JPH0435486B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an improvement in a method for producing an α-olefin polymer. More specifically, the present invention uses a highly active catalyst for the stereoregular polymerization of olefins that can be polymerized at high temperatures for long periods of time to stereoregularly polymerize α-olefins or α-olefins and other olefins such as ethylene. The present invention relates to a method for efficiently producing stereoregular α-olefin polymers by homopolymerizing or copolymerizing them. Conventional technology Conventionally, as a stereoregular polymerization catalyst for olefin, for example, a combination of a titanium halide and an organoaluminum compound such as triethylaluminum or diethylaluminum chloride has been used.
It is well known that it is used industrially. In addition, as a highly active and highly stereoregular polymerization catalyst,
A number of catalyst systems have been proposed which consist of a solid component consisting of an inorganic or organic aluminum compound, a titanium halide and a carboxylic acid ester, and triethylaluminum and an electron donor. The present inventors previously discovered that organic magnesium components and
A highly active catalyst system is formed by combining a halogen-containing magnesium solid component obtained by reacting a chlorosilane compound having an Si-H bond with a titanium halogen compound, a hydrocarbon carboxylic acid ester, and an organoaluminum compound. It was discovered that polymers with high stereoregularity could be obtained by polymerizing olefins using this (Japanese Patent Publication Nos. 57-9567, 60-10524,
Publication No. 60-11924, Publication No. 62-5925, Japanese Unexamined Patent Publication No. 1983
-104903), further comprising a solid catalyst component consisting of a reaction product of the halogen-containing magnesium or solid component, a titanium halide and a carboxylic acid ester, or a solid catalyst component formed by further treating this reaction product with a tetravalent titanium compound. It has been found that a catalyst system consisting of a combination of a solid catalyst component, an alkoxysilane, and an organoaluminum compound has less tendency for the activity of the catalyst to decline over time in the polymerization of olefins (Japanese Patent Publication No. 11924/1982). By the way, in recent years, catalysts with higher activity and higher stereoregularity have been developed, especially for the purpose of improving polymerization heat removal efficiency and applying them to gas phase polymerization processes. The development of a catalyst is desired, and furthermore, for the purpose of application to so-called block polymerization, which has a relatively long residence time in a polymerization vessel, there is a need to develop a catalyst whose activity decreases little with the passage of polymerization time. ing. However, in response to these requirements, the catalysts of the prior art are not suitable for high temperature polymerization (e.g. 75°C or higher).
Both the stereoregularity and the maintenance of activity during long-term polymerization were not always fully satisfactory. Problems to be Solved by the Invention The present invention overcomes the drawbacks of conventional stereoregular polymerization catalysts for olefins, and produces polymers with high stereoregularity even at higher polymerization temperatures and longer polymerization times. α-
The purpose of this invention is to provide a method for efficiently producing olefin polymers. Means for Solving the Problems As a result of extensive research into highly active catalysts for the stereoregular polymerization of olefins having the above-mentioned excellent characteristics, the present inventors discovered that silicon containing siloxy groups and siloxane compounds as organomagnesium components A magnesium-containing solid component obtained by reacting a chlorosilane compound having an Si-H bond in the presence or absence of an aromatic carboxylic acid ester using a magnesium-containing complex, or in the presence or absence of an aromatic carboxylic acid ester. , a reaction product of a magnesium-containing solid component obtained by further reacting the two components with a halogenated organic aluminum compound and a titanium halide, or a reaction of the solid component, a titanium halide, and an aromatic carboxylic acid ester. An α-olefin is polymerized using a catalyst consisting of a solid catalyst component consisting of a compound, or a solid catalyst component obtained by further treating these reactants with the titanium halide, in combination with an organoaluminum compound and an alkoxysilane compound. The inventors have discovered that the above object can be achieved by doing so, and have completed the present invention based on this knowledge. That is, in the present invention, in producing a stereoregular α-olefin polymer by polymerizing α-olefin in the presence of a catalyst, (A)(B)(i) (a) General Formula (M)〓(Mg)〓(R ¹ ) _p (R ² ) _q (X) _r (Y) _s・(E) _c
...() [In the formula, M is a metal atom of group 1 or group of the periodic table, α is 0 or a number larger than 0, β is a number larger than 0, p, q, r and s are each p+q+r+s=mα+2β
(However, m is 0 or a number larger than 0 that satisfies the relationship of valence of M), c is 0 or a number larger than 0, and R ¹ and R ² are the same or different hydrocarbons having 1 to 20 carbon atoms. group, X and Y are the same or different halogen atoms, -
OR ³ or -OSiR ⁴ R ⁵ R ⁶ (wherein R ³ is a hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or a hydrocarbon group), and at least one of X and Y is -OSiR ⁴ R ⁵ R ⁶ ,
E is a siloxane compound] A silicon-containing magnesium component,
or a reaction product of this silicon-containing organomagnesium component and (b) at least one electron donor selected from ether, ketone, aldehyde, alcohol, and amine; (ii) general formula H _a SiCl _b R ⁷ _4-(a+b) ...() (R ⁷ in the formula is a hydrocarbon group having 1 to 20 carbon atoms, a and b are each a number larger than 0 that satisfies the relationship a+b≦4) A solid component obtained by reacting a chlorosilane compound having a Si-H bond in the presence or absence of (iii) an aromatic carboxylic acid ester, or a solid component obtained by reacting the component (i) with the component (ii) and (iv) ) General formula AlR ⁸ _o Z _3-o ... () (R ⁸ in the formula is a hydrocarbon group having 1 to 20 carbon atoms, Z is a halogen atom, and n is a number that satisfies the relationship 0<n<3) A solid component obtained by reacting a halogenated organoaluminium compound represented by (iii) in the presence or absence of an aromatic carboxylic acid ester, and (b) a general formula Ti(OR ⁹ ) _n D _4-n ... () (R ⁹ in the formula is a hydrocarbon group having 2 to 10 carbon atoms,
(D is a halogen atom, m is a number that satisfies the relationship 0≦m<4) or a solid catalyst component consisting of a reaction product with a titanium compound represented by (A) and (B) and (C).
A solid catalyst component consisting of a reactant with an aromatic carboxylic acid ester, or a solid catalyst component formed by further treating these reactants with the component (b) above, (B) a trialkylaluminum compound, and (C) a general formula R ¹⁰ lSi(OR ¹¹ ) _4-l ...() (R ¹⁰ and R ¹¹ in the formula are the same or different hydrocarbon groups having 1 to 20 carbon atoms, and l is a number that satisfies the relationship 0≦l<4 ) Provides a method for producing an α-olefin polymer, which is characterized by using a catalyst system comprising an alkoxysilane compound shown in the following. The present invention will be explained in detail below. (A) in the catalyst used in the method of the present invention
The silicon-containing organomagnesium component (i) (i) (a), which is one of the raw materials for the solid catalyst component, has the general formula (M)〓(Mg)〓(R ¹ ) _p (R ² ) _q (X) _r (Y) _s・(E) _c …(
) (M, R ¹ , R ² , X, Y, E, α, β,
(p, q, r, s and c have the same meanings as above) A silicon-containing organomagnesium compound or a silicon-containing organomagnesium complex. The hydrocarbon group represented by R ¹ to R ² in the general formula () is an alkyl group, a cycloalkyl group, or an aryl group, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, Examples include phenyl groups, especially R ¹
is preferably an alkyl group. Further, when α>0 and X and Y are not halogen atoms, a metal element belonging to Group 1 or Group 3 of the periodic table can be used as the metal atom M, such as lithium, sodium , potassium, calcium, beryllium, zinc,
Examples include barium, boron, and aluminum, but lithium, aluminide, zinc, boron, and beryllium are particularly preferred because they facilitate the formation of hydrocarbon-soluble organomagnesium complexes. Regarding the atomic ratio β/α of magnesium to metal atom M,
Can be set arbitrarily, but preferably 0.1 to 10,
In particular, hydrocarbon soluble organomagnesium complexes in the range 1 to 10 are particularly preferred. Relational expression p+q+ of symbols α, β, p, q, r, s
r+s=mα+2β indicates the stoichiometry between the valence of the metal atom and the substituent, and
The ratio (r+s)/(α+β) of the sum of Y and Y is preferably selected in the range of 0 or more and less than 1.0, more preferably in the range of 0 to 0.8. Further, in the general formula (), examples of the siloxane compound represented by E include hexamethylsiloxane, symmetrical dihydrotetramethyldisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, methylhydrodiene polysiloxane, dimethyl Examples include polysiloxane and phenylhydropolysiloxane. C represents the amount of the siloxane compound E coordinated with M or Mg, and is 0 or a number larger than 0. Further, in the formula (), any one of r, s and c is a number larger than 0, and when r and s are 0, c is 0.1 or more, preferably 0.2≦c<
20, more preferably a number satisfying the relationship 0.4≦c<10. These organomagnesium compounds or organomagnesium complexes have the general formula R ¹ MgQ, R ¹ ₂ Mg
(R ¹ has the same meaning as above, Q is a halogen atom);
An organometallic compound represented by the general formula MR ² _n or MR ² _n-1 H (M, R ² , m have the same meanings as above) and an inert carbonized compound such as hexane, heptane, cyclohexane, benzene, toluene, etc. It can be produced by reaction in a hydrogen medium at a temperature ranging from room temperature to 150°C, followed by further reaction with a siloxane compound or a siloxane compound and an alcohol. Furthermore, the organomagnesium compound or organomagnesium complex may include MgX ₂ ,
R ¹ MgX and MR ² _n , MR ² _n-1 H, or R ¹ MgX,
MgR ¹ ₂ and R ² _o MX _no , or R ¹ MgX, MgR ₂ and _Yo
Reaction with MX _no (wherein M, R ¹ , R ² , X, and Y have the same meanings as above, including the case where X and Y are halogen atoms, and n is a number from 0 to m) It can be manufactured by Generally, the organomagnesium compound is insoluble in an inert hydrocarbon medium, and the organomagnesium complex where α>0 and where X and Y are not halogen atoms is soluble. Furthermore, even when α is 0, certain organomagnesium compounds, such as sec-Bu ₂ Mg, are soluble in hydrocarbon media, and such compounds can also be suitably used in the present invention. The organomagnesium compound has the general formula (Mg)〓(R ¹ ) _p (R ² ) _q (X) _r (Y) _s・(E) _c ...(-1) (R ¹ , R ² , X, Y, E, β, p, q,
(r, s and c have the same meanings as above), and R ¹ and R ² in the general formula (-1) are (1) at least one of R ¹ and R ² has 4 to 6 carbon atoms; a secondary or tertiary alkyl group, preferably
R ¹ and R ² both have 4 to 6 carbon atoms, and at least one is a secondary or tertiary alkyl group;
or (2) R ¹ and R ² are alkyl groups having different numbers of carbon atoms,
Preferably, R ¹ is an alkyl group having 2 or 3 carbon atoms, and R ² is an alkyl group having 4 or more carbon atoms, or (3) at least one of R ¹ and R ² is a carbonized group having 6 or more carbon atoms. It is desirable that hydrogen groups, preferably both R ¹ and R ² are alkyl groups having 6 or more carbon atoms. In the above (1), the secondary or tertiary alkyl group _having 4 to 6 carbon atoms includes sec- _C4H9 , tert- _{C4H9 ,}

【formula】

【formula】

【formula】

【formula】

【formula】 【formula】

[Formula] etc. Among these, secondary alkyl groups are preferred, and sec-C ₄ H ₉ is particularly preferred. In the above (2), examples of the alkyl group having 2 or 3 carbon atoms include ethyl group, n-propyl group, and isopropyl group, but among these, ethyl group is preferable, and the alkyl group having 4 or more carbon atoms is Examples include a butyl group, an amyl group, a hexyl group, an octyl group, and a butyl group and a hexyl group are particularly preferred. Further, in (3), examples of the hydrocarbon group having 6 or more carbon atoms include hexyl group, octyl group, decyl group, phenyl group, etc. Among these, an alkyl group, particularly hexyl group, is preferable. It is important that the organomagnesium compound used in the present invention is soluble in a hydrocarbon medium. As the number of carbon atoms in the alkyl group increases, it becomes easier to dissolve in a hydrocarbon medium, but the viscosity of the solution tends to increase, and it is not preferable to use one having an alkyl group with an unnecessarily long chain from the viewpoint of handling. The organomagnesium compound is usually used as a hydrocarbon solution, but it can be used even if a trace amount of a complexing agent such as ether, ester, or amine is contained or remains in the solution. can. In the present invention, as the organomagnesium component (a), any of the above-mentioned organomagnesium complexes and organomagnesium compounds can be preferably used, but it is particularly preferable to use an organomagnesium complex, and the organomagnesium component is Although it may be reacted as it is with (ii) a chlorosilane compound having a Si--H bond, it is preferable to react with (b) an electron donor and then react this reactant with the chlorosilane compound. The reaction between (a) the organomagnesium component and (b) the electron donor is preferably carried out in a liquid phase, and in particular, an organomagnesium component soluble in a hydrocarbon or ether solvent is used, and the electron donor is reacted in the solvent. It is preferable to react with the body. As the electron donor, ether, ketone,
At least one compound selected from aldehydes, alcohols and amines is used. The ether may be an aliphatic, aromatic or alicyclic hydrocarbon group in the general formula ROR' in which R and R' are the same or different, such as methyl, ethyl,
propyl, butyl, amyl, hexyl, decyl,
Examples include groups such as octyl, dodecyl, cyclohexyl, phenyl, and benzyl. Ketones include aliphatic groups, aromatic groups, alicyclic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, Examples include groups such as octyl, dodecyl, cyclohexyl, phenyl, and benzyl. Ketones include aliphatic groups, aromatic groups, alicyclic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, cyclohexyl, in the general formula RCOR', where R and R' are the same or different; Examples include various groups such as phenyl, and among these, dimethyl ketone and diethyl ketone are particularly preferably used. As the aldehyde, aliphatic, aromatic, alicyclic aldehydes, etc. are used. Further, alcohols include, for example, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, phenol, cresol, etc. Among these, sec-propyl alcohol, sec-butyl alcohol, tert- Secondary such as butyl alcohol, sec-amyl alcohol, tert-amyl alcohol, sec-hexyl alcohol, phenol, o, m, p-cresol,
Tertiary or aromatic alcohols are preferred. On the other hand, amines include aliphatic, alicyclic or aromatic amines, and secondary or tertiary amines such as trialkylamine, triphenylamine, pyridine and the like give preferable results. For the reaction of these electron donors with the organomagnesium component (a), an inert reaction medium such as an aliphatic hydrocarbon such as hexane or heptane,
The reaction can be carried out in an aromatic hydrocarbon such as benzene, toluene, or xylene, an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane, an ether solvent, or a mixed solvent thereof. There is no particular restriction on the reaction order, and any method can be used, such as adding an electron donor to the organomagnesium component, adding the organomagnesium component to the electron donor, or adding both at the same time. can. Regarding the reaction ratio between the organomagnesium component and the electron donor, the amount of the electron donor is 1 mol or less, preferably 0.01 mol or less, per 1 mol of the organomagnesium component.
It is desirable to use it in a proportion of 0.8 mol to 0.8 mol, particularly preferably 0.05 to 0.5 mol. (ii) The chlorosilane compound having a Si-H bond to be reacted with the organomagnesium component or a reaction product of this with an electron donor has the general formula H _a SiCl _b R ⁷ _4-(a+b) ...() ( In the formula, a, b and R ⁷ have the same meanings as above), and in the formula,
The hydrocarbon group represented by R ⁷ is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and specific examples include methyl, ethyl, propyl, butyl, amyl, hexyl, decyl, Examples include groups such as cyclohexyl and phenyl,
Among these, alkyl groups having 1 to 10 carbon atoms are preferred, and lower alkyl groups such as methyl, ethyl, and propyl groups are particularly preferred. Also, a and b are a+b
It is a number larger than 0 that satisfies the relationship of ≦4, and a is preferably 1 or 2. Examples of chlorosilane compounds having such a Si-H bond include HSiCl ₃ , HSiCl ₂ CH ₃ ,
HSiCl ₂ C ₂ H ₅ , HSiCl ₂ (n-C ₃ H ₇ ), HSiCl ₂ (iso
_-C3H7 ) _{, HSiCl2} ( _{n - C4H9} ), _{HSiCl2C6H5 ,
HSiCl2} (4-Cl- _C6H4 ) _{, HSiCl2CH} = _CH2 ,
_{HSiCl2CH2C6H5 , HSiCl2 ( 1} - _C10H7 ) _{,
HSiCl2CH2CH = CH2} , _{H2SiClCH3 ,}
H ₂ SiClC ₂ H ₅ , HSiCl(CH ₃ ) ₂ , HSiClCH ₃ (iso−
C ₃ H ₇ ), HSiClCH ₃ (C ₆ H ₅ ), HSiCl (C ₂ H ₅ ) ₂ ,
Examples include HSiCl(C ₆ H ₅ ) ₂ . These compounds may be used alone or in combination of two or more. Among the above compounds, trichlorosilane, monomethyldichlorosilane, dimethylchlorosilane, ethyldichlorosilane, etc. are preferred, and trichlorosilane is particularly preferred. , monomethyldichlorosilane is preferred. The reaction between (i) the organomagnesium component and (ii) the chlorosilane compound may be carried out in the presence or absence of (iii) the aromatic carboxylic acid ester, and by this reaction, MgCl ₂ A reactant containing . During these reactions, an inert reaction medium is used, for example aliphatic hydrocarbons such as hexane, heptane, aromatic hydrocarbons such as benzene, toluene, xylene, cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, etc. 2-dichloroethane, O
- The reaction can be carried out in a chlorinated hydrocarbon such as dichlorobenzene or dichloromethane, an ether solvent such as ether or tetrahydrofuran, or a mixed solvent thereof. Also, there are no particular restrictions on the reaction temperature, but
In terms of reaction progress, it is preferable to conduct the reaction at a temperature of 40°C or higher. When carrying out a reaction in the presence of an aromatic carboxylic acid ester, the ratio of the three components used is usually a chlorosilane compound per 1 mole of organomagnesium component (based on magnesium).
The amount of aromatic carboxylic acid ester used is usually 0.01 to 100 mol, preferably 0.1 to 10 mol, and the aromatic carboxylic acid ester is usually 0.01 to 5.0 mol, preferably 0.1 to 1.0 mol. In the above reaction, the aromatic carboxylic acid ester used as desired is preferably a mono- or diester, such as methyl or ethyl benzoate; the aromatic carboxylic acid ester is preferably a mono- or diester, such as benzoic acid. methyl, ethyl, propyl, butyl, amyl ester of p-toluic acid, methyl, ethyl, propyl, butyl, amyl ester of p-toluic acid, methyl, ethyl, propyl, butyl, amyl ester of p-anisic acid, monoster of phthalic acid dimethyl, diethyl, di-n-propyl, di-iso-propyl,
Examples include diesters such as di-n-butyl, di-iso-butyl, di-n-heptyl, di-2-ethylhexyl, and di-n-octyl. One type of these aromatic carboxylic acid esters may be used, or
You may use two or more types in combination. In the present invention, in the reaction between the (i) organomagnesium component and (ii) the chlorosilane compound, (iv) the general formula AlR ⁸ _o Z _3-o ... () (R ⁸ in the formula, A halogenated organoaluminum compound represented by (Z and n have the same meanings as above) may be added, and the reaction may be carried out in the presence or absence of (iii) aromatic carboxylic acid ester. Examples of the aluminum halide compound include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, di-iso-butylaluminum chloride,
Di-n-hexylaluminum chloride, di-
iso-hexylaluminum chloride, di(2-
ethylhexyl) aluminum chloride, di-n
-dodecylaluminum chloride, methyl-iso
-Butylaluminum chloride, ethyl-iso-
Examples include butylaluminum chloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, iso-butylaluminum sesquichloride, methylaluminum dichloride, ethylaluminum dichloride, iso-butylaluminum dichloride, diethylaluminium bromide, diethylaluminum iodide, etc., and mixtures thereof. It will be done. This reaction can be carried out in the same inert solvent as above, and there is no particular restriction on the reaction temperature, but a temperature of 40° C. or higher is preferable in view of the progress of the reaction. In addition, the amount of the halogenated organoaluminum compound used is usually 0.01 to 100 mol per 1 mol of the organomagnesium component (based on magnesium).
It is preferably selected within the range of 0.1 to 10 mol. The solid components obtained by this reaction are separated by means such as filtration or decantation, and then thoroughly washed with an inert solvent such as hexane, heptane, cyclohexane, or toluene to remove unreacted materials and by-products. It is preferable to remove objects. Further, as the cleaning method, it is also advantageous to perform washing one or more times using a halogenated hydrocarbon solvent, and then sufficiently washing using an inert solvent such as hexane. The titanium compound as the component (B) used in the preparation of the solid catalyst component (A) in the catalyst according to the present invention has the general formula Ti( ^OR9 ) _{nD4 -n} ...() (in the formula, ^R9 , D and m has the same meaning as above), and the hydrocarbon group having 2 to 10 carbon atoms represented by R ₉ in the formula includes an alkyl group,
Cycloalkyl groups and aryl groups are preferred, such as ethyl, propyl, butyl, amyl, hexyl, decyl, cyclohexyl, and phenyl, among which alkyl groups are particularly preferred. Specific examples of this titanium compound include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, dibutoxytitanium dichloride, and tributoxytitanium monochloride. Among these, titanium tetrachloride is particularly suitable. The solid catalyst component (A) in the catalyst of the present invention may be prepared by reacting the solid component (A) with the titanium compound (B);
The reaction may be carried out by reacting component (a), component (b), and further aromatic carboxylic acid ester (c). As the aromatic carboxylic acid ester (c), the mono- or diesters mentioned in the description of the aromatic carboxylic acid ester (i) and (iii) above can be used. The reaction between the (a) solid component and (b) the titanium compound, and (a)
The reaction between the solid component, (b) the titanium compound, and (c) the aromatic carboxylic acid ester may be carried out in a liquid phase or a gas phase. may be pulverized. Also,
Regarding the reactions of the three components (a), (b), and (c), (1) a method in which the solid component, a titanium compound, and an aromatic carboxylic acid ester are simultaneously reacted, and (2) a method in which the solid component and the titanium compound are first reacted. After the reaction, an aromatic carboxylic acid ester is reacted with the reaction, or (3)
There are methods such as first reacting a solid component with an aromatic carboxylic acid ester and then reacting this with a titanium compound, and any method can be used, but method (1) is particularly preferred. Next, (a) the reaction between the solid component and (b) the titanium compound,
To explain a preferred example of the reaction between (a) the solid component, (b) the titanium compound, and (c) the aromatic carboxylic acid ester, an inert organic solvent is used as the reaction medium, and the solid component is The component and the titanium compound, or the solid component, the titanium compound, and the aromatic carboxylic acid ester are added and reacted. Examples of the inert organic solvent include aliphatic hydrocarbons such as hexane and heptane, aliphatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane,
Examples include chlorinated hydrocarbons such as 1,2-dichloroethane, dichlorobenzene, and dichloromethane, and among these, aromatic hydrocarbons and chlorinated hydrocarbons are preferred. Although there are no particular restrictions on the reaction temperature or the concentration of each component, the reaction is usually carried out at a temperature of 80° C. or higher and at a titanium compound concentration of 2 moles or higher. Alternatively, without using the inert solvent, the titanium compound itself may be used as a reaction medium, and a solid component or a solid component and an aromatic carboxylic acid ester may be added thereto and reacted. Regarding the ratio of each component used in these reactions, it is preferable to carry out the reaction in the presence of a sufficiently excess amount of titanium compound relative to the magnesium component in the solid component, and the aromatic carboxylic acid ester is Usually 0.01 to 1 mole of magnesium
The amount is selected from 1.0 mol, preferably from 0.05 to 0.5 mol. In addition, as another method for the reaction of (a) the solid component, (b) the titanium compound, and (c) the aromatic carboxylic acid ester, the solid component and the aromatic carboxylic acid ester can be reacted in the above-mentioned inert organic solvent. A method can be used in which a solid component is reacted with an ester and then a titanium compound is reacted therewith, or a solid component is reacted with a titanium compound and then an aromatic carboxylic acid ester is reacted with the solid component. There are no particular restrictions on the temperature during each reaction, but it is usually room temperature or 100%
Selected in the range of °C. In addition, when reacting a solid component with an aromatic carboxylic acid ester, there is no particular restriction on the ratio of each component used, but the aromatic carboxylic acid ester is usually used per mole of magnesium contained in the solid component. 0.01-1.0 mol,
It is preferably used in a proportion of 0.05 to 0.5 mole.
When reacting an aromatic carboxylic acid ester with a reaction product of a solid component and a titanium compound, the amount of the aromatic carboxylic acid ester is usually 0.01 to 1.0 mol, preferably 0.05 to 1.0 mol, per 1 mol of titanium atoms in the reaction product.
It is used in a proportion of 0.5 mole. The reaction product of (a) solid component and (b) titanium compound, or the reaction product of (a) solid component, (b) titanium compound, and (c) aromatic carboxylic acid ester thus obtained is: It can be pulverized as desired and used in the next step. As a pulverization method, well-known mechanical pulverization means such as a rotary ball mill, a vibrating ball mill, and an impact ball mill can be employed. Grinding time is usually
The grinding temperature is usually selected within the range of 0.5 to 100 hours, preferably 1 to 30 hours, and 0 to 200°C, preferably 10 to 150°C. Note that a method in which the solid component is pulverized together with an aromatic carboxylic acid ester and then reacted with a titanium compound, or a method in which the solid component is pulverized together with a titanium compound and then reacted with an aromatic carboxylic ester is also possible. In the present invention, the method obtained as described above
(a) A reaction product of a solid component and (b) a titanium compound, (a) a reaction product of a solid component, (b) a titanium compound, and (c) an aromatic carboxylic acid ester, or a pulverized product of these; b) May be treated with a titanium compound. This treatment further increases the catalyst efficiency of the present invention. As a treatment method using this titanium compound, inert organic solvents such as aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene and toluene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, 1,2 - treatment in a solvent such as a chlorinated hydrocarbon such as dichloroethane, dichlorobenzene, dichloromethane, preferably an aromatic hydrocarbon or a chlorinated hydrocarbon, or using the titanium compound itself as a reaction medium without using an inert solvent; , a method of processing can be used. When using an inert solvent, the concentration of the titanium compound is preferably 2 mol/or more. In addition, there are no particular restrictions on the processing temperature, but usually
Processing is carried out at temperatures above 80°C. The solid catalyst component (A) thus obtained is preferably thoroughly washed with an inert solvent such as hexane, heptane, cyclohexane, toluene, etc. to remove unreacted substances and by-products. It is also advantageous to wash one or more times with a halogenated hydrocarbon solvent followed by a thorough wash with an inert solvent such as hexane. Regarding the composition and structure of the solid catalyst component (A),
Although it depends on the type of starting materials and reaction conditions, the solid catalyst component has a compositional analysis value of about 1 to 10
Surface area containing 50-300% titanium atoms by weight
m ² /g. In the catalyst according to the present invention, as component (B),
Trialkylaluminium compounds are used.
As this trialkylaluminum compound,
For example, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminium, tri-n-butylaluminum, tri-iso-butylaluminum,
Trialkylaluminiums such as tri-n-hexanealuminum, tri-n-octylaluminium, tri-n-decylaluminum, tri-n-dodecylaluminum, trihexadecylaluminum, and aluminum isoprenyl are mentioned. Mixtures of these can also be used. The alkoxysilane compound as component (C) used in the catalyst according to the present invention has the general formula R ¹⁰ lSi(OR ¹¹ ) _4-l ...() (R ¹⁰ , R ¹¹ and l in the formula have the same meanings as above. ), and in this formula, when l is 0, Si
(OR ¹¹ ) ₄ is, for example, Si(OCH ₃ ) ₄ , Si
(OC ₂ H ₅ ) ₄ , Si(O-n-C ₃ H ₇ ) ₄ , Si(O-iso-
_C3H7 ) ₄ , Si( _O -n- _C4H9 ) ₄ , _Si (O-sec-
Examples include C ₄ H ₉ ) ₄ . In addition, R ¹⁰ Si (OR ¹¹ ) ₃ when l is 1,
_For example, _CH3Si ( _OCH3 ) _{3 , C2H5Si} ( _OCH3 ) ₃ , n- _C4H9Si (OCH3) _{3 ,} n _{- C5H11Si} ( _OCH3 ) ₃ , _{C6H 5} Si(OCH ₃ ) ₃ , C ₆ H ₅ CH ₂ Si(OCH ₃ ) ₃ , CH ₂ = CHSi(OCH ₃ ) ₃ , CH[Si(OCH ₃ ) ₃ ] ₃ , (CH ₃ O) ₃ SiCH ₂ Si( _{OCH3 ) 3} , ( _CH3O ) _{3SiCH2CH2Si ( OCH3} ) ₃ ,
CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CCl ₃ Si (OCH ₃ ) ₃ , CH ₃ CHClSi (OCH ₃ ) ₃ , CH ₂ ClCH ₂ Si (OCH ₃ ) ₃ , CH ₃ Si (OC ₈ H ₅ ) _{3 , C2H5Si} ( _{OC2H5 ) 3 ,} n- _{C3H7Si (} OC2H5 _{) 3 ,} n- _C4H9Si ( _OC2H5 ) ₃ , _n - _C5 H _11Si
( _{OC2H5 ) 3} , cyclo- _{C6H11Si ( OC2H5 ) 3} , _{C6H5Si ( OC2H5 ) 3} , ₁ - _{C10H7Si ( OC2H5} ) ₃ , CH ₂ =CHSi
( _{OC2H5 ) 3} , _CH2CH =CHSi( _OC2H5 ) ₃ , _{CH2 = CHCH2Si}
(OC ₂ H ₅ ), (C ₂ H ₅ O) ₃ SiCH ₂ Si (OC ₂ H ₅ ) ₃ , CH[Si
_{( OC2H5 ) 3 ] 3} , _{CF3C6H4Si ( OC2H5} ) _{3 ,} CH2ClSi( _{OC2H5 ) 3 , CCl3Si} ( _OC2H5 ) ₃ , _{CH2ClCH 2Si} ( _{OC2H5 ) 3} , _CH2ClCHClSi ( _OC2H5 ) _{3 , CH2} =CHSi ₍ O-iso- _C3H7 ) ₃ , (iso-
_C3H7O ) _3SiCH2Si- (O- _iso - _C3H7 ) ₃ , _{( iso-
C3H7O} ) _3SiCH2CH2Si- (O _{- iso - C3H7} ) _{3 ,
CH3CHClSi} (O _- iso- _C3H7 ) ₃ , _{CH2ClCH2Si (} O-iso- _C3H7 ) ₃ , _CH3Si ( _O-
n- _{C4H9 ) 3} , _C2H5Si (O-n _{- C4H9 ) 3} , _C6H5Si (O- _{n-
C4H9 ) 3} , _CH2 =CHSi(O-n _{- C4H9} ) ₃ , ₍ n- _C4H9O ) _3SiCH2Si (O-n _- C4H9 _{) 3 ,} (n _-C4H9O ) _3SiCH2CH2Si ( _{O - n - C4H9} ) _{3 ,} CH3CHClSi(O _- n _{- C4H9} ) ₃ , _CH2CH2ClSi
(O-n- _C4H9 ) ₃ , _{CH3Si (} O-iso _{- C3H7} ) ₃ , _CH2 =CHSi(O-
iso- _{C4H9 ) 3} , _{( iso} - _C4H9O ) _3SiCH2Si (O-iso _{- C4H9} ) ₃ , ₍ iso _{- C4H9O} ) _{3SiCH2CH2Si (} O-iso-
_C4H9 ) ₃ , _CH3CHClSi ( _O -iso- _{C4H9 ) 3 , CH2ClCH2Si} (O-iso _- C4H9 _{) 3} , _CH3Si (O-
sec- _{C4H9 ) 3} , _C6H5Si (O-sec-C4H9) ₃ , _CH2 =CHSi(O _- sec _{- C4H9 ) 3} , _CH3CHClSi (O _- sec- _{C4H9 ) 3} , _CH2ClCH2Si (O _- sec _{- C4H9 ) 3 ,} CH3Si(O-t- _C4H9 ) ₃ , _C6H5Si (O _- t-
Examples include C ₄ H ₉ ) ₃ . Next, R ¹⁰ ₂ Si (OR ¹¹ ) ₂ when l is 2 is:
For example, (CH ₃ ) ₂ Si (OCH ₃ ) ₂ , (C ₂ H ₅ ) ₂ Si
(OCH ₃ ) ₂ , (n-C ₃ H ₇ ) ₂ Si (OCH ₃ ) ₂ , (n-C ₄ H ₉ ) ₂ Si
(OCH ₃ ) ₂ , (n-C ₅ H ₁₁ ) ₂ Si (OCH ₃ ) ₂ , (C ₆ H ₅ ) ₂ Si
_{( OCH3} ) ₂ , ( _CH3 ) _2SiH ( _OC2H5 ) ₂ , ( _CH3 )( _C2H5 ) _Si
( _OC2H5 ) ₂ , ( _CH3 )( _{C6H5 )} Si( _{OC2H5 ) 2 , CH3SiCl}
( _OC2H5 ) ₂ , _C2H5SiH ( _{OC2H5 ) 2 ,} ( _{C2H5 ) 2Si} ( _OC2H5 ) ₂ and _{the like} . Furthermore, as R ¹⁰ ₃ SiOR ¹¹ when l is 3,
For example _, ( _CH3 ) _{3SiOCH3 ,} ( _C2H5 ) _{3SiOCH3 ,} ( _CH3 ) _3SiOC2H5 , ( _{CH3 ) 2} ( _n - _{C3H7 )
Examples} include _SiOC2H5 , _{( CH3 ) 2} ( _{C6H5 ) SiOC2H5 ,} ( _{C2H5 ) 3SiOC3H7} , ( _CH3 ) _3SiOC4H9 , _and the _like . Among these alkoxysilane compounds,
_{CH3Si ( OC2H5 ) 3} , C2H5Si _{( OC2H5 ) 3 , C3H7Si} ( _{OC2H5 ) 3 , C4H9Si} ( _{OC2H5 ) 3} , _C5H11Si ( _{OC2H5 ) 3 , C6H5Si} ( _{OC2H5 ) 3} , ( _{C6H5 ) 2Si} ( _OCH3 ) ₂ , and Si( _OC2H5 ) _{4 are particularly} preferable. The alkoxysilane compounds may be used alone, in combination of two or more, or in the form of a reaction product or adduct with an organoaluminum compound. Furthermore, complex compounds with common ethers, esters, amines, etc. can also be used in combination. Regarding the usage ratio of each catalyst component (A), (B), and (C) in the catalyst according to the present invention, component (B) is calculated based on aluminum atoms in 1 g of component (A). The amount of component (C) is 0.01 to 1000 mmol in terms of silicon atoms, so that the amount is in the range of 1 to 3000 mmol, preferably 5 to 1000 mmol.
The amount is preferably in the range of 0.05 to 100 mmol. The catalyst components (A), (B), and (C) may be brought into contact with each other during polymerization, or may be brought into contact with each other before polymerization. Further, in this contact before polymerization, only two arbitrary members may be selected and brought into contact with each other. Further, the components may be brought into contact with each other before polymerization under an inert gas atmosphere or under an olefin atmosphere. The catalyst according to the invention prepared in this way can be used in particular for propylene, butene-1, pentene-1,
To produce polymers with high stereoregularity by polymerizing α-olefins such as 1,4-methylpentene-1,3-methylbutene-1 under conditions of higher polymerization temperature and longer polymerization time. Are suitable. In addition, since there is very little decrease in activity with the passage of polymerization time, it is suitable for so-called block polymerization in which the residence time in a polymerization vessel is relatively long, such as copolymerization of the α-olefin with ethylene or the like. In the present invention, as a polymerization method, ordinary suspension polymerization, polymerization in a liquid monomer, gas phase polymerization, etc. can be used, but in particular, in the polymerization using the catalyst according to the present invention, the polymerization rate is relatively high. Polymerization methods in liquid monomers and gas phase polymerization methods used at high temperatures can be preferably employed. In suspension polymerization, a catalyst is generally introduced into a reactor together with a polymerization solvent, such as an aliphatic hydrocarbon such as hexane or heptane, and an α-olefin such as propylene is added to the reactor under an inert gas atmosphere.
A method is used in which the polymer is injected under pressure at ~20 kg/cm ² and polymerization is carried out at a temperature usually in the range of room temperature to 150°C. In polymerization in liquid monomers, under conditions where α-olefin such as propylene is in a liquid state,
α-olefin can be polymerized using liquid α-olefin as a polymerization solvent. For example, in the case of propylene, at temperatures between room temperature and 90°C,
Polymerization can be carried out in liquid propylene under a pressure of 45 mm/cm ² . On the other hand, gas phase polymerization is carried out at room temperature or at a pressure of 1 to 50 mm/cm ² in the absence of a solvent, under conditions where α-olefin such as propylene is a gas.
At a temperature of 120℃, α of propylene etc.
- Polymerization can be carried out using means such as a fluidized bed, moving bed, or mixing using a stirrer so that the olefin and the catalyst can come into good contact. In these polymerizations, hydrogen, halogenated hydrocarbons, or organometallic compounds that tend to undergo chain transfer may be added to adjust the molecular weight of the polymer. Next, the accompanying drawings show such embodiments of the method of the present invention as a flowchart. Effects of the Invention According to the method of the present invention, a specific solid catalyst component is
By using a highly active stereoregular polymerization catalyst obtained in combination with an organoaluminum compound and an organosilicon compound, α with high stereoregularity can be obtained with an extremely small amount of catalyst, so that a non-deashing process is possible. - Olefin polymers can be efficiently produced. In addition, the catalyst has the characteristic that it can provide a polymer with high stereoregularity even at higher polymerization temperatures and longer polymerization times compared to conventional techniques, and it also Since there is very little decrease in activity due to polymerization, the method of the present invention is also suitable for so-called block polymerization, which requires a relatively long residence time in the polymerization vessel, such as gas phase polymerization and copolymerization of α-olefin with ethylene, etc. used for. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, the boiling n-heptane extraction residue in the examples is the amount of extraction residue after extracting a polymer with boiling n-heptane for 6 hours, expressed as a percentage of the polymer. Example 1 (1) Preparation of siloxane-modified organomagnesium component (a) In a flask 1 which had been sufficiently purged with nitrogen in advance,
Organomagnesium complex solution represented by the composition formula Al _0.17 Mg (C ₂ H ₅ ) _0.51 (n-C ₄ H ₉ ) ₂ [1.0 mol/Mg metal concentration, Mg (n-C ₄ H ₉ ) ₂ and Al
250 ml of n-heptane solution obtained from (C ₂ H ₅ ) ₃ was added and kept at -10°C while stirring. Next, a heptane solution containing 500mM (based on Si) of dimethylpolysiloxane (viscosity at 30℃: 30 centistokes) was added from the dropping funnel.
After adding 200 ml over 30 minutes while keeping it at -10°C, it was heated and stirred at room temperature for 1 hour. As a result of analyzing this complex, the composition was found to be It was hot. (2) Preparation of magnesium-containing solid component In a thoroughly degassed and dried flask with a capacity of 2,
Add 500 ml of trichlorosilane (1 mol/n-heptane solution) and add phthalic acid di-n-
Add 10ml (38mM) of butyl and stir.
Keep at 65℃, and add 250mM (based on magnesium) of the organic magnesium component (a) from the dropping funnel.
was added dropwise over a period of 1 hour, and the mixture was further stirred at the same temperature for 1 hour to react. Next, 250 ml of ethylaluminum dichloride (1 mol/n-heptane solution) was added dropwise to this solution over a period of 1 hour.
The reaction was continued for 1 hour while maintaining the temperature at ℃ and stirring. Next, the white solid produced is filtered out,
After washing with n-hexane and drying, 25.3 g of white solid substance (A-1) was obtained. As a result of analyzing this solid substance, it was found that Mg8.85mmol per gram of solid.
Cl19.20mmol, Si2.23mmol, alkyl group
0.63mmol, di-n-butyl phthalate 0.45mmol
The specific surface area measured by BET method was 186 m ² /g. (3) Preparation of solid catalyst component Add 10 g of the solid (A-1) obtained in (2) and 200 ml of titanium tetrachloride to a 500 ml container purged with nitrogen, and add 1.4 ml (5 mM) of di-n-butyl phthalate. In addition, the mixture was reacted at 80°C for 1 hour while stirring. After the reaction, the solid was collected by hot filtration, suspended again in 200 ml of titanium tetrachloride, and heated at 110°C.
The mixture was allowed to react for 2 hours. After the reaction was completed, the solid was separated by hot filtration, thoroughly washed with hot n-heptane, further washed with n-hexane, and made into an n-hexane slurry to obtain a catalyst component (B-1). A portion of this was sampled and analyzed, and the Ti content in the catalyst solid was 2.5% by weight. (4) Polymerization in liquefied propylene 350 g of liquefied propylene was introduced into a 1.5 autoclave that had been thoroughly purged with nitrogen and vacuum dried, and then hydrogen gas was introduced in an amount such that the MFI of the produced polymer was 5. 80℃
7 mg of the solid catalyst component slurry (B-1) obtained in (3) above, 1.0 mmol of triethylaluminum, and 0.1 mmol of phenyltriethoxysilane were added to the autoclave, and heated at 80°C with stirring. Polymerization was carried out for 4 hours,
192 g of polymer was obtained. The activity per gram of solid catalyst component is 27400 g-pp/g-solid, and the boiling n-heptane extraction residue of this polymer is 97.2%.
It was hot. Example 2 (1) Preparation of siloxy group-containing organomagnesium component (a) In a 500 ml flask that had been sufficiently purged with nitrogen in advance,
The same organomagnesium complex solution used in Example 1 (1) (1.0 mol/Mg metal concentration)
250 ml of n-heptane solution) was added and kept at -10°C while stirring. Next, 100ml of n-heptane solution containing 250mlmM of polymethylhydrodiene polysiloxane was added to this from the dropping funnel.
ml was added dropwise over a period of 30 minutes while maintaining the temperature at -10°C, the temperature was raised to 80°C, and the reaction was allowed to proceed at this temperature for 3 hours while stirring. As a result of analyzing the obtained complex, the composition was found to be It was hot. (2) Preparation of solid catalyst component A solid catalyst component (B-2) was prepared in the same manner as in Example 1, except that the siloxane group-containing organomagnesium component (a) obtained in (1) above was used. A portion of this was sampled and analyzed, and the Ti content in the catalyst solid was 3.1% by weight. (3) Polymerization in liquefied propylene Using this solid catalyst component (B-2), polymerization was carried out in the same manner as in Example 1, and 178 g of polymer was obtained. The activity per gram of solid catalyst component was 25,400 g-pp/g-solid, and the activity per unit time was 6,350 g-pp/g-solid.Hr. Further, the residual content of this polymer after extraction with boiling n-heptane was 96.9%. Reference example Example 2 except that the polymerization time was changed to 2 hours.
Polymerization was carried out using the catalyst component (B-2) in the same manner as
102 g of polymer was obtained. Activity per gram of solid catalyst component per unit time is 7290g-pp/g-solid・Hr
The residual content of this polymer after extraction with boiling n-heptane was 97.5%. Examples 3 to 10 In the preparation of the solid catalyst of Example 1, the same procedure as in Example 1 was carried out, except that the substances shown in Table 1 were used as the siloxane-modified or siloxy group-containing organomagnesium complex component and the chlorosilane compound.
Solid catalyst components (B-3 to B-10) were prepared and polymerized in the same manner as in Example 1 to obtain the results shown in Table 1.

【table】

[Table] Examples 11 to 14 When preparing the solid substance (A-1) of Example 1, the following steps were carried out except that the aromatic carboxylic acid ester coexisting in advance was changed to the carboxylic acid ester shown in Table 2. Catalyst component (B) was prepared in the same manner as in Example 1.
-11 to B-14) were prepared and polymerized in the same manner as in Example 1, and the results shown in Table 2 were obtained.

[Table] Examples 15 to 17 The catalyst component (B-1) prepared in Example 1 was used, except that the alkoxysilane compound used in the polymerization in liquefied propylene was changed to the compound shown in Table 3. Polymerization was carried out in exactly the same manner as in Example 1, and the results shown in Table 3 were obtained.

[Table] Example 18 The solid component (A-18 ) 24.6g was obtained. As a result of analyzing this solid component, Mg8.92mmol per gram of solid.
Cl19.35mmol, Si2.30mmol, alkyl group
It contained 0.57 mmol, and the specific surface area measured by the BET method was 154 m ² /g. This solid component (A-
18) A solid catalyst component (B-18) was prepared in the same manner as in Example 1 using 10 g. Ti in solid catalyst component
The content was 2.7% by weight. Polymerization was carried out under the same conditions as in Example 1, except that 7 mg of this catalyst component was used in terms of solid component, and 184 g of polymer was obtained. Activity per gram of solid catalyst component is 26300g-pp/g-
The residual content of this polymer after extraction with boiling n-heptane was 95.7%. Example 19 In Example 1, as a method for preparing solid component (A-1), the amount of trichlorosilane solution used was
A solid component (A-19) was obtained in the same manner as in Example 1 (2), except that the volume was changed to 750 ml, the reaction time was changed to 3 hours, and ethylaluminum dichloride was not used. Pour a mixed solution of 100 ml of titanium tetrachloride and 100 ml of 1,2-dichloroethane into a 500 c.c. container that has been sufficiently purged with nitrogen in advance, and add 2.8 ml of di-n-butyl phthalate.
(10mM), and then the solid component (A-
19) 10g was added and reacted at 80°C for 2 hours while stirring. After the reaction, collect the solid by hot filtration,
The suspension was again suspended in 200 ml of titanium tetrachloride and reacted at 110°C for 2 hours. After the reaction was completed, the solid was separated by hot filtration and heated to 50°C. 1,2-dichloroethane
Suspend in 200ml, stir for 30 minutes, filter,
After thorough washing with n-hexane, it was made into an n-hexane slurry to obtain a catalyst component (B-19). The Ti content in the catalyst solid was 2.1% by weight. Polymerization was carried out in the same manner as in Example 1, except that 7 mg of this catalyst component (B-19) was used in terms of solid component, and polymer 182
I got g. Activity per 1g of solid catalyst component is 26000
g-pp/g-solid, and the residue after boiling n-heptane extraction of this polymer was 96.5%.

[Brief explanation of drawings]

The figure is a schematic flowchart illustrating aspects of the invention.

Claims (1)

[Scope of Claims] 1. In producing a stereoregular α-olefin polymer by polymerizing α-olefin in the presence of a catalyst, (A)(B)(i) (a) General formula (M)〓(Mg)〓(R ¹ ) _p (R ² ) _q (X) _r (Y) _s・(E) _c [M in the formula is a metal atom of Group 1 or Group 1 of the periodic table. , α is 0 or a number larger than 0, β is a number larger than 0, p, q, r and s are each p+q+r+s=mα+2β
(However, m is 0 or a number larger than 0 that satisfies the relationship of valence of M), c is 0 or a number larger than 0, and R ¹ and R ² are the same or different hydrocarbons having 1 to 20 carbon atoms. group, X and Y are the same or different halogen atoms, -
OR ³ or -OSiR ⁴ R ⁵ R ⁶ (wherein R ³ is a hydrocarbon group, R ⁴ , R ⁵ and R ⁶ are each a hydrogen atom or a hydrocarbon group), and at least one of X and Y is -OSiR ⁴ R ⁵ R ⁶ ,
E is a siloxane compound] or this silicon-containing organomagnesium component and (b) ether, ketone, aldehyde,
A reaction product with at least one electron donor selected from alcohols and amines, (ii) General formula H _a SiCl _b R ⁷ _4-(a+b) (R ⁷ in the formula has 1 carbon number) ~20 hydrocarbon groups, a and b are each a number larger than 0 that satisfies the relationship a+b≦4) and (iii) an aromatic carboxylic acid ester. A solid component formed by reacting in the presence or absence of the above components (i) and (ii) and (iv) general formula AlR ⁸ _o Z _3-o (R ⁸ in the formula has 1 carbon number) (iii) in the presence of an aromatic carboxylic acid ester or (b) General formula Ti(OR ⁹ ) _n D _4-n (R ⁹ in the formula is a hydrocarbon group having 2 to 10 carbon atoms,
(D is a halogen atom, m is a number that satisfies the relationship 0≦m<4) or a solid catalyst component consisting of a reaction product with a titanium compound represented by (A) and (B) and (C).
A solid catalyst component consisting of a reactant with an aromatic carboxylic acid ester, or a solid catalyst component formed by further treating these reactants with the component (b) above, (B) a trialkylaluminum compound, and (C) a general formula R ¹⁰ lSi(OR ¹¹ ) _4-l (R ¹⁰ and R ¹¹ in the formula are the same or different hydrocarbon groups having 1 to 20 carbon atoms, l is a number satisfying the relationship 0≦l<4) A method for producing an α-olefin polymer, the method comprising using a catalyst system comprising an alkoxysilane compound.