaminoethyl group, nonylaminomethyl group, dinonylaminomethyl group, decylaminomethyl group, didecylamino group, cyclohexylaminomethyl group, dicyclohexylaminomethyl group; phenylaminomethyl group An arylaminoalkyl group or an alkylarylaminoalkyl group such as a diphenylaminomethyl group, a ditolylaminomethyl group, a dinaphthylamino group methyl, a methylphenylaminoethyl group; a polycyclic aminoalkyl group; an anilino group, a dimethylaminophenyl group; Amino group-containing aromatic hydrocarbon group such as bisdimethylaminophenyl group; imino such as methyliminomethyl, ethyliminoethyl, propyliminomethyl, butyliminoethyl, phenyliminomethyl Alkyl group, and the like. Preferably it is a 2-12 nitrogen atom containing hydrocarbon group. In R ¹ and R ² , the bond terminal is an atom or group on the carbon atom side to which R ¹ and R ² are bonded. In R ³ and R ⁴ , the bond terminal is R ³ and R ^4. An atom or group on the oxygen atom side to be bonded. Hereinafter, the bond ends in R ^{1 to} R ⁴ have the same meaning.

In addition, in R ^{1 to} R ⁴ in the general formula (1), the oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms excluding those having a bond terminal being a carbonyl group is a group having a bond terminal being a carbon atom. For example, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, isopropoxymethyl group, isobutoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, isopropoxyethyl Group, ether group-containing hydrocarbon group such as isobutoxyethyl group; aryloxyalkyl group such as phenoxymethyl group, methylphenoxymethyl group, dimethylphenoxymethyl group and naphthoxymethyl group; alkoxy such as methoxyphenyl group and ethoxyphenyl group Aryl group; acetoxymethyl group and the like Preferably it is a 2-12 oxygen atom containing hydrocarbon group.

Moreover, in R < ¹ > -R < ⁴ > in the said General formula (1), as a phosphorus containing hydrocarbon group of carbon numbers 2-24 except a thing whose bond terminal is a C = P group, a bond terminal is a carbon atom. A dialkylphosphinoalkyl group such as a dimethylphosphinemethyl group, a dibutylphosphinomethyl group, a dicyclohexylphosphinomethyl group, a dimethylphosphineethyl group, a dibutylphosphinoethyl group, a dicyclohexylphosphinoethyl group; Groups, diarylphosphinoalkyl groups such as ditolylphosphinomethyl group; phosphino group-substituted aryl groups such as dimethylphosphinophenyl group and diethylphosphinophenyl group. Preferably it is a 2-12 phosphorus containing hydrocarbon group.

In R ^{1 to} R ⁴ in the general formula (1), the silicon-containing hydrocarbon group having 1 to 24 carbon atoms includes a hydrocarbon-substituted silyl group, a hydrocarbon-substituted siloxy group, a siloxyalkyl group, and a hydrocarbon-substituted group. Examples include silylalkyl groups, hydrocarbon-substituted silylaryl groups, and specific examples include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, and tolylsilylsilyl. Hydrocarbon substituted silyl groups such as trinaphthylsilyl; hydrocarbon substituted silyl ether groups such as trimethylsilyl ether; silicon substituted alkyl groups such as trimethylsilylmethyl; silicon substituted aryl groups such as trimethylsilylphenyl;

When R ¹ is a hydrogen atom or a methyl group, R ² has 2 or more carbon atoms. Further, in the general formula (1), R ¹ and R ² may be bonded to each other to form a cyclic group. For example, R ¹ and R ² and R ¹ and R ² Examples of the cyclic group to be formed include a cycloalkyl ring, a fluorenyl ring, an indenyl ring, an imidazole ring, and a piperidinyl ring.

Preferred specific examples of the compound represented by formula (1) (component (A)) include methyl 2- (methoxymethyl) -3-phenyl-2-propenoate and 2- (methoxymethyl) -3-phenyl. 2-propenoic acid ethyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid isobutyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid-t-butyl 2- (methoxymethyl) -3-phenyl-2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid- n-propyl, isopropyl 2- (ethoxymethyl) -3-phenyl-2-propenoate, 2- (ethoxymethyl) -3-phenyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3- Isobutyl phenyl-2-propenoate, 2- (ethoxymethyl) -3-phenyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3-phenyl-2-propenoate-n-hexyl,
2- (n-propoxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (n-propoxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (n-propoxymethyl) -3-phenyl 2-propenoic acid-n-propyl, 2- (n-propoxymethyl) -3-phenyl-2-propenoic acid isopropyl, 2- (n-propoxymethyl) -3-phenyl-2-propenoic acid-n-butyl 2- (n-propoxymethyl) -3-phenyl-2-propenoate, 2- (n-propoxymethyl) -3-phenyl-2-propenoate-t-butyl, 2- (n-propoxymethyl) -3-phenyl-2-propenoic acid-n-hexyl,
2- (isopropoxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (isopropoxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (isopropoxymethyl) -3-phenyl-2- N-propyl propenoate, 2- (isopropoxymethyl) -3-phenyl-2-propenoate, 2- (isopropoxymethyl) -3-phenyl-2-propenoate-n-butyl, 2- (iso Propoxymethyl) -3-phenyl-2-propenoate isobutyl, 2- (isopropoxymethyl) -3-phenyl-2-propenoate-t-butyl, 2- (isopropoxymethyl) -3-phenyl-2-propene Acid-n-hexyl,
2-isobutoxymethyl-3-phenyl-2-propenoic acid methyl, 2-isobutoxymethyl-3-phenyl-2-propenoic acid ethyl, 2-isobutoxymethyl-3-phenyl-2-propenoic acid-n-propyl 2-isobutoxymethyl-3-phenyl-2-propenoic acid-isopropyl, 2-isobutoxymethyl-3-phenyl-2-propenoic acid-n-butyl, 2-isobutoxymethyl-3-phenyl-2-propene Acid-isobutyl, 2-isobutoxymethyl-3-phenyl-2-propenoate-t-butyl, 2-isobutoxymethyl-3-phenyl-2-propenoate-n-hexyl,
Methyl 2- (n-butoxymethyl) -3-phenyl-2-propenoate, ethyl 2- (n-butoxymethyl) -3-phenyl-2-propenoate, 2- (n-butoxymethyl) -3-phenyl 2-propenoic acid-n-propyl, 2- (n-butoxymethyl) -3-phenyl-2-propenoic acid isopropyl, 2- (n-butoxymethyl) -3-phenyl-2-propenoic acid-n-butyl 2- (n-butoxymethyl) -3-phenyl-2-propenoic acid isobutyl, 2- (n-butoxymethyl) -3-phenyl-2-propenoic acid-t-butyl, 2- (n-butoxymethyl) -3-phenyl-2-propenoic acid-n-hexyl,
Methyl 2- (t-butoxymethyl) -3-phenyl-2-propenoate, ethyl 2- (t-butoxymethyl) -3-phenyl-2-propenoate, 2- (t-butoxymethyl) -3-phenyl 2-propenoic acid-n-propyl, 2- (t-butoxymethyl) -3-phenyl-2-propenoic acid isopropyl, 2- (t-butoxymethyl) -3-phenyl-2-propenoic acid-n-butyl 2- (t-butoxymethyl) -3-phenyl-2-propenoate, 2- (t-butoxymethyl) -3-phenyl-2-propenoate-t-butyl, 2- (t-butoxymethyl) -3-phenyl-2-propenoic acid-n-hexyl,
2- (n-hexyloxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (n-hexyloxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (n-hexyloxymethyl)- 3-phenyl-2-propenoic acid-n-propyl, 2- (n-hexyloxymethyl) -3-phenyl-2-propenoic acid isopropyl, 2- (n-hexyloxymethyl) -3-phenyl-2-propene Acid-n-butyl, 2- (n-hexyloxymethyl) -3-phenyl-2-propenoate, 2- (n-hexyloxymethyl) -3-phenyl-2-propenoate-t-butyl, 2 -(N-hexyloxymethyl) -3-phenyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate, ethyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate, 2- (methoxymethyl) -3-cyclohexyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid-n-butyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid isobutyl, 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid-t-butyl, 2- (methoxymethyl) -3 -Cyclohexyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3-cyclohexyl-2-propenoate, ethyl 2- (ethoxymethyl) -3-cyclohexyl-2-propenoate, 2- (ethoxymethyl) -3-cyclohexyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid-n-butyl 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid isobutyl, 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid-t-butyl, 2- (ethoxymethyl) -3 -Cyclohexyl-2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3 -(N-butyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid isopropyl, 2- (methoxymethyl) -3- (n-butyl ) -2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid, 2- (methoxymethyl) -3- (n-butyl) -2-propene Acid-t-butyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3- (n-butyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid ethyl, 2- (ethoxymethyl) -3 -(N-butyl) -2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid isopropyl, 2- (ethoxymethyl) -3- (n-butyl) ) -2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid isobutyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propene Acid-t-butyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3,3-diphenyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid-n-butyl 2- (methoxymethyl) -3,3-diphenyl-2-propenoate isobutyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3 , 3-diphenyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate, ethyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate, 2- (ethoxymethyl) -3,3-diphenyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-diphenyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3,3-diphenyl-2-propenoic acid-n-butyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate, isobutyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3 , 3-diphenyl-2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3 , 3-Dicyclohexyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3,3-dicyclo Xyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid isobutyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propene Acid-t-butyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3 , 3-Dicyclohexyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3,3-dicyclo Xyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoate, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propene Acid-t-butyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate, ethyl 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propene Isopropyl, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate-n-butyl, 2- (methoxymethyl) -3,3- (di-n-butyl)- Isobutyl 2-propenoate, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate-t-butyl, 2- (methoxymethyl) -3,3- (di-n- Butyl) -2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3- (isobutyl) 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid isopropyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid-n-butyl 2- (methoxymethyl) -3- (isobutyl) -2-propenoate, 2- (methoxymethyl) -3- (isobutyl) -2-propenoate-t-butyl, 2- (methoxymethyl) -3 -(Isobutyl) -2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3- (isobutyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid ethyl, 2- (ethoxymethyl) -3- (isobutyl) 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid isopropyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid-n-butyl 2- (ethoxymethyl) -3- (isobutyl) -2-propenoate, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoate-t-butyl, 2- (ethoxymethyl) -3 -(Isobutyl) -2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3 , 3- (Diisobutyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid isopropyl, 2- (methoxymethyl) -3,3- (diisobutyl) ) -2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid isobutyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propene Acid-t-butyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid ethyl, 2- (ethoxymethyl) -3 , 3- (Diisobutyl) -2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid isopropyl, 2- (ethoxymethyl) -3,3- (diisobutyl) ) -2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid isobutyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propene Acid-t-butyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3-vinyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- Isobutyl vinyl-2-propenoate, 2- (methoxymethyl) -3-vinyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3-vinyl-2-propenoate-n-hexyl,
2- (Ethoxymethyl) -3-vinyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-vinyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-vinyl-2-propenoic acid- n-propyl, isopropyl 2- (ethoxymethyl) -3-vinyl-2-propenoate, 2- (ethoxymethyl) -3-vinyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3- Isobutyl vinyl-2-propenoate, 2- (ethoxymethyl) -3-vinyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3-vinyl-2-propenoate-n-hexyl,
2- (methoxymethyl) -3,3-divinyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3,3-divinyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid-n-butyl 2- (methoxymethyl) -3,3-divinyl-2-propenoate, isobutyl 2- (methoxymethyl) -3,3-divinyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3 , 3-Divinyl-2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3,3-divinyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3,3-divinyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid-n-butyl 2- (ethoxymethyl) -3,3-divinyl-2-propenoate, isobutyl 2- (ethoxymethyl) -3,3-divinyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3 , 3-Divinyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3-cyclohexenyl-2-propenoate, ethyl 2- (methoxymethyl) -3-cyclohexenyl-2-propenoate, 2- (methoxymethyl) -3-cyclohexenyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid-n-butyl 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid isobutyl, 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid-t-butyl, 2- (methoxymethyl) -3 -Cyclohexenyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate, ethyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate, 2- (ethoxymethyl) -3-cyclohexenyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoic acid-n-butyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate, isobutyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3 -Cyclohexenyl-2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoate methyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoate, 2- (methoxymethyl) -3 , 3-Dicyclohexenyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3,3-dicyclo Xenyl-2-propenoate-n-butyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoate isobutyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propene Acid-t-butyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid-n-hexyl,
2- (Ethoxymethyl) -3,3-dicyclohexenyl-2-propenoate methyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoate, 2- (ethoxymethyl) -3 , 3-Dicyclohexenyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3,3-dicyclo Xenyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoate isobutyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propene Acid-t-butyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid-n-hexyl,
2- (methoxymethyl) -3-naphthyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- Naphthyl-2-propenoate isobutyl, 2- (methoxymethyl) -3-naphthyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3-naphthyl-2-propenoate-n-hexyl,
2- (Ethoxymethyl) -3-naphthyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoic acid- n-propyl, isopropyl 2- (ethoxymethyl) -3-naphthyl-2-propenoate, 2- (ethoxymethyl) -3-naphthyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3- Naphthyl-2-propenoate isobutyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoate-n-hexyl,
2- (methoxymethyl) -3-indenyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- Isobutyl indenyl-2-propenoate, 2- (methoxymethyl) -3-indenyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3-indenyl-2-propenoate-n-hexyl,
2- (Ethoxymethyl) -3-indenyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-indenyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-indenyl-2-propenoic acid- n-propyl, isopropyl 2- (ethoxymethyl) -3-indenyl-2-propenoate, 2- (ethoxymethyl) -3-indenyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3- Isobutyl indenyl-2-propenoate, 2- (ethoxymethyl) -3-indenyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3-indenyl-2-propenoate-n-hexyl,
Methyl 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (methoxymethyl) -3 -Phenyl-3-methyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-phenyl-3- N-butyl methyl-2-propenoate, 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (methoxymethyl) -3-phenyl-3-methyl-2-propene Acid-t-butyl, 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (ethoxymethyl) -3 -Phenyl-3-methyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoic acid isopropyl, 2- (ethoxymethyl) -3-phenyl-3- N-butyl methyl-2-propenoate, 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propene Acid-t-butyl, 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propene Isopropyl, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate-n-butyl, 2- (methoxymethyl) -3- (n-butyl) -3-methyl- Isobutyl 2-propenoate, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3- (n-butyl) -3 -Methyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, 2- (Ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propene Isopropyl, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl- 2-butyl propenoate, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3- (n-butyl) -3 -Methyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (methoxy Methyl) -3- (isobutyl) -3-methyl-2-propenoate-n-propyl, 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (methoxymethyl) ) -3- (isobutyl) -3-methyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid isobutyl, 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid-t-butyl, 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid-n-hexyl,
Methyl 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (ethoxy Methyl) -3- (isobutyl) -3-methyl-2-propenoate-n-propyl, 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (ethoxymethyl) ) -3- (isobutyl) -3-methyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid isobutyl, 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid-t-butyl, 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoic acid-n-hexyl,
Methyl 2- (methoxymethyl) -3-benzyl-2-propenoate, ethyl 2- (methoxymethyl) -3-benzyl-2-propenoate, 2- (methoxymethyl) -3-benzyl-2-propenoate- n-propyl, isopropyl 2- (methoxymethyl) -3-benzyl-2-propenoate, 2- (methoxymethyl) -3-benzyl-2-propenoate-n-butyl, 2- (methoxymethyl) -benzyl- Isobutyl 2-propenoate, 2- (methoxymethyl) -3-benzyl-2-propenoate-t-butyl, 2- (methoxymethyl) -3-benzyl-2-propenoate-n-hexyl,
2- (ethoxymethyl) -3-benzyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-benzyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-benzyl-2-propenoic acid- n-propyl, isopropyl 2- (ethoxymethyl) -3-benzyl-2-propenoate, 2- (ethoxymethyl) -3-benzyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -benzyl- Isobutyl 2-propenoate, 2- (ethoxymethyl) -3-benzyl-2-propenoate-t-butyl, 2- (ethoxymethyl) -3-benzyl-2-propenoate-n-hexyl,
2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid isopropyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -cyclopentyl- Examples thereof include isobutyl 2-propenoate, 2- (methoxymethyl) -3-cyclopentyl-2-propenoate-t-butyl, and 2- (methoxymethyl) -3-cyclopentyl-2-propenoate-n-hexyl.
Among the esters of general formula (1), particularly preferred are
2- (methoxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3-phenyl-2-propenoic acid isobutyl;
2- (Ethoxymethyl) -3-phenyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid- n-propyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3-phenyl-2-propenoic acid isobutyl;
Methyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate, ethyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate, 2- (methoxymethyl) -3-cyclohexyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid isobutyl 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-cyclohe Xyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-cyclohexyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3-cyclohexyl Isobutyl-2-propenoic acid;
2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3 -(N-butyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (n-butyl) -2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- ( n-butyl) -2-propenoic acid isobutyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propene Ethyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (n-butyl) -2-propenoic acid-n-butyl 2- (Ethoxymethyl) -3- (n-butyl Isobutyl-2-propenoic acid;
2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3,3-diphenyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3-diphenyl-2-propenoic acid isobutyl , Methyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate, ethyl 2- (ethoxymethyl) -3,3-diphenyl-2-propenoate, 2- (ethoxymethyl) -3,3- Diphenyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-diphenyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3,3-dipheny Isobutyl-2-propenoic acid;
2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3 , 3-Dicyclohexyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-dicyclohexyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3 -Isobutyl dicyclohexyl-2-propenoate, methyl 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoate, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propene Acid ethyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-dicyclohexyl-2-propenoic acid n- butyl, 2- (ethoxymethyl) -3,3-dicyclohexyl hexyl-2-propenoic acid isobutyl,
Methyl 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate, ethyl 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propene Acid-n-butyl, 2- (methoxymethyl) -3,3- (di-n-butyl) -2-propenoate,
2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3- (isobutyl) 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid-n-butyl, 2- (methoxymethyl) -3- (isobutyl) -2-propenoic acid isobutyl ,
2- (Ethoxymethyl) -3- (isobutyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid ethyl, 2- (ethoxymethyl) -3- (isobutyl) 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3- (isobutyl) -2-propenoic acid isobutyl ,
2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid methyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid ethyl, 2- (methoxymethyl) -3 , 3- (Diisobutyl) -2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3- (diisobutyl) -2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3 -(Diisobutyl) -2-propenoic acid isobutyl,
2- (Ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid methyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid ethyl, 2- (ethoxymethyl) -3 , 3- (Diisobutyl) -2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3- (diisobutyl) -2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3,3 -(Diisobutyl) -2-propenoic acid isobutyl,
2- (methoxymethyl) -3-vinyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-vinyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-vinyl-2-propenoate-n-butyl, 2- (methoxymethyl) -3-vinyl-2-propenoate isobutyl,
2- (Ethoxymethyl) -3-vinyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-vinyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-vinyl-2-propenoic acid- n-propyl, 2- (ethoxymethyl) -3-vinyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3-vinyl-2-propenoate isobutyl,
2- (methoxymethyl) -3,3-divinyl-2-propenoic acid methyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3,3-divinyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3-divinyl-2-propenoic acid isobutyl ,
2- (Ethoxymethyl) -3,3-divinyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3,3-divinyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3,3-divinyl-2-propenoic acid isobutyl ,
Methyl 2- (methoxymethyl) -3-cyclohexenyl-2-propenoate, ethyl 2- (methoxymethyl) -3-cyclohexenyl-2-propenoate, 2- (methoxymethyl) -3-cyclohexenyl 2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3-cyclohexenyl-2-propenoic acid isobutyl ,
Methyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate, ethyl 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoate, 2- (ethoxymethyl) -3-cyclohexenyl 2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3-cyclohexenyl-2-propenoic acid isobutyl ,
2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoate methyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoate, 2- (methoxymethyl) -3 , 3-Dicyclohexenyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3,3 -Isobutyl dicyclohexenyl-2-propenoate,
2- (Ethoxymethyl) -3,3-dicyclohexenyl-2-propenoate methyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoate, 2- (ethoxymethyl) -3 , 3-Dicyclohexenyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3,3-dicyclohexenyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3,3 -Isobutyl dicyclohexenyl-2-propenoate,
2- (methoxymethyl) -3-naphthyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-naphthyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-naphthyl-2-propenoate-n-butyl, 2- (methoxymethyl) -3-naphthyl-2-propenoate isobutyl,
2- (Ethoxymethyl) -3-naphthyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoic acid- n-propyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3-naphthyl-2-propenoate isobutyl,
2- (methoxymethyl) -3-indenyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-indenyl-2-propenoic acid- n-propyl, 2- (methoxymethyl) -3-indenyl-2-propenoate-n-butyl, 2- (methoxymethyl) -3-indenyl-2-propenoate isobutyl,
2- (Ethoxymethyl) -3-indenyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-indenyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-indenyl-2-propenoic acid- n-propyl, 2- (ethoxymethyl) -3-indenyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -3-indenyl-2-propenoate isobutyl,
Methyl 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (methoxymethyl) -3 -Phenyl-3-methyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3-phenyl-3-methyl-2-propenoic acid-n-butyl, 2- (methoxymethyl) -3-phenyl -3-methyl-2-propenoate isobutyl,
Methyl 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoate, 2- (ethoxymethyl) -3 -Phenyl-3-methyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3-phenyl-3-methyl-2-propenoic acid-n-butyl, 2- (ethoxymethyl) -3-phenyl -3-methyl-2-propenoate isobutyl,
Methyl 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoic acid-n-propyl, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propene Acid-n-butyl, 2- (methoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate isobutyl,
Methyl 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate, 2- (Ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoic acid-n-propyl, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propene Acid-n-butyl, 2- (ethoxymethyl) -3- (n-butyl) -3-methyl-2-propenoate,
Methyl 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, ethyl 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (methoxy Methyl) -3- (isobutyl) -3-methyl-2-propenoate-n-propyl, 2- (methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate-n-butyl, 2- (Methoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate isobutyl,
Methyl 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, ethyl 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate, 2- (ethoxy Methyl) -3- (isobutyl) -3-methyl-2-propenoate-n-propyl, 2- (ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate-n-butyl, 2- (Ethoxymethyl) -3- (isobutyl) -3-methyl-2-propenoate isobutyl,
Methyl 2- (methoxymethyl) -3-benzyl-2-propenoate, ethyl 2- (methoxymethyl) -3-benzyl-2-propenoate, 2- (methoxymethyl) -3-benzyl-2-propenoate- n-propyl, 2- (methoxymethyl) -3-benzyl-2-propenoate-n-butyl, 2- (methoxymethyl) -benzyl-2-propenoate isobutyl,
2- (ethoxymethyl) -3-benzyl-2-propenoic acid methyl, 2- (ethoxymethyl) -3-benzyl-2-propenoic acid ethyl, 2- (ethoxymethyl) -3-benzyl-2-propenoic acid- n-propyl, 2- (ethoxymethyl) -3-benzyl-2-propenoate-n-butyl, 2- (ethoxymethyl) -benzyl-2-propenoate isobutyl,
2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid methyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid ethyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid- Examples include n-propyl, 2- (methoxymethyl) -3-cyclopentyl-2-propenoic acid-n-butyl, and 2- (methoxymethyl) -cyclopentyl-2-propenoic acid isobutyl. These compounds can be used alone or in combination of two or more.

Of the compounds represented by the general formula (1), more preferred are those in which at least one of R ¹ and R ² is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. A vinyl group, a C3-C12 linear alkenyl group or branched alkenyl group, a C1-C12 linear halogen-substituted alkyl group, a C3-C12 branched halogen-substituted alkyl group, a C3-C3 The compound is a cycloalkyl group having 12 cycloalkyl, a cycloalkenyl group having 3 to 12 carbons, or an aromatic hydrocarbon group having 6 to 12 carbons. More preferably, R ³ and R ⁴ are linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, vinyl groups, linear alkenyl groups having 3 to 12 carbon atoms, or branched. An alkenyl group, a linear halogen-substituted alkyl group having 1 to 12 carbon atoms, a branched halogen-substituted alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or It is a compound which is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
More preferably, R ¹ and R ² are the above preferred compounds, and at least one of R ³ and R ⁴ is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl having 3 to 12 carbon atoms. Group, vinyl group, linear alkenyl group or branched alkenyl group having 3 to 12 carbon atoms, linear halogen-substituted alkyl group having 1 to 12 carbon atoms, branched halogen-substituted alkyl group having 3 to 12 carbon atoms, carbon number 2 -12 linear halogen-substituted alkenyl group, branched halogen-substituted alkenyl group having 3 to 12 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms, halogen having 3 to 12 carbon atoms A group selected from a substituted cycloalkyl group, a halogen-substituted cycloalkenyl group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms; Preferably, at least one of R ³ and R ⁴ is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms whose bonding terminal is —CH ₂ —. It is a certain compound.

  In the solid catalyst component (I) in the present invention, an electron donating compound other than the compound represented by the general formula (1) (component (A)) (hereinafter 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, diether compounds and succinic acid esters other than component (A), maleic acid esters, malonic acid. Examples thereof include organic acid esters such as esters, glutaric acid esters, cyclohexane dicarboxylic acid esters, cyclohexene dicarboxylic acid esters, and phthalic acid diesters. Two or more of these electron donating compounds (D) can be used in combination.

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

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

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

  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 a compound (component) represented by the general formula (1) (A)) are prepared by bringing them into contact with each other.

  Examples of the magnesium compound used in the method for producing a solid catalyst component of the present invention (hereinafter sometimes simply referred to as “component (B)”) include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, One or more selected from 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 dialkoxymagnesium 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 handling operability of the produced polymer powder during the polymerization operation is improved, and the produced polymer Problems such as blockage caused by fine powder contained in the powder are solved.

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

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

  Furthermore, the particle size distribution is ln (D90 / D10) (where D90 is the cumulative particle size in the volume cumulative particle size distribution and 90% of the particle size, and D10 is the cumulative particle size in the volume cumulative particle size distribution of 10%). Is preferably 3 or less, more preferably 2 or less.

  For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, and JP-A-8-73388 can be used to produce spherical dialkoxymagnesium as described above. It is exemplified in the publication.

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

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

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

Examples of the titanium compound (hereinafter sometimes referred to as “component (C)”) used for the preparation of component (I) in the present invention include, for example, general formula (6);
^{_{Ti (OR 15) j X 4}} -j (6)
(R ¹⁵ is a hydrocarbon group having 1 to 10 carbon atoms, and when a plurality of OR ¹⁵ groups are present, the plurality of R ¹⁵ may be the same or different, X is a halogen group, In the case where a plurality of are present, each X may be the same or different, and j is 0 or an integer of 1 to 4.).

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

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

  The component (A) used in the preparation of the solid catalyst component (I) of the present invention is the same as the component (A) of the solid catalyst component (I) of the present invention, and the description thereof is omitted. The electron donating compound (D) 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, component (A) and titanium halide, and an adduct such as alcohol. Contacting magnesium halide compound, component (A) and titanium halide in the presence of inert hydrocarbon solvent, dialkoxymagnesium, component (A) and titanium halide in the presence of inert hydrocarbon solvent And a method in which a solid catalyst is deposited by bringing the reducing magnesium compound, component (A) and titanium halide into contact with each other.

Below, the specific preparation method of the solid catalyst component (I) for olefin polymerization is illustrated. In the following methods (1) to (16), in addition to the component (A), an electron donating compound (D) other than the component (A) may be used in combination. Furthermore, you may perform the said contact in coexistence of other reaction reagents, such as silicon, phosphorus, aluminum, and surfactant, for example.
(1) After dissolving magnesium halide in an alkoxytitanium compound, the organosilicon compound is contacted to obtain a solid product, the solid product is reacted with titanium halide, and then component (A) is contacted. To prepare a solid catalyst component (I) for olefin polymerization. At this time, the component (I) can be further subjected to preliminary polymerization treatment with an organoaluminum compound, an organosilicon compound and olefins.
(2) After reacting magnesium halide and alcohol to make a uniform solution, the carboxylic acid anhydride is brought into contact with the homogeneous solution, and then the titanium halide and component (A) are contacted with the solution to obtain a solid product. A solid catalyst component (I) for olefin polymerization is prepared by further contacting a titanium halide with the solid product.
(3) An organomagnesium compound is synthesized by reacting magnesium metal, butyl chloride, and dialkyl ether, and the organomagnesium compound is contacted with alkoxytitanium to obtain a solid product. And a method of preparing a solid catalyst component (I) for olefin polymerization by catalytically reacting titanium halide. At this time, the solid component can be preliminarily polymerized with an organoaluminum compound, an organosilicon compound and an olefin to prepare a solid catalyst component (I) for olefin polymerization.
(4) An organomagnesium compound such as dialkylmagnesium and an organoaluminum compound are brought into contact with alcohol in the presence of a hydrocarbon solvent to form a homogeneous solution, and a silicon compound such as silicon tetrachloride is brought into contact with this solution to form a solid. Then, the solid product is contacted with titanium halide and component (A) in the presence of an aromatic hydrocarbon solvent, and further contacted with titanium tetrachloride to solid catalyst component for olefin polymerization. A method of obtaining (I).
(5) Magnesium chloride, tetraalkoxytitanium and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to obtain a homogeneous solution, and after contacting the solution and titanium halide, the temperature is raised to precipitate a solid, A method of obtaining the solid catalyst component (I) for olefin polymerization by bringing the solid (B) into contact with the component and further reacting with titanium halide.
(6) Metal magnesium powder, alkyl monohalogen compound and iodine are contact-reacted, and then tetraalkoxytitanium, acid halide and aliphatic alcohol are contact-reacted in the presence of a hydrocarbon solvent to form a homogeneous solution, and the solution After adding titanium tetrachloride to the mixture, the temperature is raised to precipitate a solid product. The solid product is contacted with component (A) and further reacted with titanium tetrachloride to solidify the solid catalyst component (I) for olefin polymerization. How to prepare.
(7) Suspend dialkoxymagnesium in a hydrocarbon solvent, then contact with titanium tetrachloride, raise the temperature, contact with component (A) to obtain a solid product, and convert the solid product to hydrocarbon A method of preparing a solid catalyst component (I) for olefin polymerization by washing with a solvent and then contacting with titanium tetrachloride again in the presence of a hydrocarbon solvent. At this time, the solid component can be heat-treated in the presence or absence of a hydrocarbon solvent.
(8) After dialkoxymagnesium is suspended in a hydrocarbon solvent, it is contacted with titanium halide and component (A) to obtain a solid product. After washing the solid product with an inert organic solvent, A method for obtaining a solid catalyst component (I) for olefin polymerization by contacting and reacting with a titanium halide again in the presence of a hydrocarbon solvent. At this time, the solid component and the titanium halide can be contacted twice or more.
(9) dialkoxymagnesium, calcium chloride and alkoxy group-containing silicon compound are co-ground, and the obtained pulverized solid is suspended in a hydrocarbon solvent, and then contacted with titanium halide and component (A), Next, a method for preparing a solid catalyst component (I) for olefin polymerization by further contacting a titanium halide.
(10) The dialkoxymagnesium and component (A) are suspended in a hydrocarbon solvent, the suspension is contacted with titanium halide and reacted to obtain a solid product, and the solid product is washed with a hydrocarbon solvent. Thereafter, the method further comprises contacting a titanium halide in the presence of a hydrocarbon solvent to obtain a solid catalyst component (I) for olefin polymerization.
(11) A solid catalyst component (I) for olefin polymerization is prepared by contacting aliphatic magnesium such as magnesium stearate with titanium halide and component (A), and then further contacting with titanium halide. Method.
(12) The dialkoxymagnesium is suspended in a hydrocarbon solvent, brought into contact with the titanium halide, heated, and contacted with the component (A) to obtain a solid product. The solid product is treated with a hydrocarbon solvent. In the presence of a hydrocarbon solvent and again contacting with a titanium halide to prepare the solid catalyst component (I) for olefin polymerization, which is one of the above suspension / contact and catalytic reaction In the step, the solid catalyst component (I) for olefin polymerization is prepared by contacting aluminum chloride.
(13) Dialkoxymagnesium, 2-ethylhexyl alcohol, and carbon dioxide are contact-reacted in the presence of a hydrocarbon solvent to form a homogeneous solution, and this solution is contacted with titanium halide and component (A) to form a solid product. The solid product is further dissolved in tetrahydrofuran, and then a solid product is further precipitated. The solid product is contacted with titanium halide, and if necessary, contact reaction with titanium halide is repeated to obtain olefins. A method for preparing a solid catalyst component (I) for polymerization. In this case, for example, a silicon compound such as tetrabutoxysilane may be used in any of the contact, contact reaction, and dissolution steps.
(14) After suspending magnesium chloride, an organic epoxy compound and a phosphoric acid compound in a hydrocarbon solvent, the mixture is heated to obtain a homogeneous solution, and this solution is contacted with a carboxylic acid anhydride and a titanium halide to form a solid. A product is obtained, and the solid product is allowed to react with the component (A). The obtained reaction product is washed with a hydrocarbon solvent, and then again contacted with a titanium halide in the presence of the hydrocarbon solvent. To obtain a solid catalyst component (I) for olefin polymerization.
(15) Contact reaction of dialkoxymagnesium, titanium compound and component (A) in the presence of a hydrocarbon solvent, contact reaction of the resulting reaction product with a silicon compound such as polysiloxane, and further contact with a titanium halide A method of obtaining a solid catalyst component (I) for olefin polymerization by reacting, then contacting a metal salt of an organic acid, and then contacting a titanium halide again.
(16) After dialkoxymagnesium and component (A) are suspended in a hydrocarbon solvent, the temperature is raised and brought into contact with the silicon halide, and then brought into contact with the titanium halide to obtain a solid product. A method of preparing a solid catalyst component (I) for polymerizing olefins by washing the product with a hydrocarbon solvent and then again contacting with a titanium halide in the presence of the hydrocarbon solvent. At this time, the solid component may be heat-treated in the presence or absence of a hydrocarbon solvent.
In addition, in order to further improve the polymerization activity at the time of olefin polymerization and the stereoregularity of the produced polymer, a titanium halide is newly added to the solid catalyst component (I) after washing in the methods (1) to (16). And a hydrocarbon solvent are contacted at 20 to 100 ° C., the temperature is raised, a reaction treatment (secondary reaction treatment) is performed, and then an operation of washing with a liquid inert organic solvent at room temperature is repeated 1 to 10 times. May be.

  As a method for preparing component (I) in the present invention, any of the above methods can be suitably used. Among them, (1), (3), (4), (5), (7), The method (8) or (10) is preferred, and the method (3), (4), (7), (8), (10) provides a solid catalyst component for olefin polymerization having high stereoregularity. Are particularly preferable. The most preferred preparation method is to suspend dialkoxymagnesium and component (A) 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 to obtain olefins. This is a method for obtaining a solid catalyst component (I) for polymerization.

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

  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.

(II) The organoaluminum compound is not particularly limited as long as it is a compound represented by the above general formula (2), but R ⁵ is preferably an ethyl group or an isobutyl group, and Q is a hydrogen atom, a chlorine atom, A bromine atom, an ethoxy group, and a phenoxy group are preferable, and p is preferably 2, 2.5, or 3, and particularly preferably 3.

  Specific examples of such organoaluminum compounds include trialkylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trialkylaluminum such as triisobutylaluminum, diethylaluminum chloride, diethylaluminum bromide, etc. Alkyl aluminum halide, diethyl aluminum hydride, etc. are mentioned. Among them, alkyl aluminum halides such as diethyl aluminum chloride, or trialkyl aluminums such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum are preferably used. Triethylaluminum and triisobutylaluminum are preferred. 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, isocyanates, organosilicon compounds, especially organosilicon compounds having a Si—O—C bond or Si—N—C bonds An aminosilane compound etc. are mentioned.

  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 and 1,3-diether compounds.

Among the external electron donating compounds of the above (III), as the organosilicon compound having a Si—O—C bond, the following general formula (3);
R ⁶ _q Si (OR ⁷ ) _4-q (3)
(In the formula, R ⁶ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, or an aromatic having 6 to 15 carbon atoms. R ⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon atom. A cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, which may be the same or different. (It is an integer of 0 ≦ q ≦ 3.)
The organosilicon compound represented by these is mentioned.

Among the external electron donating compounds of the above (III), as the aminosilane compound having a Si—N—C bond, the following general formula (4);
(R ⁸ R ⁹ N) _s SiR ¹⁰ _4-s (4)
Wherein R ⁸ and R ⁹ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group or a cycloalkenyl group having 3 to 20 carbon atoms, or carbon R ⁸ and R ⁹ may be the same or different and may be bonded to each other to form a ring, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, Vinyl group, alkenyl group having 3 to 12 carbon atoms, alkoxy group having 1 to 20 carbon atoms, vinyloxy group, alkenyloxy group having 3 to 20 carbon atoms, cycloalkyl group or cycloalkyloxy group having 3 to 20 carbon atoms, or an aryl group or an aryloxy group having 6 to 20 carbon atoms, when there are a plurality of R ¹⁰ s, the plurality of R ¹⁰ good .s be different even in the same is an integer from 1 to 3.) in table And aminosilane compounds.

  Examples of the organosilicon compound and aminosilane compound include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, alkyl (cycloalkyl) alkoxysilane, (alkylamino) alkoxysilane, and alkyl (alkylamino). ) Alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, tetraalkoxysilane, tetrakis (alkylamino) silane, alkyltris (alkylamino) silane, dialkylbis (alkylamino) silane, trialkyl (alkylamino) silane, etc. Specifically, phenyltrimethoxysilane, t-butyltrimethoxysilane, diisopropyldimethoxysilane, isopropyl Sobutyldimethoxysilane, diisopentyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylmethyl Dimethoxysilane, tetraethoxysilane, tetrabutoxysilane, bis (ethylamino) methylethylsilane, t-butylmethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis ( Methylamino) (methylcyclopentylamino) methylsilane, diethylaminotriethoxysilane, bis (cyclohexylamino) Methoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, ethyl (isoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, trimethylsilyltrimethoxysilane, or trimethylsilyltriethoxysilane Among them, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, Cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butyl Rumethylbis (ethylamino) silane, bis (ethylamino) dicyclohexylsilane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, trimethylsilyltrimethoxysilane, Alternatively, trimethylsilyltriethoxysilane or the like is preferably used. Moreover, this organosilicon compound can also be used individually by 1 type or in combination of 2 or more types selected from the organosilicon compound represented by General formula (3) and the organosilicon compound represented by General formula (4).

Among the external electron donating compounds of the above (III), the 1,3-diether compound includes the following general formula (5);
R ¹¹ OCH ₂ CR ¹² R ¹³ CH ₂ OR ¹⁴ (5)
Wherein R ¹² and R ¹³ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group. , An aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a carbon number 2 to 12 dialkylamino groups which may be the same or different and may be bonded to each other to form a ring, and R ¹¹ and R ¹⁴ are each an alkyl group having 1 to 12 carbon atoms, a vinyl group, a carbon number; 3-12 alkenyl group, C3-C6 cycloalkyl group, C6-C12 aromatic hydrocarbon group or halogen-substituted aromatic hydrocarbon group, or C7-C12 having a substituent Of aromatic hydrocarbon groups, which may be the same or different)
1,3-diether compounds represented by the formula:

  Specifically, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-di-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane, 9,9-bis (methoxymethyl) fluorene and the like, among others, 2-isopropyl- A 1,3-diether compound having a substituent at the 2-position, such as 2-isobutyl-1,3-dimethoxypropane and 9,9-bis (methoxymethyl) fluorene, is preferably used.

  Further, as the external electron donating compound of (III), the organosilicon compound represented by the general formula (3), the organosilicon compound represented by the general formula (4), and the diether represented by the general formula (5) One or a combination of two or more of the compounds can also be used.

In the present invention, olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. Ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene.
When propylene is polymerized, it can be copolymerized with other olefins. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

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

  The order of contacting the components is arbitrary, but the organoaluminum compound (F) is first charged into the polymerization system, and then the external electron donating compound (G) is contacted and then the component (I) is contacted. desirable. The polymerization of olefin in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Furthermore, in the present invention, when polymerizing an olefin using a catalyst containing a solid catalyst component for olefin polymerization, an organoaluminum compound, and an external electron donating compound (also referred to as main polymerization), catalytic activity, stereoregularity and In order to further improve the particle properties and the like of the polymer produced, it is desirable to carry out prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used.

  In carrying out the prepolymerization, the order of contacting the 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 α-olefins include ethylene, 1-butene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, 1-octene and the like. Specifically, polymerization is carried out by adjusting the polymerization temperature and time so that the proportion of the polypropylene part is 20 to 80% by weight in the first stage, and then in the second stage, ethylene and propylene or other α -Olefin is introduced and polymerized so that the proportion of rubber part such as ethylene-propylene rubber (EPR) is 20 to 80% by weight. The polymerization temperatures in the first and second stages are both 200 ° C. or less, preferably 100 ° C. or less, and the polymerization pressure is 10 MPa or less, preferably 5 MPa or less. In the case of polymerization time in each polymerization stage or continuous polymerization, the residence time is usually 1 minute to 5 hours.

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

  In the compound represented by the general formula (1), the C = O oxygen of the ester group having a strong coordinating power and the ether group having a weak coordinating power are controlled to an appropriate distance and the direction of the coordinating direction on the magnesium compound. It is presumed to selectively coordinate to some appropriate site. In addition, due to this effect, restrictions are imposed on the position where the titanium compound that forms the active site is supported, and as a result, a large amount of titanium active sites that generate stereoregularity and high activity can be formed selectively. In addition, since the ether group has a weak coordination power, it has a feature that it easily deviates from the site once coordinated, and it is considered that the molecular weight distribution is prevented from being narrowed more than necessary due to its effect. Therefore, in the present invention, as the electron-donating compound, the solid catalyst component (I) contains the compound represented by the general formula (1), so that the olefin has an appropriate molecular weight distribution that is not wide or narrow. A similar polymer is obtained in high yield.

  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.

[Synthesis of Ether-Ester Compound (A)]
(Production Example 1)
[Synthesis of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate (A-1)]
A mixture of 130 mmol NaH (50% oil) and 30 ml THF was slowly added to anhydrous THF containing 123 mmol methanol cooled and stirred at room temperature for 30 min. Thereafter, the reaction solution was bathed in ice, and a mixture of 72 mmol benzaldehyde, 106 mmol methyl acrylate and 30 ml anhydrous THF was quickly added. After stirring for 90 minutes at room temperature, 20 ml of water was added and THF was distilled off. To the residue was added 60 ml of a 15% aqueous sodium hydroxide solution and heated under reflux for 30 minutes. The obtained solution was washed with toluene, acidified with concentrated hydrochloric acid, extracted with trichloromethane, and trichloromethane was distilled off to distill off the trichloromethane (2- (methoxymethyl) -3-phenyl- 2-propenoic acid) was obtained. Next, 233 mmol of thionyl chloride was added to 2- (methoxymethyl) -3-phenyl-2-propenoic acid dissolved in 50 ml of anhydrous methanol, and the mixture was stirred at room temperature for 15 hours. Subsequently, the reaction solution was neutralized with 160 ml of 3M sodium hydroxide and extracted with ethyl acetate, and then the organic layer was recovered. The obtained organic layer was washed with 100 ml of brine, dried over magnesium sulfate and dried, and the solvent was distilled off to obtain the desired product.
As a result of analyzing the ¹ H-NMR spectrum with a nuclear magnetic resonance apparatus, the chemical shift values were 3.45 (s, 2H), 3.75 (s, 6H), 4.52 (s, 1H), It was 7.43-7.66 (m, 5H) ppm, and from this, it was confirmed that the obtained product was methyl 2- (methoxymethyl) -3-phenyl-2-propenoate.
In addition, as a result of measuring by gas chromatography, the purity of the obtained methyl 2- (methoxymethyl) -3-phenyl-2-propenoate was 97.3%, and the yield was 95%. .

Example 1
[Synthesis of solid catalyst components]
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 Were added 30 ml of titanium tetrachloride and 15.3 mmol (3.1 g) of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate, and the temperature was raised to 90 ° C. Then, it was made to react for 90 minutes in the state holding 90 degreeC temperature. After completion of the reaction, the supernatant was extracted, 20 ml of TiCl ₄ was added, and further reacted at 100 ° C. for 2 hours. After completion of the reaction, the reaction product was washed 4 times with 75 ml of 100 ° C. toluene. Next, the solid catalyst component was obtained by washing 6 times with 75 ml of n-heptane at 40 ° C. When the solid content of the solid catalyst component was separated and the titanium content in the solid content was measured, it was 2.7% by weight.

[Formation and polymerization of polymerization catalyst]
In an autoclave with a stirrer having an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS), and 0.0026 as a titanium atom as the solid catalyst component. A millimolar charge was formed 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.). While maintaining the temperature of p-xylene at the boiling point (137 to 138 ° C.), the polymer was dissolved over 2 hours. Thereafter, the liquid temperature was cooled to 23 ° C. over 1 hour, and insoluble components and dissolved components were separated by filtration. A solution of the dissolved component was collected, p-xylene was distilled off by heating under reduced pressure, and the resulting residue was defined as xylene solubles (XS), and the weight was relative to the polymer (polypropylene) (wt% ).

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

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

(Example 2)
Polymerization was carried out in the same manner as in Example 1 except that 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS) was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS). The polymerization results are shown in Table 1.

(Comparative Example 1)
A solid component was prepared in the same manner as in Example 1, except that 15.3 mmol of diethyl diisobutylmalonate was used instead of 15.3 mmol of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate. Furthermore, formation of a polymerization catalyst and polymerization were performed. As a result, the titanium content in the obtained solid catalyst component was 3.9% by weight. The polymerization results are shown in Table 1.

(Comparative Example 2)
A solid component was prepared in the same manner as in Example 1, except that 15.3 mmol of diethyl diisopropyl succinate was used instead of 15.3 mmol of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate. Furthermore, formation of a polymerization catalyst and polymerization were performed. As a result, the titanium content in the obtained solid catalyst component was 2.9% by weight. The polymerization results are shown in Table 1.

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

(Comparative Example 4)
Example 1 except that 15.3-mmol ethyl 2-t-butyl-3-ethoxy-propionate was used instead of 15.3-mmol methyl 2- (methoxymethyl) -3-phenyl-2-propenoate A solid component was prepared in the same manner as described above, and a polymerization catalyst was formed and polymerized. As a result, the titanium content in the obtained solid catalyst component was 2.8% by weight. The polymerization results are shown in Table 1.

(Comparative Example 5)
Polymerization was carried out in the same manner as in Comparative Example 4 except that 0.13 mmol of dicyclopentyldimethoxysilane (DCPDMS) was used instead of 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS). The polymerization results are shown in Table 1.

(Example 3)
(Preparation of solid catalyst component)
120 ml of purified n-heptane was introduced into a 500 ml round-bottom flask thoroughly substituted with nitrogen. Further, 15 g of anhydrous magnesium chloride and 106 ml of Ti (On-Bu) ₄ were added and reacted at 90 ° C. for 1.5 hours to obtain a uniform solution. The homogeneous lysate was then cooled to 40 ° C. 24 ml of methyl hydrogen polysiloxane (20 centistokes) was added while maintaining the temperature at 40 ° C., and a precipitation reaction was performed for 5 hours. The precipitated solid product was thoroughly washed with purified n-heptane.
Next, 40 g of the precipitated solid product was introduced into a 500 ml round bottom flask equipped with a stirrer sufficiently substituted with nitrogen, and further purified n-heptane was introduced, so that the concentration of the solid product was 200 mg / ml. I tried to become. To this, 12 ml of SiCl ₄ was added and reacted at 90 ° C. for 3 hours. The reaction product was thoroughly washed with purified n-heptane, and purified n-heptane was introduced so that the concentration of the reaction product was 100 mg / ml.
10 mmol of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate (A-1) was added, and the reaction was performed at 70 ° C. for 1 hour. The reaction product was thoroughly washed with purified n-heptane, and 100 ml of purified n-heptane was introduced. Next, 20 ml of TiCl ₄ was added, followed by reaction at 95 ° C. for 3 hours. After completion of the reaction, the supernatant was extracted, and 20 ml of TiCl ₄ was further added, followed by reaction at 100 ° C. for 2 hours. The reaction product was thoroughly washed with purified n-heptane. The obtained solid product was dried under reduced pressure to obtain a powdery solid catalyst component. The titanium content in the obtained solid catalyst component was 2.5% by weight.

<Formation of polymerization catalyst, polymerization of olefin and evaluation of polymer>
The polymerization catalyst was formed, the olefin was polymerized, and the obtained polymer was evaluated in the same manner as in Example 1, except that the solid catalyst component was used in place of the solid catalyst component of Example 1. The results are shown in Table 1.

(Comparative Example 6)
A solid component was prepared in the same manner as in Example 3 except that 10 mmol of diethyl diisobutylmalonate was used instead of 10 mmol of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate. Formation and polymerization took place. As a result, the titanium content in the obtained solid catalyst component was 3.4% by weight. The polymerization results are shown in Table 1.

(Production Example 2)
[Synthesis of 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid ethyl ester (A-2)]
A mixture of 130 mmol NaH (50% oil) and 30 ml THF was slowly added to anhydrous THF containing 123 mmol methanol cooled and stirred at room temperature for 30 min. Thereafter, the reaction solution was bathed in ice, and a mixed solution consisting of 72 mmol cyclohexanealdehyde, 106 mmol methyl acrylate and 30 ml anhydrous THF was quickly added. After stirring for 90 minutes at room temperature, 20 ml of water was added and THF was distilled off. To the residue was added 60 ml of a 15% aqueous sodium hydroxide solution and heated under reflux for 30 minutes. The resulting solution was washed with toluene, acidified with concentrated hydrochloric acid, extracted with trichloromethane, and the trichloromethane was distilled off to distill off the trichloromethane (2- (methoxymethyl) -3-cyclohexane. Xyl-2-propenoic acid) was obtained. Next, 233 mmol of thionyl chloride was added to 2- (methoxymethyl) -3-cyclohexyl-2-propenoic acid dissolved in 50 ml of absolute ethanol, and the mixture was stirred at room temperature for 15 hours. The reaction solution was neutralized with 160 ml of 3M sodium hydroxide and extracted with ethyl acetate. The organic layer was collected, washed with 100 ml of brine, dried over magnesium sulfate, and the solvent was distilled off to obtain the desired product.
As a result of analyzing the ¹ H-NMR spectrum by a nuclear magnetic resonance apparatus, the chemical shift values are 1.27 (m, 4H), 1.33 (t, 3H), 1.75 (m, 6H), 2 .40 (m, 1H), 3.43 (s, 3H), 4.23 (s, 2H), 4.45 (q, 2H), 6.78 (s, 1H). It was confirmed that the obtained product was ethyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate. As a result of measurement by gas chromatography, the purity of the obtained ethyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate was 98%, and the yield was 51%. .

Example 4
In place of 15.3-mmol of methyl 2- (methoxymethyl) -3-phenyl-2-propenoate, 15.3-mmol of ethyl 2- (methoxymethyl) -3-cyclohexyl-2-propenoate of Preparation Example 2 A solid component was prepared in the same manner as in Example 1 except that a polymerization catalyst was formed and polymerized. As a result, the titanium content in the obtained solid catalyst component was 2.5% by weight. The results are shown in Table 1.

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

Claims (9)

A solid catalyst component for olefin polymerization containing titanium, magnesium, halogen and a compound represented by the following general formula (1).
General formula (1);

(1)
(In the formula, R ¹ and R ² are a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, and a linear chain having 3 to 20 carbon atoms. Alkenyl group or branched alkenyl group, linear halogen-substituted alkyl group having 1 to 20 carbon atoms, branched halogen-substituted alkyl group having 3 to 20 carbon atoms, linear halogen-substituted alkenyl group having 2 to 20 carbon atoms, carbon number Branched halogen-substituted alkenyl group having 3 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, halogen substitution having 3 to 20 carbon atoms Including a cycloalkenyl group, an aromatic hydrocarbon group having 6 to 24 carbon atoms, a halogen-substituted aromatic hydrocarbon group having 6 to 24 carbon atoms, and a nitrogen atom having 2 to 24 carbon atoms whose bond ends are carbon atoms. A hydrocarbon group, a C2-C24 oxygen atom-containing hydrocarbon group whose bond terminal is a carbon atom, a C2-C24 phosphorus-containing hydrocarbon group whose bond terminal is a carbon atom, or C1-C24 A silicon-containing hydrocarbon group, wherein R ¹ and R ² may be the same or different, and may be bonded to each other to form a cyclic group, provided that R ¹ is hydrogen or methyl; When it is a group, the carbon number of R ² is 2 or more, and R ³ and R ⁴ are a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a vinyl group, and a carbon number. 3-20 linear alkenyl group or branched alkenyl group, C1-C20 linear halogen-substituted alkyl group, C3-C20 branched halogen-substituted alkyl group, C2-C20 linear halogen Substituted alkenyl group, C3-C20 branch Halogen-substituted alkenyl group, cycloalkyl group having 3 to 20 carbon atoms, cycloalkenyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkyl group having 3 to 20 carbon atoms, halogen-substituted cycloalkenyl group having 3 to 20 carbon atoms, carbon A C6-C24 aromatic hydrocarbon group, a C6-C24 halogen-substituted aromatic hydrocarbon group, a C2-C24 nitrogen atom-containing hydrocarbon group in which the bond terminal is a carbon atom, and a bond terminal in the carbon atom An oxygen atom-containing hydrocarbon group having 2 to 24 carbon atoms, a phosphorus-containing hydrocarbon group having 2 to 24 carbon atoms whose bond ends are carbon atoms, or a silicon-containing hydrocarbon group having 1 to 24 carbon atoms; ³ and R ⁴ may be the same or different, provided that the nitrogen atom-containing hydrocarbon group having 2 to 24 carbon atoms in R ^{1 to} R ⁴ is a group in which the bond terminal is a C═N group. , The carbon number 2 Oxygen atom-containing hydrocarbon group of 24, those coupling terminal is a carbonyl group, a phosphorus-containing hydrocarbon group of carbon number 2 to 24 are excluded respectively those bond terminus is C = P group. ) R ¹ or R ² in the general formula (1) is a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, or a linear alkenyl having 3 to 12 carbon atoms. The group according to claim 1, which is a group or a branched alkenyl group, a cycloalkyl group having 5 to 12 carbon atoms, a cycloalkenyl group having 5 to 12 carbon atoms, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. Solid catalyst component for olefin polymerization. The R ³ or R ⁴ in the general formula (1) is a linear alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 3 to 12 carbon atoms. Solid catalyst component for olefin polymerization. (I) The solid catalyst component for olefin polymerization according to any one of claims 1 to 3,
(II) the following general formula (2);
R ⁵ _p AlQ _3-p (2)
(In the formula, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, Q represents a hydrogen atom, a hydrocarbyloxy group having 1 to 6 carbon atoms, or a halogen atom, p is a real number of 0 <p ≦ 3, and In which R ⁵ may be the same or different.) And (III) an olefin polymerization catalyst characterized by being formed from (III) an external electron donating compound. The external electron donating compound (III) is one or more selected from an organosilicon compound represented by the following general formula (3) and an aminosilane compound represented by the following general formula (4). The olefin polymerization catalyst according to claim 4, wherein:
General formula (3);
R ⁶ _q Si (OR ⁷ ) _4-q (3)
(In the formula, R ⁶ is an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group, or an aromatic having 6 to 15 carbon atoms. R ⁷ is an alkyl group having 1 to 4 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, or a carbon atom. A cycloalkyl group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, which may be the same or different. (It is an integer of 0 ≦ q ≦ 3.)
General formula (4);
(R ⁸ R ⁹ N) _s SiR ¹⁰ _4-s (4)
Wherein R ⁸ and R ⁹ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a vinyl group, an alkenyl group having 3 to 20 carbon atoms, a cycloalkyl group or a cycloalkenyl group having 3 to 20 carbon atoms, or carbon R ⁸ and R ⁹ may be the same or different and may be bonded to each other to form a ring, R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, Vinyl group, alkenyl group having 3 to 12 carbon atoms, alkoxy group having 1 to 20 carbon atoms, vinyloxy group, alkenyloxy group having 3 to 20 carbon atoms, cycloalkyl group or cycloalkyloxy group having 3 to 20 carbon atoms, or an aryl group or an aryloxy group having 6 to 20 carbon atoms, when there are a plurality of R ¹⁰ s, the plurality of R ¹⁰ may optionally be the same or different .s is an integer from 1 to 3.)   The external electron donating compound (III) is phenyltrimethoxysilane, n-butyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, phenyltriethoxysilane, n-butyltriethoxysilane, cyclopentyltriethoxysilane. , Cyclohexyltriethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylcyclopentyl Dimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis ( Tilamino) silane, dicyclohexylbis (ethylamino) silane, dicyclopentylbis (ethylamino) silane, bis (perhydroisoquinolino) dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, trimethylsilyltrimethoxysilane or trimethylsilyltriethoxy 6. The olefin polymerization catalyst according to claim 5, which is silane. 5. The olefin polymerization according to claim 4, wherein the external electron donating compound (III) is at least one selected from diether compounds represented by the following general formula (5): catalyst.
General formula (5);
R ¹¹ OCH ₂ CR ¹² R ¹³ CH ₂ OR ¹⁴ (5)
Wherein R ¹² and R ¹³ are a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a vinyl group, an alkenyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a cycloalkenyl group. , An aromatic hydrocarbon group having 6 to 12 carbon atoms or a halogen-substituted aromatic hydrocarbon group, an aromatic hydrocarbon group having 7 to 12 carbon atoms having a substituent, an alkylamino group having 1 to 12 carbon atoms, or a carbon number 2 to 12 dialkylamino groups which may be the same or different and may be bonded to each other to form a ring, and R ¹¹ and R ¹⁴ are each an alkyl group having 1 to 12 carbon atoms, a vinyl group, a carbon number; 3-12 alkenyl group, C3-C6 cycloalkyl group, C6-C12 aromatic hydrocarbon group or halogen-substituted aromatic hydrocarbon group, or C7-C12 having a substituent Of aromatic hydrocarbon groups, which may be the same or different)   The diether compound represented by the general formula (5) is 2-isopropyl-2-isobutyl-1,3-dimethoxypropane or 9,9-bis (methoxymethyl) fluorene. Catalyst for polymerization of olefins.   A method for producing an olefin polymer, wherein olefins are polymerized in the presence of the olefin polymerization catalyst according to any one of claims 4 to 8.