JP4903360B2 - Solid catalyst component for producing propylene block copolymer, catalyst for producing propylene block copolymer, and method for producing propylene block copolymer - Google Patents

Description

  The present invention relates to a solid catalyst component for producing a propylene block copolymer, a catalyst for producing a propylene block copolymer, and a method for producing a propylene block copolymer.

Polypropylene has shown significant demand growth in recent years due to its excellent physical properties.
In the production of polypropylene, a so-called Ziegler-Natta catalyst obtained by bringing a solid catalyst component obtained using a group 4-6 transition metal compound of the periodic table into contact with an organoaluminum compound is widely used. In contrast to the conventional titanium trichloride type catalyst, a highly active catalyst comprising a combination of a magnesium compound and a titanium compound has also been developed, making it possible to produce crystalline polypropylene having high stereoregularity with high efficiency.
For example, by using a combination of a supported solid catalyst component obtained by supporting tetravalent titanium halide on magnesium halide, an organoaluminum compound as a cocatalyst, and an organosilicon compound as a polymerization third component, It is known that highly stereoregular polymerization can be realized (Patent Documents 1 to 3).

  In addition, after treating a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound with an ester compound, a halogenated compound (for example, titanium tetrachloride) and an electron donor (for example, A trivalent titanium compound-containing solid catalyst component obtained by contact treatment with an ether compound, a mixture of an ether compound and an ester compound), a co-catalyst organoaluminum compound, and an electron donating compound as a polymerization third component It is known that highly stereoregular polymerization of α-olefin can be realized even in combination (Patent Document 4).

  Further, a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound is converted into a halogenated compound (for example, titanium tetrachloride), an electron donor (for example, an ether compound, an ether compound). A mixture of a trivalent titanium compound-containing solid catalyst component obtained by contact treatment with an organic acid halide, an organic aluminum compound as a co-catalyst, and an electron donating compound as a polymerization third component It is also known that highly stereoregular polymerization of α-olefin can be realized in (Patent Document 5).

  In either case, it is possible to produce a highly stereoregular polymer without extraction and with high efficiency, but it is hoped that a higher stereoregular polymerization ability will be realized for higher rigidity. It is rare.

JP 57-63310 A JP 58-83006 A JP 61-78803 A JP-A-7-216017 Japanese Patent Laid-Open No. 10-212319

By the way, crystalline polypropylene has excellent rigidity and heat resistance, but it has the disadvantage that it becomes brittle at low temperatures, so an amorphous copolymer component with an olefin other than propylene such as ethylene can be used in a multistage polymerization method, etc. In some cases, an improved method may be taken. However, in the resulting propylene block copolymer, the amorphous component becomes a highly tacky component, so in the production, polymer particle migration failure in the polymerization reaction apparatus, polymer particles on the inner wall of the polymerization reaction apparatus Adhesion, polymer particle fixation in the polymerization reaction apparatus, etc. are likely to occur, and in particular, when it is desired to increase the amount of amorphous components, there is a problem that long-term stable operation becomes difficult.
An object of the present invention is to provide a solid catalyst component for producing a propylene block copolymer, a catalyst for producing a propylene block copolymer, and a propylene block copolymer that can produce a propylene block copolymer having excellent powder properties. It is to provide a manufacturing method.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。）
（ｂ）ハロゲン化化合物
（ｃ）電子供与体
（ｄ）有機酸ハライド
さらに本発明は、該プロピレンブロック共重合体製造用固体触媒成分（Ａ）、有機アルミニウム化合物（Ｂ）、ならびに電子供与性化合物（Ｃ）を接触させて得られるプロピレンブロック共重合体製造用触媒にかかるものであり、また、該プロピレンブロック共重合体製造用触媒を用いたプロピレンブロック共重合体の製造方法にかかるものである。 The present invention provides a solid catalyst component for producing a propylene block copolymer obtained by contacting the following (a), (b) and (c), and the following (a), (b), (c) and The solid catalyst component for producing a propylene block copolymer obtained by bringing (d) into contact is concerned.
(A) It is obtained by reducing a titanium compound (a2) represented by the following general formula [I] with an organomagnesium compound (a3) in the presence of an organosilicon compound (a1) having a Si—O bond. Solid catalyst component precursor having an average particle size of 25 microns or more

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
(B) Halogenated compound (c) Electron donor (d) Organic acid halide Further, the present invention provides a solid catalyst component (A) for producing the propylene block copolymer, an organoaluminum compound (B), and an electron donating compound. It relates to a catalyst for producing a propylene block copolymer obtained by contacting (C), and also relates to a method for producing a propylene block copolymer using the catalyst for producing a propylene block copolymer. .

  According to the present invention, a solid catalyst component for producing a propylene block copolymer capable of producing a propylene block copolymer having excellent powder properties, a catalyst for producing a propylene block copolymer, and a propylene block copolymer A manufacturing method is provided.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。）
（ｂ）ハロゲン化化合物
（ｃ）電子供与体
（ｄ）有機酸ハライド
また、この還元反応に際して、任意成分としてエステル化合物（ａ４）を共存させると、重合活性や立体規則性重合能がさらに向上するため好ましい。 The solid catalyst component (A) for producing the propylene block copolymer of the present invention is obtained by contacting the following (a), (b) and (c). Furthermore, it is more preferable to use an organic acid halide as a component for contacting the organic acid halide, since the stereoregular polymerization ability is more excellent. That is, the solid catalyst component (A) for producing a propylene block copolymer of the present invention is preferably a propylene block copolymer produced by contacting the following (a), (b), (c) and (d): It is a solid catalyst component for use.
(A) It is obtained by reducing a titanium compound (a2) represented by the following general formula [I] with an organomagnesium compound (a3) in the presence of an organosilicon compound (a1) having a Si—O bond. Solid catalyst component precursor having an average particle size of 25 microns or more

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
(B) Halogenated compound (c) Electron donor (d) Organic acid halide Further, when the ester compound (a4) is present as an optional component in the reduction reaction, the polymerization activity and stereoregular polymerization ability are further improved. Therefore, it is preferable.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。）
このとき任意成分としてエステル化合物（ａ４）を共存させると、重合活性や立体規則性重合能がさらに向上するため好ましい。 (A) Solid catalyst component precursor The solid catalyst component precursor (a) is a titanium compound (a2) represented by the following general formula [I] in the presence of an organosilicon compound (a1) having a Si-O bond. Is obtained by reduction with an organomagnesium compound (a3).

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
At this time, it is preferable to allow the ester compound (a4) to coexist as an optional component because the polymerization activity and stereoregular polymerization ability are further improved.

Examples of the organosilicon compound (a1) having a Si—O bond include those represented by the following general formula.
Si (OR ¹⁰ ) _t R ¹¹ _4-t
R ¹² (R ¹³ ₂ SiO) _u SiR ¹⁴ ₃ or
(R ¹⁵ ₂ SiO) _v
R ¹⁰ represents a hydrocarbon group having 1 to 20 carbon atoms, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms. Represents. t represents an integer satisfying 0 <t ≦ 4, u represents an integer of 1 to 1000, and v represents an integer of 2 to 1000.

  Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxy-diisopropylsilane, tetrapropoxy. Silane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldi Siloxane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane Emissions, diphenyl polysiloxane, may be exemplified methylhydropolysiloxane, phenyl hydropolysiloxane like.

Among these organosilicon compounds, preferred are alkoxysilane compounds represented by the general formula Si (OR ¹⁰ ) _t R ¹¹ _4-t , in which case t is preferably a number satisfying 1 ≦ t ≦ 4, In particular, t = 4 tetraalkoxysilane is preferable, and tetraethoxysilane is most preferable.

（式中、ａは１〜２０の数を表し、Ｒ²は炭素原子数１〜２０の炭化水素基を表す。Ｘ²はハロゲン原子または炭素原子数１〜２０の炭化水素オキシ基を表し、全てのＸ²は同一であっても異なっていてもよい。） The titanium compound (a2) is a titanium compound represented by the following general formula [I].

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)

Specific examples of R ² include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, decyl, dodecyl and the like. And aryl groups such as phenyl group, cresyl group, xylyl group and naphthyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group, allyl groups such as propenyl group, and aralkyl groups such as benzyl group.
Of these groups, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable.

Examples of the halogen atom for X ² include a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is particularly preferable. The hydrocarbon oxy group having 1 to 20 carbon atoms in X ² is a hydrocarbon oxy group having a hydrocarbon group having 1 to 20 carbon atoms similar to R ² . X ² is particularly preferably an alkoxy group having a linear alkyl group having 2 to 18 carbon atoms.

  In the titanium compound represented by the general formula [I], a represents a number of 1 to 20, and is preferably a number satisfying 1 ≦ a ≦ 5.

  Specific examples of such titanium compounds include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetra-iso-propoxy titanium, tetra-n-butoxy titanium, tetra-iso-butoxy titanium, and n-butoxy titanium. Trichloride, di-n-butoxytitanium dichloride, tri-n-butoxytitanium chloride, di-n-tetraisopropylpolytitanate (a mixture in the range of a = 2 to 10), tetra-n-butylpolytitanate (a = 2) 10), tetra-n-hexylpolytitanate (a = 2 to 10 range), and tetra-n-octylpolytitanate (a = 2 to 10 range). Moreover, the condensate of the tetraalkoxy titanium obtained by making a small amount of water react with tetraalkoxy titanium can also be mentioned.

The titanium compound (a2) is preferably a titanium compound in which a is 1, 2, or 4 in the titanium compound represented by the above general formula [I].
Particularly preferred is tetra-n-butoxytitanium, tetra-n-butyltitanium dimer or tetra-n-butyltitanium tetramer.
In addition, a titanium compound (a2) can also be used in the state which mixed multiple types.

The organomagnesium compound (a3) is any type of organomagnesium compound having a magnesium-carbon bond. Particularly, a Grignard compound represented by the general formula R ¹⁶ MgX ⁵ (wherein Mg represents a magnesium atom, R ¹⁶ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁵ represents a halogen atom) or a general formula R Dihydrocarbyl magnesium represented by ¹⁷ R ¹⁸ Mg (wherein Mg represents a magnesium atom and R ¹⁷ and R ¹⁸ each represent a hydrocarbon group having 1 to 20 carbon atoms) is preferably used. Here, R ¹⁷ and R ¹⁸ may be the same or different. Specific examples of R ¹⁶ to R ¹⁸ are methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isoamyl group, hexyl group, octyl group, 2-ethylhexyl group, respectively. , A phenyl group, a benzyl group and the like, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and an alkenyl group. In particular, it is preferable from the viewpoint of catalyst performance to use a Grignard compound represented by R ¹⁶ MgX ⁵ in an ether solution.

  It is also possible to use a hydrocarbon-soluble complex of the above organic magnesium compound and an organic metal that solubilizes the organic magnesium compound in a hydrocarbon. Examples of organometallic compounds include Li, Be, B, Al or Zn compounds.

  As the ester compound (a4), mono- or polyvalent carboxylic acid esters are used, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, and aromatic carboxylic acids. Mention may be made of esters. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-phthalate n-octyl, phthalate Di (2-ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

  Among these ester compounds, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as phthalic acid esters are preferred, and dialkyl esters of phthalic acid are particularly preferred.

  In the presence of the organosilicon compound (a1) or in the presence of the organosilicon compound (a1) and the ester compound (a4), the solid catalyst component precursor (a) is obtained by replacing the titanium compound (a2) with the organomagnesium compound (a3). Obtained by reduction.

The titanium compound (a2), the organosilicon compound (a1) and the ester compound (a4) are preferably used by dissolving or diluting in an appropriate solvent.
Such solvents include aliphatic hydrocarbons such as hexane, heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl ether, dibutyl ether, di- Examples include ether compounds such as isoamyl ether and tetrahydrofuran.

The reduction reaction temperature is usually in the temperature range of −50 to 70 ° C., preferably −30 to 50 ° C., particularly preferably −25 to 35 ° C.
The reaction time is not particularly limited, but is usually about 30 minutes to 10 hours.

In the reduction reaction, a porous carrier such as an inorganic oxide or an organic polymer can be allowed to coexist, and the porous product can be impregnated with the porous product. The porous carrier used may be a known one. Porous inorganic oxides represented by SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , ZrO _2, etc., or polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol-methyl methacrylate copolymer, Polymethyl acrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, Examples thereof include organic porous polymers such as polyethylene and polypropylene. Of these, an organic porous polymer is preferably used, and a styrene-divinylbenzene copolymer or an acrylonitrile-divinylbenzene copolymer is particularly preferable.

  The porous carrier preferably has a pore volume at a pore radius of 200 to 2000 mm of 0.3 cc / g or more, more preferably 0.4 cc / g or more. The pore volume at ˜75000 kg is preferably 35% or more, more preferably 40% or more. If the pore volume of the porous carrier is small, the catalyst component may not be effectively immobilized, which is not preferable. In addition, even when the pore volume of the porous carrier is 0.3 cc / g or more, the catalyst component cannot be effectively immobilized unless it is sufficiently present in the pore radius of 200 to 2000 mm. Is not preferable.

The average particle size of the solid catalyst component precursor used in the present invention is 25 microns or more, more preferably 27 to 80 microns, still more preferably 30 to 55 microns. The average particle diameter here means the median diameter (particle diameter corresponding to 50% of the cumulative distribution) in the volume-based cumulative distribution curve obtained from the light transmission method.
In the solid catalyst component precursor used in the present invention, the amount of fine powder component having a particle size of 16 microns or less is preferably 3% by weight or less in order to obtain a propylene block copolymer having good powder properties. Yes, more preferably 2% by weight or less.

The average particle diameter and fine powder component amount of the solid catalyst component precursor used in the present invention are adjusted by performing the above reduction reaction under conditions where the stirring efficiency is low.
When the stirring efficiency is expressed by the unit volume stirring power factor (P / V) represented by the formula (1), the reduction during the production of the solid catalyst component precursor having the specific average particle diameter and fine powder component amount used in the present invention. The reaction is usually P / V = 0.05 to 100 m ² / s ³ , preferably 0.1 to 50 m ² / s ³ , more preferably 0.2 to 30 m ² / s ³ .
P / V = Np × (n ³ ) × (d ⁵ ) ÷ V (1)
Here, Np: power number [−], n: rotational speed [rps], d: stirring blade diameter [m], V: reaction liquid volume [m ³ ], P / V: unit volume stirring power factor [m ^2] / S ³ ].
In such stirring efficiency, the reaction temperature is usually −5 ° C. to 50 ° C., preferably 0 ° C. to 25 ° C., more preferably 5 ° C. to 10 ° C.
In such stirring efficiency, the amount of solvent is usually (a1 + a2) / (a1 + a2 + solvent) = 20-60 ml / ml, more preferably 30-50 ml / ml.
In such stirring efficiency, the reaction component ratio is such that the ratio of a1 and a3 is usually Si / Mg = 0.4-5 mol / mol, preferably 0.6-2 mol as the atomic ratio of Si atoms to Mg atoms contained. / Mol, more preferably 0.8 to 1 mol / mol. The ratio of a2 and a3 is usually Ti / Mg = 0.01 to 0.15 mol / mol, preferably 0.03 to 0.1 mol / mol, more preferably as the atomic ratio of Ti atoms to Mg atoms contained. 0.05 to 0.07 mol / mol. Furthermore, when using a4 which is an arbitrary component, the ratio of a4 and a3 is usually ester group / Mg = 0.003 to 0.08 mol / mol, preferably 0.006 to 0 as the ratio of the ester group and Mg atom contained. 0.06 mol / mol.

  The solid catalyst component precursor obtained by the reduction reaction is usually subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane, heptane, and toluene.

  In addition, the solid catalyst component precursor used in the present invention is preferably preliminarily heat-treated in preparation of the solid catalyst component from the viewpoints of polymerization activity and stereoregularity. The heat treatment is preferably performed in a slurry state in an inert hydrocarbon solvent. Processing temperature is 40-120 degreeC normally, Preferably it is 60 to 100 degreeC. The treatment time is usually in the range of 30 minutes to 10 hours.

  The solid catalyst component precursor thus obtained contains a trivalent titanium atom, a magnesium atom and a hydrocarbon oxy group, and generally exhibits amorphous or very weak crystallinity. From the viewpoint of catalyst performance, an amorphous structure is particularly preferable.

(B) Halogenated Compound As the halogenated compound, a compound capable of substituting the hydrocarbon oxy group in the solid catalyst component precursor (a) with a halogen atom is preferable. Among these, halogen compounds of Group 4 elements, halogen compounds of Group 13 elements, or halogen compounds of Group 14 elements are preferable.

As the halogen compound of Group 4 element, general formula M (OR ⁹ ) _b X ⁴ _4-b (wherein M represents a Group 4 element and R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms). X ⁴ represents a halogen atom, and b represents a number satisfying 0 ≦ b <4). Specific examples of M include titanium, zirconium, and hafnium, and titanium is particularly preferable. Specific examples of R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, heptyl group, octyl group. And an alkyl group such as a decyl group and a dodecyl group, an aryl group such as a phenyl group, a cresyl group, a xylyl group and a naphthyl group, an allyl group such as a propenyl group, and an aralkyl group such as a benzyl group. Among these, an alkyl group having 2 to 18 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. A linear alkyl group having 2 to 18 carbon atoms is particularly preferable. It is also possible to use halogen compounds of Group 4 elements having two or more different OR ⁹ groups.

Examples of the halogen atom represented by X ⁴ include a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom gives particularly favorable results.

In the halogen compound of the Group 4 element represented by the general formula M (OR ⁹ ) _b X ⁴ _4-b , b is a number satisfying 0 ≦ b <4, and preferably 0 ≦ b ≦ 2. It is a number, particularly preferably b = 0.

Specifically, titanium compounds represented by the general formula M (OR ⁹ ) _b X _4-b include titanium tetrachlorides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, and methoxy titanium trichloride. , Ethoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, trihalogenated alkoxy titanium such as ethoxy titanium tribromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium Dihalogenated dialkoxytitanium such as dibromide, zirconium compounds corresponding to the respective compounds, and hafnium compounds can be exemplified. Most preferred is titanium tetrachloride

The halogen compound of the group 13 element or the group 14 element includes a general formula MR _ma X _a (wherein M is a group 13 or group 14 atom, and R is a hydrocarbon group having 1 to 20 carbon atoms). , X represents a halogen atom, m represents a valence of M, and a represents a number satisfying 0 <a ≦ m).
Examples of Group 13 atoms include B, Al, Ga, In, and Tl. B or Al is preferable, and Al is more preferable. Examples of the Group 14 atom include C, Si, Ge, Sn, and Pb. Si, Ge, or Sn is preferable, and Si or Sn is more preferable.

m is the valence of M. For example, when M is Si, m = 4.
a represents a number satisfying 0 <a ≦ m. When M is Si, a is preferably 3 or 4.
Examples of the halogen atom represented by X include F, Cl, Br, and I, and Cl is preferable.

  Specific examples of R include alkyl such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, decyl group and dodecyl group. Group, phenyl group, tolyl group, cresyl group, xylyl group, aryl group such as naphthyl group, cycloalkyl group such as cyclohexyl group and cyclopentyl group, alkenyl group such as propenyl group, and aralkyl group such as benzyl group. Preferred R is an alkyl group or an aryl group, and particularly preferred R is a methyl group, an ethyl group, a normal propyl group, a phenyl group or a paratolyl group.

  Specific examples of Group 13 element halogen compounds include trichloroboron, methyldichloroboron, ethyldichloroboron, phenyldichloroboron, cyclohexyldichloroboron, dimethylchloroboron, methylethylchloroboron, trichloroaluminum, methyldichloroaluminum, ethyldichloro. Aluminum, phenyldichloroaluminum, cyclohexyldichloroaluminum, dimethylchloroaluminum, diethylchloroaluminum, methylethylchloroaluminum, ethylaluminum sesquichloride, gallium chloride, gallium dichloride, trichlorogallium, methyldichlorogallium, ethyldichlorogallium, phenyldichlorogallium, cyclohexyl Dichlorogallium, dimethylchlorogalli , Methyl ethyl chlorogallium, indium chloride, indium trichloride, methyl indium dichloride, phenyl indium dichloride, dimethyl indium chloride, thallium chloride, thallium trichloride, methyl thallium dichloride, phenyl thallium dichloride, dimethyl thallium chloride, etc. Also included are compounds in which chloro in the compound name is changed to fluoro, bromo, or iodo.

  Specific examples of halogen compounds of Group 14 elements include tetrachloromethane, trichloromethane, dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2 , 2-tetrachloroethane, tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, Methyldichlorosilane, ethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethylchloro Silane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane, diethyldichlorogermane, diphenyldichlorogermane, monocrologermane, trimethylchlorogermane, triethylchlorogermane , Trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichlorotin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, Examples include dichlorolead, methylchlorolead, and phenylchlorolead. Oro, bromo or compound is changed to iodine, it is also included.

As the halogenated compound (b), tetrachlorotitanium, methyldichloroaluminum, ethyldichloroaluminum, tetrachlorosilane, phenyltrichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane or tetrachlorotin are used from the viewpoint of polymerization activity. Are particularly preferably used.
As the halogenated compound (b), only one kind of the above compounds may be used, or a plurality of kinds may be used.

(C) Electron Donor In the present invention, a contact treatment using the electron donor (c) can be appropriately performed in the preparation of the solid catalyst component. In some cases, high stereoregular polymerization ability can be imparted by contact treatment with an electron donor. As electron donors, oxygen-containing electron donating compounds such as ethers, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, acid amides of organic or inorganic acids, acid anhydrides, Nitrogen-containing electron donating compounds such as ammonia, amines, nitriles and isocyanates can be mentioned. Of these electron donating compounds, esters of organic acids and / or ethers are preferred, and carboxylic acid esters (c1) and / or ethers (c2) are more preferred.

  Examples of the carboxylic acid esters (c1) include mono- and polyvalent carboxylic acid esters, and examples thereof include saturated aliphatic carboxylic acid esters, unsaturated aliphatic carboxylic acid esters, alicyclic carboxylic acid esters, Aromatic carboxylic acid esters can be mentioned. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, toluyl Ethyl acetate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl phthalate Ethyl, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dipentyl phthalate, di-n-hexyl phthalate, diheptyl phthalate, di-phthalate n-octyl, phthalate Di (2-ethylhexyl), diisodecyl phthalate, dicyclohexyl phthalate, may be mentioned diphenyl phthalate.

  Of these carboxylic acid esters, unsaturated aliphatic carboxylic acid esters such as methacrylic acid esters and maleic acid esters or aromatic carboxylic acid esters such as benzoic acid esters and phthalic acid esters are preferably used. Particularly preferred are aromatic polycarboxylic esters, and most preferred are dialkyl phthalates.

（但し、Ｒ⁵ 〜Ｒ⁸ はそれぞれ独立に炭素原子数１〜２０の直鎖状、分岐状もしくは脂環式のアルキル基、アリール基またはアラルキル基であり、Ｒ⁶ およびＲ⁷ はそれぞれ独立に水素原子であってもよい。）で表されるジエーテル化合物を挙げることができ、これらのうちの１種または２種以上が好適に用いられる。 Examples of ethers (c2) include dialkyl ethers and general formulas

(However, R ^{5 to} R ⁸ are each independently a linear, branched or alicyclic alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ are each independently It may be a hydrogen atom.), And one or more of these are preferably used.

Specific examples include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl. -1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl -1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxy Propane, 2,2-diiso Lopyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxy Examples include propane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane, and one or more of these are preferred. Used.
The ethers (c2) are particularly preferably dialkyl ethers, and most preferably di-n-butyl ether. Di-n-butyl ether may be simply referred to as dibutyl ether or butyl ether.

(D) Organic acid halide As the organic acid halide (d) used for the preparation of the solid catalyst component of the present invention, mono- or polyvalent carboxylic acid halides are preferably used, examples of which are aliphatic carboxylic acid halides, Examples thereof include alicyclic carboxylic acid halides and aromatic carboxylic acid halides. Specific examples include acetyl chloride, propionic acid chloride, butyric acid chloride, valeric acid chloride, acrylic acid chloride, methacrylic acid chloride, benzoic acid chloride, toluic acid chloride, anisic acid chloride, succinic acid chloride, malonic acid chloride, maleic acid chloride. Itaconic acid chloride, phthalic acid chloride and the like.

  Of these organic acid halides, aromatic carboxylic acid chlorides such as benzoic acid chloride, toluic acid chloride, and phthalic acid chloride are preferred, aromatic dicarboxylic acid dichlorides are more preferred, and phthalic acid chloride is particularly preferred.

(A) Preparation of solid catalyst component The solid catalyst component (A) of the present invention is obtained by bringing the solid catalyst component precursor (a), the halogenated compound (b), and the electron donor (c) into contact with each other. The solid catalyst component precursor (a), the halogenated compound (b), the electron donor (c), and the organic acid halide (d) are contacted. All of these contact treatments are usually performed in an inert gas atmosphere such as nitrogen or argon.

As a specific method of contact treatment for obtaining a solid catalyst component,
-A method in which (b) or (c) (arbitrary order) is input to (a) and contact processing is performed,
-A method in which (b) and (d) (arrangement order is arbitrary) are input to (a) and contact processing is performed,
-A method in which the mixture of (b), (c), and (d) is charged into (a) and subjected to contact treatment,
-A method in which a mixture of (b) and (c), (d) (arbitrary order) is added to (a), and contact treatment is performed,
A method in which (c) is introduced into (a) and subjected to contact treatment, and then (b) is introduced and subjected to contact treatment,
-A method in which (c) is added to (a) and contact processing is performed, and then (b) and (c) (arbitrary order is input) and contact processing is performed,
A method in which (c) is charged into (a) and contact-treated, and then a mixture of (b) and (c) is charged and contact-treated,
A method of performing contact processing by putting (a), (c) (arbitrary order) into (b),
-A method in which (a), (d) (arrangement order is arbitrary) is input to (b) and contact processing is performed,
A method of performing contact processing by introducing (a), (c), (d) (arbitrary order) into (b),
In addition, after these contact treatments, a method in which contact treatment is further performed once or more in (b) and a method in which contact treatment is performed once or more with a mixture of (b) and (c) can be mentioned.

Among these, (b), (d) (arrangement order is arbitrary) are charged into (a), and contact processing is performed. (A) is a mixture of (b) and (c). (D) (arrangement order is arbitrary) (A), a mixture of (b) and (c), (d) (arrangement order is arbitrary), and after contact treatment, a mixture of (b) and (c) is introduced. A method of performing contact treatment more than once, a method in which (c) is charged into (a), contact treatment, and then contact treatment with a mixture of (b) and (c) at least once,
(A) A mixture of (b) and (c), each in the order of (d) and contact treatment, (a) a mixture of (b) and (c), (d) in the order Each is charged and contact-treated, then a mixture of (b) and (c) is charged and contact-treated one or more times, or (c) is charged into (a) and contact-treated (b) ) And a mixture of (c) are more preferably subjected to contact treatment at least once. Particularly preferably, the mixture of (b) and (c2) and the mixture of (b), (c2), and the mixture of (b), (c1), and (c2) are respectively added to (a) in the order (d). A method of performing a contact treatment and further performing a contact treatment with the mixture of (b) and (c2) at least once, or (c) is added to (a), and after the contact treatment, (b) and (c1) In this method, the mixture of (c2) is charged, contact treatment is performed, and contact treatment is further performed once or more with the mixture of (b) and (c2).

The contact treatment is preferably performed in the presence of a diluent from the viewpoint of suppressing the generation of fine powder.
Further, after the contact treatment, the next operation can be performed as it is, but in order to remove surplus, it is preferable to perform a washing treatment with a diluent.

The diluent is preferably inert to the component to be treated, aliphatic hydrocarbons such as pentane, hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, cyclopentane, etc. Halogenated hydrocarbons such as alicyclic hydrocarbons, 1,2-dichloroethane, and monochlorobenzene can be used.
The amount of the diluent used in the contact treatment is usually 0.1 ml to 1000 ml per 1 g of the solid catalyst component precursor (a) per one-step contact treatment. The amount is preferably 1 ml to 100 ml per 1 g. In addition, the amount of diluent used in a single washing operation is similar. The number of washing operations in the washing treatment is usually 1 to 5 times per one-step contact treatment.

The contact treatment and / or washing treatment temperature is usually −50 to 150 ° C., preferably 0 to 140 ° C., more preferably 60 to 135 ° C.
The contact treatment time is not particularly limited, but is preferably 0.5 to 8 hours, and more preferably 1 to 6 hours. The washing operation time is not particularly limited, but is preferably 1 to 120 minutes, and more preferably 2 to 60 minutes.

The usage-amount of a halogenated compound (b) is 0.5-1000 mmol normally with respect to 1g of solid catalyst component precursor (a), Preferably it is 1-200 mmol, More preferably, it is 2-100 mmol.
In using the halogenated compound (b), it is preferable to use the electron donor (c) together. In this case, the amount of (c) used relative to 1 mol of (b) is usually 1 to 100 mol, preferably 1.5 to 75 mol, and more preferably 2 to 50 mol.

  The amount of the electron donor (c) used is usually 0.01 to 100 mmol, preferably 0.05 to 50 mmol, more preferably 0.1 to 20 mmol with respect to 1 g of the solid catalyst component precursor (a). is there.

The amount of the organic acid halide (d) used is usually 0.1 to 100 mmol, preferably 0.3 to 50 mmol, more preferably 0.5 to 20 mmol with respect to 1 g of the solid catalyst component precursor (a). is there. Moreover, the usage-amount of the organic acid halide (d) per 1 mol of magnesium atoms in a solid catalyst component precursor (a) is 0.01-1.0 mol normally, Preferably it is 0.03-0.5 mol. is there.
When the amount of (c) or (d) used is excessively large, particle collapse may occur.

  When the contact treatment is performed using each compound a plurality of times, the amount of each compound described above represents the amount of each compound used once and for each kind of compound.

  The obtained solid catalyst component may be used for polymerization in a slurry state in combination with an inert diluent, or may be used for polymerization as a fluid powder obtained by drying. Examples of the drying method include a method of removing volatile components under reduced pressure conditions, and a method of removing volatile components under the flow of an inert gas such as nitrogen and argon. The temperature at the time of drying is preferably 0 to 200 ° C, more preferably 50 to 100 ° C. The drying time is preferably 0.01 to 20 hours, and more preferably 0.5 to 10 hours.

  The catalyst for producing a propylene block copolymer of the present invention is obtained by contacting the solid catalyst component (A) of the present invention, the organoaluminum compound (B), and the electron donating compound (C).

(B) Organoaluminum compound The organoaluminum compound (B) has at least one Al-carbon bond in the molecule. A typical one is shown in the following general formula.
R ¹⁹ _w AlY _3-w
R ²⁰ R ²¹ Al—O—AlR ²² R ²³
(Wherein R ^{19 to} R ²³ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and w is a number satisfying 2 ≦ w ≦ 3.)
Specific examples of such organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum hydride such as diethylaluminum hydride and diisobutylaluminum hydride, dialkylaluminum halide such as diethylaluminum chloride, and triethylaluminum. Examples thereof include a mixture of a trialkylaluminum and a dialkylaluminum halide such as a mixture of benzene and diethylaluminum chloride, and an alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane.

  Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylalumoxane is preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyl is particularly preferable. Dialumoxane is preferred.

(C) Electron-donating compound Examples of the electron-donating compound (C) include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, and a sulfur-containing compound. Among them, an oxygen-containing compound or a nitrogen-containing compound is preferable. Oxygen-containing compounds are preferred.
Examples of the oxygen-containing compound include alkoxy silicons, ethers, esters, ketones, etc. Among them, alkoxy silicons or ethers are preferable.

Examples of the alkoxysilicon compounds include a general formula R ³ _r Si (OR ⁴ ) _4-r (wherein R ³ represents a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a heteroatom-containing substituent, and R ⁴ Represents a hydrocarbon group having 1 to 20 carbon atoms, and r represents a number satisfying 0 ≦ r <4, and all R ³ and all R ⁴ may be the same or different. ) Is preferably used.
When R ³ is a hydrocarbon group, a linear alkyl group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, isopropyl group, sec-butyl group, tert-butyl group, tert-amyl group, etc. A branched alkyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group such as a cyclopentenyl group, an aryl group such as a phenyl group and a tolyl group. Among these, it is preferable that the carbon atom directly bonded to the silicon atom of the alkoxysilicon compound has at least one R ³ which is a secondary or tertiary carbon.
When R ³ is a heteroatom-containing substituent, examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specifically, dimethylamino group, methylethylamino group, diethylamino group, ethyl n-propylamino group, di-n-propylamino group, pyrrolyl group, pyridyl group, pyrrolidinyl group, piperidyl group, perhydroindolyl group, perhydro Examples include isoindolyl group, perhydroquinolyl group, perhydroisoquinolyl group, perhydrocarbazolyl group, perhydroacridinyl group, furyl group, pyranyl group, perhydrofuryl group, and thienyl group. However, a substituent in which the hetero atom can be directly chemically bonded to the silicon atom of the alkoxysilicon compound is preferable.

  Specific examples of the alkoxysilicon compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amylnpropyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butyl Isopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutene Rudimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl Isopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane , Phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyl Diethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldi Ethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxy Sisilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino ) (Perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) ethyldimethoxysilane , (Perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl) dimethoxy Silane, and (perhydroisoquinolino) (tert-butyl) dimethoxysilane.

（但し、Ｒ⁵ 〜Ｒ⁸ はそれぞれ独立に炭素原子数１〜２０の直鎖状、分岐状もしくは脂環式のアルキル基、アリール基またはアラルキル基であり、Ｒ⁶ およびＲ⁷ はそれぞれ独立に水素原子であってもよい。）で表されるジエーテル化合物を挙げることができ、これらのうちの１種または２種以上が好適に用いられる。 Examples of ethers include dialkyl ethers and general formulas

(However, R ^{5 to} R ⁸ are each independently a linear, branched or alicyclic alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ are each independently It may be a hydrogen atom.), And one or more of these are preferably used.

Specific examples include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl. -1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl -1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxy Propane, 2,2-diiso Lopyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxy Examples include propane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane, and one or more of these are preferred. Used.
The ethers (e2) are particularly preferably dialkyl ethers, and most preferably di-n-butyl ether. Di-n-butyl ether may be simply referred to as dibutyl ether or butyl ether.

  Nitrogen-containing compounds include 2,6-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine and other 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ′, N Examples thereof include substituted methylenediamines such as '-tetramethylmethylenediamine and N, N, N', N'-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine. Of these, 2,6-substituted piperidines are preferable.

The contact method for obtaining the block copolymer production catalyst of the present invention by bringing the components into contact with each other may be any method as long as the components are brought into contact with each other to form a catalyst. As the method, the above components are diluted with a solvent or not diluted, and (1) the above components are mixed and contacted before being supplied to the polymerization tank, or (2) the above components are separated. (3) A part of the above components are mixed and contacted before being supplied to the polymerization tank, and the remaining components are separately supplied to the polymerization tank. Can be exemplified.
The supply of the catalyst to the polymerization tank in the above method (1) and the supply of the components to the polymerization tank in the methods (2) and (3) are usually in an inert gas such as nitrogen or argon, in a state free of moisture. Will be implemented.

[Block copolymerization]
The method for producing a propylene block copolymer according to the present invention is a method for producing a propylene block copolymer in the presence of the catalyst for producing the propylene block copolymer according to the present invention, and the propylene block copolymer according to the present invention. A method for producing a propylene block copolymer comprising the following steps using a production catalyst is preferred.
Step 1: (1) Step of homopolymerizing propylene to form homopolypropylene, or (2) Copolymerization of propylene with an olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A step of producing a copolymer A. Here, the copolymerization is carried out so that the content of polymerized units of the olefin in the copolymer A is 10% by weight or less, preferably 5% by weight or less (the copolymer A is 100% by weight). Is done.
Step 2: In the presence of the homopolypropylene or copolymer A obtained in Step 1, propylene is copolymerized with an olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A step of producing a block copolymer by producing the combined B. Here, in the copolymerization, the content of polymerized units of the olefin in the copolymer B is 10 to 60% by weight (the copolymer B is 100% by weight), and the copolymer in the block copolymer It implements so that content of the copolymer B may be 2 to 60 weight% (a block copolymer shall be 100 weight%).

In the present invention, the propylene block copolymer production catalyst of the present invention may be used as it is in the production method of the block copolymer (polymerization at this time is hereinafter referred to as “main polymerization”). After preliminarily obtaining a prepolymerized catalyst obtained by performing a prepolymerization treatment, it may be used for the main polymerization.
The prepolymerization catalyst is usually produced by polymerizing a small amount of olefin (prepolymerization) in the presence of the solid catalyst component (A) and the organoaluminum compound (B). As the prepolymerization method, a slurry polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent is preferable. A part or all of the solvent may be changed to a liquid olefin.
The amount of the organoaluminum compound (B) used in the prepolymerization is usually 0.5 to 700 moles, preferably 0.8 to 500 moles, particularly preferably 1 to 1 mole per mole of titanium atoms in the solid catalyst component (A). 200 moles.
The amount of the prepolymerized olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component (A).

The slurry concentration in the slurry polymerization method is preferably 1 to 500 g-solid catalyst component / liter-solvent, particularly preferably 3 to 300 g-solid catalyst component / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 0.01 to 20 kg / cm ² , particularly preferably 0.1 to 10 kg / cm ² , but the olefin that is liquid at the prepolymerization pressure and temperature is used. This is not the case. The prepolymerization time is not particularly limited, and is preferably usually 2 minutes to 15 hours.

  In the prepolymerization, as a method of supplying the solid catalyst component, the organoaluminum compound and the olefin to the polymerization tank, (1) a method of supplying the olefin after supplying the solid catalyst component and the organoaluminum compound, and (2) a solid A method of supplying an organoaluminum compound after supplying a catalyst component and an olefin can be exemplified. As a method of supplying olefins to the polymerization tank, (1) a method of sequentially supplying olefins so that the pressure in the polymerization tank is maintained at a predetermined pressure, and (2) a total supply of a predetermined amount of olefins is collectively supplied. Can be exemplified. In order to adjust the molecular weight of the olefin polymer obtained by the preliminary polymerization, a chain transfer agent such as hydrogen may be used.

In the prepolymerization, part or all of the electron donating compound (C) used in the main polymerization may be used as necessary. The amount of the electron donating compound used in the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, particularly preferably 0 to 1 mol of titanium atom contained in the solid catalyst component. 0.03 to 100 mol, and usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol, relative to 1 mol of the organoaluminum compound.
In the prepolymerization, the method for supplying the electron donating compound to the polymerization tank is not particularly limited. Examples of the method include (1) a method of supplying only an electron donating compound and (2) a method of supplying a contact product between an electron donating compound and an organoaluminum compound. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization.

As the main polymerization method, (1) a method of polymerizing an olefin in the presence of a catalyst obtained by contacting a solid catalyst component, an organoaluminum compound and an electron donating compound, and (2) an olefin in the presence of a prepolymerization catalyst. Examples of the polymerization method and (3) a method of polymerizing an olefin in the presence of a contact product of the prepolymerization catalyst, an organoaluminum compound, and an electron-donating compound.
The usage-amount of the organoaluminum compound in this superposition | polymerization is 1-1000 mol normally with respect to 1 mol of titanium atoms in a solid catalyst component, Preferably it is 5-600 mol.

  The amount of the electron donating compound used in the main polymerization is usually 0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably 0.5 to 1 mol of titanium atom contained in the solid catalyst component. It is -800 mol, and is 0.001-5 mol normally with respect to 1 mol of organoaluminum compounds, Preferably it is 0.005-3 mol, Most preferably, it is 0.01-1 mol.

The polymerization temperature in the main polymerization is usually −30 to 300 ° C., preferably 20 to 180 ° C., more preferably 50 to 95 ° C. The polymerization pressure is not particularly limited, and is generally from normal pressure to 100 kg / cm ² , preferably from about ² to 50 kg / cm ² from the viewpoint of being industrial and economical. The polymerization format may be batch or continuous. As a polymerization method, a slurry polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane and octane, a solution polymerization method using the solvent, and an olefin which is liquid at the polymerization temperature as a medium. Examples of the bulk polymerization method and the gas phase polymerization method can be given. In particular, the step 2 is preferably a gas phase polymerization method from the viewpoint of obtaining good powder properties.

Further, in step 2, from the viewpoint of improving powder properties, improving polymer physical properties, and controlling polymerization activity, step 2 may be performed by adding a polymerization activity inhibitor to the polymerization system. preferable.
The polymerization activity inhibitor used here is a compound having an effect of reducing the polymerization activity of the catalyst in Step 2. For example, electron-donating compounds such as alkoxysilanes, esters, and ethers, active hydrogen compounds such as alcohols and water, and oxygen-containing gases that are gaseous at normal temperature and pressure, such as oxygen, carbon monoxide, and carbon dioxide Compounds, and one or more of these are preferably used. Among these, tetraethoxysilane, tetramethoxysilane, methanol, ethanol, propanol, butanol, oxygen, or carbon monoxide are preferably used, and tetraethoxysilane, ethanol, or oxygen is particularly preferably used.

  The substance for suppressing the polymerization activity is used by adding it to the polymerization system in carrying out the step 2, and it is considered that the improvement effect is manifested by the contact with the polymer particles existing in the polymerization system. The addition method may be a batch type or a continuous type. The timing of addition may be at the start of Step 2 or immediately before the end of Step 1. The polymerization activity-inhibiting substance may be used as it is, or may be diluted with an inert hydrocarbon solvent or the like.

  In the main polymerization, a chain transfer agent such as hydrogen may be used in order to adjust the molecular weight of the resulting olefin polymer.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not specifically limited by the following examples. In the examples, the evaluation methods of various physical properties of the catalyst component and the polymer are as follows.

(1) Average particle size and particle size distribution: The average particle size of the solid catalyst component precursor and the amount of fine powder components having a particle size of 16 μm or less were measured using an ultracentrifugal automatic particle size distribution analyzer (CAPA-700 manufactured by Horiba, Ltd.). did. Decahydronaphthalene was used as the dispersion medium.

(2) Composition analysis: Ti content was determined by decomposing solid components with dilute sulfuric acid, adding excess hydrogen peroxide solution, and measuring 410 nm characteristic absorption using Hitachi double beam spectrophotometer U-2001 type. It was determined by a calibration curve. The alkoxy group content was determined by decomposing the solid component with water and then measuring the corresponding alcohol amount using a gas chromatography internal standard method. The phthalate content was determined by dissolving a solid sample in N, N-dimethylacetamide and then determining the amount of phthalate in the solution by gas chromatography internal standard method.

(3) Intrinsic viscosity ([η]): Measured using an Ubbelohde viscometer at a temperature of 135 ° C. using tetralin as a solvent. In addition, for each component of the polymer, [η] P: the intrinsic viscosity of the propylene homopolymer portion and [η] EP: the intrinsic viscosity of the ethylene / propylene copolymer portion are shown. [Η] EP was calculated according to the following formula when the intrinsic viscosity of the entire block copolymer was [η] TOTAL.

(4) Bulk density: Measured according to JIS K-6721 (1966).

(5) Flowing volume of polymer powder Weight of polymer powder falling in 5 seconds when polymer powder is flowed constantly using a stainless steel funnel (FIG. 2) having an inner diameter of 13.5 mm under the funnel ( g / 5 sec)), (weight of polymer powder falling in 5 seconds (g / 5 sec)) × 2 ÷ (bulk density of the polymer powder (g / ml)) = (polymer per 10 seconds) The powder drop volume (ml / 10 sec) was calculated. The larger this value, the easier the polymer powder moves and the better the powder properties.

[Example 1]
(1) Synthesis of solid catalyst component precursor 200 liter cylindrical reactor shown in FIG. 2 (diameter 0 having three pairs of stirring blades having a diameter of 0.35 m and four baffle plates having a width of 0.05 m) 0.5 m) was replaced with nitrogen, and 54 liters of hexane, 780 g of diisobutyl phthalate, 20.6 kg of tetraethoxysilane and 2.23 kg of tetrabutoxytitanium were added and stirred. Next, 51 liters of dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / liter) was dropped into the stirred mixture over 4 hours while maintaining the temperature in the reactor at 5 ° C. At this time, the rotational speed of stirring was 120 rpm. After completion of the dropwise addition, the mixture was stirred at 20 ° C. for 1 hour and filtered. The obtained solid was washed with 70 liters of toluene at room temperature three times, and toluene was added to obtain a solid catalyst component precursor slurry.
The solid catalyst component precursor contained Ti: 1.9% by weight, OEt (ethoxy group): 35.9% by weight, and OBu (butoxy group): 3.6% by weight. The average particle size was 36 μm, and the amount of fine powder components having a particle size of 16 μm or less was 0.4% by weight.

(2) Synthesis of solid catalyst component A 200-liter cylindrical reactor having the same shape as that used in (1) above was purged with nitrogen, and the solid catalyst component precursor slurry obtained in (1) above was transferred. After standing, toluene was withdrawn so that the volume of the slurry was 49.7 liters, and with stirring, a mixed solution of 30 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added, and 4.23 kg of orthophthalic acid chloride was further added. I put it in. The temperature in the reactor was set at 110 ° C. and stirred for 3 hours, followed by filtration. The obtained solid was washed with 90 liters of toluene at 95 ° C. three times.
Toluene was added to form a slurry. After standing, the toluene was withdrawn so that the slurry volume was 49.7 liters. Under stirring, 15 liters of tetrachlorotitanium, 1.16 kg of dibutyl ether, 0.87 kg of diisobutyl phthalate Was added. The temperature in the reactor was set at 105 ° C. and stirred for 1 hour, followed by filtration. The obtained solid was washed twice with 90 liters of toluene at 95 ° C.
Toluene was added to form a slurry, and after standing, toluene was extracted so that the volume of the slurry was 49.7 liters, and a mixed liquid of 15 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added with stirring. The temperature in the reactor was set at 105 ° C. and stirred for 1 hour, followed by filtration. The obtained solid was washed twice with 90 liters of toluene at 95 ° C.
Toluene was added to form a slurry, and after standing, toluene was extracted so that the volume of the slurry was 49.7 liters, and a mixed liquid of 15 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether was added with stirring. The temperature in the reactor was set at 105 ° C. and stirred for 1 hour, followed by filtration. The obtained solid was washed with 90 liters of toluene three times at 95 ° C. and twice with 90 liters of hexane. The obtained solid component was dried to obtain a solid catalyst component.
The solid catalyst component contained Ti: 2.2% by weight and phthalate ester component: 9.4% by weight.

(3) Polymerization of block copolymer The inside of a stainless steel autoclave having an internal volume of 1 liter was evacuated, and hydrogen corresponding to a partial pressure of 0.08 MPa was added. (B) Triethylaluminum 1.0 mmol, (C) cyclohexylethyldimethoxysilane 0.1 mmol, and (A) 7.2 mg of the solid catalyst component synthesized in (2) above were charged, and then 150 g Liquefied butane and 150 g of liquefied propylene were charged, and the temperature of the autoclave was raised to 80 ° C. to initiate polymerization. After 36 minutes, when the internal pressure of the autoclave reached approximately 1.7 MPa, 0.1 mmol of tetraethoxysilane was added, and after 3 minutes, the liquid component was purged. After purging, 3.5 g of powder was sampled from inside the autoclave and the weight of the autoclave was measured. The amount of polymer in the autoclave was 102 g.
Thereafter, hydrogen having a partial pressure of 0.02 MPa, propylene having a partial pressure of 0.45 MPa, and ethylene having a partial pressure of 0.25 MPa were charged, and polymerization was performed at 65 ° C. for 90 minutes. At this time, a propylene / ethylene mixed gas (propylene content: 50% by weight) was fed so as to maintain the pressure in the autoclave. After polymerization, unreacted monomers were purged and the weight of the autoclave was measured. The amount of polymer in the autoclave was 162 g.
The EP content calculated from the change in the weight of the autoclave was 37% by weight, the intrinsic viscosity [η] P = 1.5 (measured using a small amount of sample extracted after the former polymerization), and the intrinsic viscosity of the latter polymerization part. [Η] EP = 3.0. The flowing-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 232 ml / 10 sec.

[Example 2]
(1) Polymerization of block copolymer A block copolymer was produced in the same manner as in Example 1 (3) except that 0.3 mmol of ethanol was added instead of 0.1 mmol of tetraethoxysilane.
The EP content calculated from the change in the weight of the autoclave was 37% by weight, the intrinsic viscosity [η] P = 1.5 of the former polymerization part, and the intrinsic viscosity [η] EP = 3.2 of the latter polymerization part. The flowing-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 295 ml / 10 sec.

[Example 3]
(1) Polymerization of block copolymer A block copolymer was produced in the same manner as in Example 1 (3) except that 0.1 mmol of tetraethoxysilane was not added.
The EP content calculated from the change in the weight of the autoclave was 35% by weight, the intrinsic viscosity [η] P = 1.5 of the former polymerization part, and the intrinsic viscosity [η] EP = 3.0 of the latter polymerization part. The flowing-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 202 ml / 10 sec.

[Example 4]
(1) Synthesis of Solid Catalyst Component Precursor In the same reactor as in Example 1 (1), 54 liters of hexane, 100 g of diisobutyl phthalate, 20.6 kg of tetraethoxysilane and 2.23 kg of tetrabutoxytitanium were charged and stirred. Next, 51 liters of dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / liter) was dropped into the stirred mixture over 4 hours while maintaining the temperature in the reactor at 7 ° C. At this time, the stirring rotation speed was 150 rpm. After completion of the dropping, the mixture was stirred at 20 ° C. for 1 hour and then filtered. The obtained solid was washed with 70 liters of toluene at room temperature three times, and toluene was added to obtain a solid catalyst component precursor slurry.
The solid catalyst component precursor contained Ti: 1.9% by weight, OEt (ethoxy group): 35.6% by weight, and OBu (butoxy group): 3.5% by weight. The average particle diameter was 39 μm, and the amount of fine powder components having a particle diameter of 16 μm or less was 0.5% by weight.

(2) Synthesis of solid catalyst component In Example 1 (2), the solid catalyst component precursor slurry was changed to that obtained in (1) above, and the solid catalyst component precursor slurry was transferred and allowed to stand. Then, after extracting toluene so that the volume of the slurry becomes 49.7 liters, before introducing a mixed solution of 30 liters of tetrachlorotitanium and 1.16 kg of dibutyl ether, “stir at 80 ° C. for 1 hour. Thereafter, the same operation as in Example 1 (2) was carried out except that a heat treatment of “cooling the slurry to 40 ° C. or lower” was performed to obtain a solid catalyst component.
The solid catalyst component contained Ti: 2.1% by weight and phthalate ester component: 10.8% by weight.

(3) Polymerization of block copolymer The inside of a stainless steel autoclave similar to that in Example 1 (3) was evacuated, and hydrogen corresponding to a partial pressure of 0.08 MPa was added. As component (B), 1.0 mmol of triethylaluminum, as component (C), 0.1 mmol of cyclohexylethyldimethoxysilane, and as component (A), 7.0 mg of the solid catalyst component synthesized in the above (2) were charged, and then 150 g of Liquefied butane and 150 g of liquefied propylene were charged, and the temperature of the autoclave was raised to 80 ° C. to initiate polymerization. After 42 minutes, the liquid component was purged when the internal pressure of the autoclave reached approximately 1.7 MPa. After purging, 3.0 g of powder was sampled from inside the autoclave, and the weight of the autoclave was measured. The amount of polymer in the autoclave was 103 g. Thereafter, 2 ml of oxygen, hydrogen having a partial pressure of 0.02 MPa, propylene having a partial pressure of 0.45 MPa, and ethylene having a partial pressure of 0.25 MPa were charged, and polymerization was performed at 65 ° C. for 133 minutes. At this time, a propylene / ethylene mixed gas (propylene content: 50% by weight) was fed so as to maintain the pressure in the autoclave. After polymerization, unreacted monomers were purged and the weight of the autoclave was measured. The amount of polymer in the autoclave was 159 g.
The EP content calculated from the change in the weight of the autoclave was 35% by weight, the intrinsic viscosity [η] P = 1.4 of the former polymerization part, and the intrinsic viscosity [η] EP = 2.5 of the latter polymerization part. The flow-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 339 ml / 10 sec.

[Example 5]
(1) Polymerization of block copolymer The inside of a stainless steel autoclave similar to that in Example 1 (3) was evacuated, and hydrogen corresponding to a partial pressure of 0.12 MPa was added. (B) component triethylaluminum 1.0 mmol, component (C) t-butyl n-propyldimethoxysilane 0.1 mmol and component (A) 8.4 mg of the solid catalyst component synthesized in Example 4 (2). Then, 150 g of liquefied butane and 150 g of liquefied propylene were charged, and the temperature of the autoclave was raised to 80 ° C. to initiate polymerization. After 34 minutes, the liquid component was purged when the internal pressure of the autoclave reached approximately 1.7 MPa. After purging, 4.5 g of powder was sampled from inside the autoclave and the weight of the autoclave was measured. The amount of polymer in the autoclave was 113 g. Thereafter, 2 ml of oxygen, hydrogen having a partial pressure of 0.03 MPa, propylene having a partial pressure of 0.45 MPa, and ethylene having a partial pressure of 0.25 MPa were charged, and polymerization was performed at 65 ° C. for 145 minutes. At this time, a propylene / ethylene mixed gas (propylene content: 50% by weight) was fed so as to maintain the pressure in the autoclave. After polymerization, unreacted monomers were purged and the weight of the autoclave was measured. The amount of polymer in the autoclave was 171 g.
The EP content calculated from the change in the weight of the autoclave was 34% by weight, the intrinsic viscosity [η] P = 1.7 in the former polymerization part, and the intrinsic viscosity [η] EP = 2.3 in the latter polymerization part. The flow-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 296 ml / 10 sec.

[Example 6]
(1) Polymerization of block copolymer t-butyl n-propyldimethoxysilane The block copolymer was the same as in Example 5 (1) except that 0.1 mmol of dicyclopentyldimethoxysilane was used instead of 0.1 mmol. A coalescence was produced.
The EP content calculated from the change in the weight of the autoclave was 34% by weight, the intrinsic viscosity [η] P = 1.7 of the former polymerization part, and the intrinsic viscosity [η] EP = 3.0 of the latter polymerization part. The flow-down volume of the powder after heat treatment at 80 ° C. for 2 hours was 337 ml / 10 sec.

[Comparative Example 1]
(1) Synthesis of solid catalyst component precursor In the same reactor as in Example 1 (1), 46 liters of hexane, 820 g of diisobutyl phthalate, 19.9 kg of tetraethoxysilane and 2.19 kg of tetrabutoxytitanium were added and stirred. Next, 51 liters of dibutyl ether solution of butyl magnesium chloride (concentration 2.1 mol / liter) was dropped into the stirred mixture over 4 hours while maintaining the temperature in the reactor at 10 ° C. At this time, the stirring rotation speed is 200 rpm. After completion of the dropping, the mixture was stirred at 20 ° C. for 1 hour and then filtered. The obtained solid was washed with 70 liters of toluene at room temperature three times, and toluene was added to obtain a solid catalyst component precursor slurry.
The solid catalyst component precursor contained Ti: 1.9% by weight, OEt (ethoxy group): 34.0% by weight, and OBu (butoxy group): 3.5% by weight. The average particle size was 20 μm, and the amount of fine powder components having a particle size of 16 μm or less was 3.9% by weight.

(2) Synthesis of solid catalyst component Using the solid catalyst component precursor obtained in (1) above, the same synthesis as in Example 1 (2) was performed to obtain a solid catalyst component.
The solid catalyst component contained Ti: 1.9% by weight and phthalate ester component: 7.6% by weight.

(3) Polymerization of block copolymer A block copolymer was produced in the same manner as in Example 1 (3) using the solid catalyst component obtained in (2) above.
The EP content calculated from the change in the weight of the autoclave was 38% by weight, the intrinsic viscosity [η] P = 1.6 of the former polymerization part, and the intrinsic viscosity [η] EP = 3.0 of the latter polymerization part. The flowing volume of the powder after heat treatment at 80 ° C. for 2 hours was 108 ml / 10 sec, and it was a polymer powder having relatively poor flowing properties.

[Comparative Example 2]
(1) Polymerization of block copolymer A block copolymer was produced in the same manner as in Comparative Example 1 (3) except that 0.3 mmol of ethanol was added instead of 0.1 mmol of tetraethoxysilane.
The EP content calculated from the change in the weight of the autoclave was 36% by weight, the intrinsic viscosity [η] P = 1.6 of the former polymerization part, and the intrinsic viscosity [η] EP = 2.9 of the latter polymerization part. The flowing volume of the powder after heat treatment at 80 ° C. for 2 hours was 168 ml / 10 sec, and it was a polymer powder having relatively poor flowing properties.

  As described above in detail, according to the present invention, a solid catalyst component for producing a propylene block copolymer capable of producing a propylene block copolymer having excellent powder properties, a catalyst for producing a propylene block copolymer, and A method for producing a propylene block copolymer is provided. Further, according to the present invention, a solid catalyst component for α-olefin polymerization that exhibits high stereoregular polymerization ability, a catalyst for α-olefin polymerization, and a method for producing a highly stereoregular α-olefin polymer can also be provided.

FIG. 1 is a flowchart for helping understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this. FIG. 2 shows a top view (a) and a side view (b) of the cylindrical reactor used in Example 1 (1) and others. FIG. 3 is a side view of a stainless steel funnel and support used for measuring the flow-down volume of the polymer powder carried out in the examples.

Claims (4)

A solid catalyst component for producing a propylene block copolymer obtained by bringing the following (a), (b) and (c) into contact with each other.
(A) It is obtained by reducing a titanium compound (a2) represented by the following general formula [I] with an organomagnesium compound (a3) in the presence of an organosilicon compound (a1) having a Si—O bond. , an average particle diameter of Ri 27-55 microns der, the solid catalyst component precursor fine powder component of less 16 microns is 3 wt% or less

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
(B) General formula M (OR ⁹ ) _b X ⁴ _4-b (wherein M represents a Group 4 element, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁴ represents a halogen atom) Wherein b represents a number satisfying 0 ≦ b <4), or a general formula MR _ma X _a (wherein M is a Group 13 or Group 14 atom, R is A halogenated compound represented by a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, m represents a valence of M, and a represents a number satisfying 0 <a ≦ m. c) electron donor A solid catalyst component for producing a propylene block copolymer obtained by bringing the following (a), (b), (c) and (d) into contact with each other.
(A) It is obtained by reducing a titanium compound (a2) represented by the following general formula [I] with an organomagnesium compound (a3) in the presence of an organosilicon compound (a1) having a Si—O bond. , an average particle diameter of Ri 27-55 microns der, the solid catalyst component precursor fine powder component of less 16 microns is 3 wt% or less

(In the formula, a represents a number of 1 to 20, R ² represents a hydrocarbon group having 1 to 20 carbon atoms, X ² represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, All X ² may be the same or different.)
(B) General formula M (OR ⁹ ) _b X ⁴ _4-b (wherein M represents a Group 4 element, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X ⁴ represents a halogen atom) Wherein b represents a number satisfying 0 ≦ b <4), or a general formula MR _ma X _a (wherein M is a Group 13 or Group 14 atom, R is A halogenated compound represented by a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, m represents a valence of M, and a represents a number satisfying 0 <a ≦ m. c) Electron donor (d) Organic acid halide A catalyst for producing a propylene block copolymer obtained by contacting the solid catalyst component (A) according to claim 1 or 2 , the organoaluminum compound (B), and the electron donating compound (C). Method for producing a propylene block copolymer composed of the following steps using the propylene block copolymer production catalyst according to claim 3, wherein.
Step 1: (1) Step of homopolymerizing propylene to form homopolypropylene, or (2) Copolymerization of propylene with an olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A step of producing a copolymer A. Here, the copolymerization is carried out so that the content of polymerized units of the olefin in the copolymer A is 10% by weight or less (the copolymer A is 100% by weight).
Step 2: In the presence of the homopolypropylene or copolymer A obtained in Step 1, propylene is copolymerized with an olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms. A step of producing a block copolymer by producing the combined B. Here, in the copolymerization, the content of polymerized units of the olefin in the copolymer B is 10 to 60% by weight (the copolymer B is 100% by weight), and the copolymer in the block copolymer It implements so that content of the copolymer B may be 2 to 60 weight% (a block copolymer shall be 100 weight%).

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