JPH08176223A - Catalyst for polymerization of alpha-olefin and production of alpha-olefin polymer - Google Patents

Abstract

PURPOSE: To obtain a catalyst system which can give an α-olefin polymer having a broad molecular weight distribution and high stereoregularity by combining a Ti-containing solid catalyst component treated with a specified organic transition metal compound with an organoaluminum compound and an electron- donating compound. CONSTITUTION: The catalyst system comprises a solid catalyst component prepared by treating a solid catalyst component containing a titanium (III) compound with a cyclopentadienyl-containing organic transition metal compound represented by the formlula (Cp is cyclopentadienyl; M is a group IV transition metal; X is a halogen; R is alkyl, aryl or alkyl or aryl containing O, N, S or P; and m, n and p are numbers in the ranges: 1<=m<=3, 0<=n<=3, 0<=p<=3, and m+n+p=4), an organoaluminum compound and an electron-donating compound (e.g. an ester or ether of an inorganic acid).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst system for .alpha.-olefin polymerization. The present invention also relates to a method for producing an α-olefin polymer using such a polymerization catalyst. More specifically, a novel catalyst system for α-olefin polymerization giving an α-olefin polymer having a wide molecular weight distribution and high stereoregularity excellent in mechanical properties and processability, and an α-olefin having a wide molecular weight distribution and high stereoregularity The present invention relates to a method for producing an olefin polymer.

[0002]

The fluidity of α-olefin polymers generally greatly affects the processability and physical properties when they are used after being processed into molded products, films, fibers and other processed products. . By the way, as a method for producing an α-olefin polymer such as propylene or butene-1, a supported solid catalyst obtained by supporting a tetravalent titanium halide on magnesium halide, or a tetravalent titanium compound. In the presence of a composite type solid catalyst obtained by reducing methane with organomagnesium to form a eutectic of magnesium and titanium, or an organosilicon compound.
It is possible to realize highly stereoregular and highly active polymerization of α-olefins by a Ti-Mg composite solid catalyst obtained by reducing a valent titanium compound with an organomagnesium compound to form a eutectic of magnesium and titanium. Known (Japanese Patent Publication No. 3-43283, JP-A-1
-319508). However, while all of these catalyst systems can produce an α-olefin polymer with high stereoregularity and high polymerization activity, the produced polymer has a narrow molecular weight distribution and has a difficulty in fluidity.

As means for broadening the molecular weight distribution in order to overcome this drawback, JP-A-3-43406 and JP-A-3-56508 disclose a solid composite containing titanium, magnesium, halogen and an electron donating compound. Component obtained by contacting a reaction product of an organic transition metal compound having a substituted or unsubstituted cyclopentadienyl group with an alkylaluminum compound and / or a mixture thereof, an organometallic compound of Groups I to III of the periodic table There is a description that a highly ordered polymer having a wide molecular weight distribution can be obtained in a high yield by using a catalyst system composed of an electron donating compound. Further, in JP-A-5-301920, a carrier from the reaction of an aluminum halide, a silicon compound and a magnesium compound is treated with an electron donor and a titanium compound, and further, an organic transition having a titanium compound and a cyclopentadienyl group. Α-Olefin polymer with high activity, high stereoregularity, and wide molecular weight distribution, using a catalyst system consisting of a solid catalyst component, an organoaluminum component, and an electron donor component which are contact-treated with a reaction product of a metal compound and an alkylaluminum compound. There is a statement to get. JP-A-5-331231 discloses a solid catalyst component (A) containing titanium, magnesium, halogen and an electron donating compound as essential components, and a solid component containing titanium, magnesium, halogen and an electron donating compound as essential components. By using a catalyst system obtained from a solid catalyst component (B) obtained by treating a compound with an organic transition metal compound, an organoaluminum compound (C), and an electron donor (D), high activity, high stereoregularity, and wide range. It is described that an α-olefin polymer having a molecular weight distribution is obtained. These known techniques certainly give α-olefin polymers having a wide molecular weight distribution, but both are characterized by treatment with a reaction product of an organic transition metal compound having a cyclopentadienyl group and an alkylaluminum compound. However, the adjustment takes a long time, the productivity is poor industrially, and the polymer obtained is still insufficient in stereoregularity.

Further, in Japanese Patent Application Laid-Open No. 5-287018, electron donation is carried out when an α-olefin is polymerized by a catalyst composed of a solid catalyst component obtained by supporting titanium halide on magnesium halide and an organometallic compound. The addition of a cyclopentadiene compound of a metal of Group 2, Group 3, Group 5, Group 12 or Group 13 of the periodic table gives a highly stereoregular polyolefin having a relatively wide molecular weight distribution. There is a description. However, the metal cyclopentadiene compound used is very expensive and special,
High production cost and industrial disadvantage. Furthermore, JP-A-4-227707 and JP-A-4-359904.
In the publication, a catalyst system is used in which a solid catalyst component obtained by supporting titanium halide on magnesium halide and an organoaluminum compound are contacted with an alkoxysilane compound containing a branched hydrocarbon group and an alicyclic hydrocarbon group. It is described that an α-olefin polymer having high activity, high stereoregularity and wide molecular weight distribution is obtained. However, all of these techniques require the use of a very expensive alkoxysilane compound having a sterically bulky hydrocarbon group in a larger amount than the solid catalyst component, resulting in high production cost and industrial disadvantage. Is. JP-A-4-110308 and JP-A-4-4-2
No. 22804 discloses a solid catalyst component obtained by pulverizing magnesium chloride, phthalic acid ester, titanium tetrachloride and dicyclopentadienyltitanium dichloride with a ball mill, an organoaluminum, and a catalyst system of an alkoxysilane compound, which has a wide molecular weight distribution α. -It discloses that an olefin polymer is obtained. Also, in the specification, a catalyst system such as a solid solution of magnesium chloride, phthalic acid ester, titanium tetrachloride pulverized in the same manner, organoaluminum, an alkoxysilane compound and a toluene solution of dicyclopentadienyl titanium dichloride may be used. There is also a description that a polyolefin having a wide molecular weight distribution was obtained. However, these catalyst systems are still insufficient in terms of broad molecular weight distribution, and since they are pulverized by a ball mill, the solid catalyst has a wide particle size distribution and a large amount of fine powder. Therefore, it is not preferable in handling the catalyst,
The obtained polyolefin also has the drawbacks of low bulk density and a large amount of fine powder.

In any case, the bulk density and stereoregularity of the α-olefin polymer having a high activity, a high bulk density, a high stereoregularity and a wide molecular weight distribution, to some extent, can be obtained. Further improvement of the balance of molecular weight distribution is desired. Specifically, in order to improve the quality and processability of the α-olefin polymer, it is desired to realize a wider molecular weight distribution and a higher stereoregular polymerization. In particular, in applications where high rigidity and high fluidity of polymers are desired, such as in the field of molding, it is a high stereoregular polymer with a wide molecular weight distribution that direct high rigidity quality and good processing Therefore, the advent of a catalyst system having a high stereoregular polymerization ability and having a wide molecular weight distribution is urgently desired.

[0006]

Under the present circumstances,
The problem to be solved by the present invention, that is, the object of the present invention, is to provide a catalyst system for α-olefin polymerization having a wide molecular weight distribution and high stereoregularity, and a wide molecular weight distribution using the catalyst system. It is intended to provide a method for producing a highly stereoregular α-olefin polymer. Further, the present invention provides a catalyst for α-olefin polymerization having a wide molecular weight distribution, high stereoregularity and high bulk density, and α-olefin using the same.
It is to provide a method for producing an olefin polymer.

[0007]

That is, the present invention provides (A)
By treatment with an organic transition metal compound having a cyclopentadienyl group represented a trivalent titanium compound-containing solid catalyst component by the following equation (1), the resulting solid catalyst component _{Cp m MX n R p (1} ) ( In the formula, Cp represents a substituted or unsubstituted cyclopentadienyl group, M represents a Group 4 transition metal, X represents a halogen atom, R represents an alkyl group, an aryl group or O, N,
An alkyl group and an aryl group containing S and P atoms are shown. Further, m, n, and p are integers that satisfy the following formula.
1 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 ≦ p ≦ 3, m + n + p =
4), (B) an organoaluminum compound, and (C) an electron-donating compound.

Further, the present invention has (A) Si-O bond.
In the presence of an organosilicon compound¹)
_aX_4-a(R¹Is a hydrocarbon group having 1 to 20 carbon atoms, and X is
A halogen atom and a represent a number of 0 <a ≦ 4. )
Reduction of titanium compounds with organic magnesium compounds
The solid product obtained was treated with an ester compound.
A mixture of ether compound and titanium tetrachloride, or
Mixing of ether compound, titanium tetrachloride and ester compound
Trivalent titanium compound obtained by treating with a substance
The solid catalyst component containing cyclopentadiene represented by the following formula
With an organic transition metal compound (1) having a ruthenium group
The solid catalyst component Cp obtained by_mMX_nR_p (1) (B) organoaluminum compound, and (C) electron donating property
Related to α-olefin polymerization catalysts composed of compounds
is there.

Further, the present invention relates to a method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using the catalyst system for α-olefin polymerization according to the present invention.

The present invention will be specifically described below. The solid catalyst component obtained by treating the trivalent titanium compound-containing solid catalyst component (A) with the organic transition metal compound (1) having a cyclopentadienyl group represented by the following formula will be described. Cp _m MX _n R _p (1)

As the solid catalyst component containing a trivalent titanium compound of the present invention, a general titanium trichloride composition can be preferably used. Particularly, a solid component containing titanium, magnesium, a halogen and an electron donating compound as an essential component is preferably used, and the atomic ratio of titanium / magnesium is 0.01 to.
It is 0.8, preferably 0.02-0.2. The chlorine / magnesium atomic ratio is 1.8 to 10, preferably 2.0 to 5.0. As a method for producing such a catalyst component, for example, JP-B-53-3356 and JP-B-53-53
-44958, JP-A-59-126402, JP-B-3-46001, JP-B-3-43283, JP-B3
-43284, Japanese Examined Patent Publication No. 3-43285, Japanese Patent Laid-Open No. 1-3
19508, JP-A-2-163104, JP-A-2-
Examples thereof include the method disclosed in Japanese Patent No. 283703.

The titanium compound used in the present invention has a general formula of Ti (OR ¹ ) _a X _4-a (R ¹ has ¹ carbon atom.
To 20 hydrocarbon groups, X is a halogen atom, and a is 0 ≦ a ≦.
Represents the number 4. ) And a titanium compound represented by the formula (1). Specific examples of R ¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Alkyl groups such as t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc., cycloalkyl groups such as phenyl, cresyl, xylel, naphthyl, allyl groups such as propenyl, aralkyl such as benzyl. Examples include groups. Of these, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable. It is also possible to use a titanium compound having two or more different OR ¹ groups. Examples of the halogen atom represented by X include chlorine, bromine and iodine. Of these, chlorine gives particularly favorable results. Here, the value of a of the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a is 0 <a ≦ 4, preferably 2 ≦ a ≦ 4, and particularly preferably a = 4. Is.

As _a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) _a X _4-a , known methods can be used. For example, a method of reacting Ti (OR ¹ ) ₄ and TiX ₄ in a predetermined ratio, or a method of reacting TiX ₄ and a corresponding alcohol in a predetermined amount can be used. Also,
These titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound before use.

Specific examples of the titanium compound include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and other tetrahalogenated titanium compounds, methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, and phenoxytitanium trioxide. Chloride, trihalogenated alkoxytitanium compounds such as ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, dihalogenated dialkoxytitanium compounds such as diethoxytitanium dibromide,
Trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, triphenoxytitanium chloride, triethoxytitanium bromide and other monohalogenated trialkoxytitanium compounds, tetramethoxytitanium, tetraethoxytitanium, tetrabutoxytitanium, tetraphenoxytitanium, etc. The tetraalkoxy titanium compound can be mentioned.

Next, it is used in the synthesis of the solid catalyst component of the present invention.
As an organosilicon compound having a Si-O bond
Can be represented by the following general formula. Si (OR²)_mR³ _4-m R^Four(R^Five ₂SiO)_pSiR⁶ ₃ Or (R⁷ ₂SiO)_q Where R²Is a hydrocarbon group having 1 to 20 carbon atoms, R³,
R^Four, R^Five, R⁶And R⁷Is carbonized with 1 to 20 carbon atoms
It is a hydrogen group or a hydrogen atom, and m is a number of 0 <m ≦ 4.
Yes, p is an integer of 1 to 1000, and q is 2 to 100
It is an integer of 0. Preferred of these organosilicon compounds
The new one is the general formula Si (OR²)_mR ³ _4-mRepresented by
An alkoxysilane compound, preferably 1 ≦ m ≦
4 and especially m = 4 tetraalkoxysilane compound
Is preferred.

Specific examples of such organosilicon compounds include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxydiisopropyl. Silane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane,
Examples include tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane. be able to.

As the ester compound used in the present invention, mono- and polyvalent carboxylic acid esters are used.
Examples thereof include aliphatic carboxylic acid ester, olefinic carboxylic acid ester, alicyclic carboxylic acid ester, and aromatic carboxylic acid ester. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate,
Ethyl valerate, methyl acrylate, ethyl acrylate,
Methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, itaconic acid Diethyl, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-isopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, phthal Examples thereof include acid diphenyl. Of these ester compounds, olefinic carboxylic acid esters such as methacrylic acid esters and maleic acid esters and phthalic acid esters are preferred, and diesters of phthalic acid are particularly preferred.

Next, as the organomagnesium used in the present invention, any type of organomagnesium compound containing a Mg-carbon bond can be used. Especially the general formula R ⁸
MgX (in the formula, R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms,
X represents halogen. ) And a dialkyl magnesium compound or diaryl magnesium compound represented by the general formula R ⁹ R ¹⁰ Mg (wherein R ⁹ and R ¹⁰ represent a hydrocarbon group having 1 to 20 carbon atoms). It is preferably used. Here, R ⁸ , R ⁹ and R ¹⁰ may be the same or different and are methyl, ethyl, propyl,
It represents an alkyl group having 1 to 20 carbon atoms such as isopropyl, butyl, sec-butyl, amyl, isoamyl, hexyl, octyl, 2-ethylhexyl, phenyl and benzyl, an aryl group, an aralkyl group and an alkenyl group.

Specifically, as the Grignard compound,
Methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, se
c-butyl magnesium chloride, sec-butyl magnesium bromide, tert-butyl magnesium chloride, tert-butyl magnesium bromide, amyl magnesium chloride, isoamyl magnesium chloride, hexyl magnesium chloride,
Phenylmagnesium chloride, phenylmagnesium bromide and the like are compounds represented by the general formula R ⁹ R ¹⁰ Mg, and include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, di-sec-butylmagnesium, di- Examples thereof include tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, dihexyl magnesium, diphenyl magnesium and butyl ethyl magnesium.

As the synthetic solvent for the above-mentioned organomagnesium compound, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether, Ether solvents such as phenetole, anisole, tetrahydrofuran and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used.

The organic magnesium compound is preferably used in the state of an ether solution. In this case, the ether compound is an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure. Used. It is particularly preferable to use the Grignard compound represented by the general formula R ⁸ MgX in the state of an ether solution from the viewpoint of catalytic performance. Further, a hydrocarbon-soluble complex of the above organomagnesium compound and an organometallic compound can also be used. Examples of such organic metal compounds include organic compounds of Li, Be, B, Al or Zn.

Next, as the ether compound used in the present invention, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, Dialkyl ethers such as methyl butyl ether, methyl isoamyl ether and ethyl isobutyl ether can be mentioned. Of these, dibutyl ether and diisoamyl ether are particularly preferably used.
A solid catalyst component is obtained by subjecting the solid component prepared as described above to contact treatment with an organometallic compound.

The organic transition metal compound used in the present invention is preferably an organic transition metal compound having a cyclopentadienyl group, and in particular, a compound represented by the general formula Cp _m MX _n R _p (1) (wherein Cp is substituted or non-substituted) Represents a substituted cyclopentadienyl group, M represents a Group 4 transition metal of the periodic table (IUPAC Inorganic Chemistry Nomenclature revised edition, 1989), X represents a halogen atom, R represents an alkyl group, an aryl group. Or O,
An alkyl group and an aryl group containing N, S and P atoms are shown. Further, m, n, and p are integers that satisfy the following formula. 1 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 ≦ p ≦ 3, m + n + p
= 4) is more preferable, and examples of the substituent of the substituted cyclopentadienyl group in the above general formula include lower alkyl groups such as methyl, ethyl, propyl, and butyl. It may be crosslinked with another metal atom. Examples of the transition metal of Group 4 include zirconium, hafnium, and titanium, and of these, titanium is more preferably used.

Examples of the organic transition metal compound (1) having a cyclopentadienyl group used in the present invention include bis (cyclopentadienyl) titanium monochloride monohydride and bis (cyclopentadienyl) titanium monobromide mono. Hydride, bis (cyclopentadienyl) methyltitanium chloride, bis (cyclopentadienyl) ethyltitanium hydride, bis (cyclopentadienyl) phenyltitanium hydride, bis (cyclopentadienyl) benzyltitanium hydride, bis (cyclopentadiene) Dienyl) neopentyl titanium hydride, bis (methylcyclopentadier) titanium monochloride hydride, bis (indenyl) titanium monochloride monohydride, bis Cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) titanium dibromide, bis (cyclopentadienyl) methyltitanium monochloride, bis (cyclopentadienyl) ethyltitanium monochloride, bis (cyclopentadienyl) Ethyl titanium monochloride, bis (cyclopentadienyl) cyclohexyl titanium monochloride, bis (cyclopentadienyl) benzyl titanium monochloride, bis (cyclopentadienyl) phenyl titanium monochloride, bis (methylcyclopentadienyl) titanium Dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (n-butylcyclopentadienyl) titanium dicloid, bis (indenyl) Data pyridinium dichloride, bis (indenyl) titanium dibromide,
Bis (cyclopentadienyl) titanium dimethyl, bis (cyclopentadienyl) titanium diphenyl, bis (cyclopentadienyl titanium) dibenzyl, bis (cyclopentadienyl) titanium methoxy chloride, bis (cyclopentadienyl) titanium ethoxy Chloride, bis (methylcyclopentadienyl) titanium ethoxy chloride, bis (cyclopentadienyl) titanium phenoxycyclolide, bis (fluorenyl) titanium dichloride, ethylenebis (indenyl) dimethyltitanium, ethylenebis (indenyl) diethyltitanium, ethylenebis (Indenyl)
Diphenyltitanium, ethylenebis (indenyl) methyltitanium chloride, ethylenebis (indenyl) ethyltitanium chloride, ethylenebis (indenyl) methyltitanium bromide, ethylenebis (indenyl) titanium dichloride, ethylenebis (indenyl) titanium dibromide, ethylenebis ( 4,5,6,7-tetrahydro-1-indenyldimethyltitanium, ethylenebis (4,5,6,7-tetrahydroindenylmethyltitanium monochloride,
Ethylenebis (4,5,6,7-tetrahydro-1-indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dibromide, ethylenebis (4-methyl-1-indenyl) Titanium dichloride, ethylenebis (5-
Methyl-1-indenyl) titanium dichloride, ethylenebis (6-methyl-1-indenyl) titanium dichloride, ethylenebis (7-methyl-1-indenyl) titanium dichloride, ethylenebis (5-methoxy-1-indenyl) titanium dichloride Ethylenebis (2,3-dimethyl-1-indenyl) titanium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) titanium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl) titanium dichloride, dimethyl Silylene bis (cyclopentadienyl) titanium dichloride, dimethylsilylenebis (indenyl) titanium dicloid, dimethylsilylenebis (methylcyclopentadienyl) titanium dichloride, iso Ropiriden (indenyl) titanium dichloride, isopropylidene (cyclopentadienyl - fluorenyl) titanium dichloride and the like. Two or more kinds of these organic transition metal compounds may be used in combination.

Next, the synthesis of the solid catalyst will be described more specifically. The solid catalyst of the present invention is a solid product obtained by reducing a titanium compound with an organomagnesium compound in the presence of an organosilicon compound and an ester compound, after treating the solid product with an ester compound, a mixture of an ether compound and titanium tetrachloride or , Treated with a mixture of ether compound, titanium tetrachloride and ester compound. All of these synthetic reactions are performed in an atmosphere of an inert gas such as nitrogen or argon.

As the method of reducing the titanium compound with the organomagnesium compound, the method of adding the organomagnesium compound to the mixture of the titanium compound, the organosilicon compound and the ester compound, or conversely, the titanium compound in the solution of the organomagnesium compound, Any method of adding a mixture of an organosilicon compound and an ester compound may be used. Among these, the method of adding the organomagnesium compound to the mixture of the titanium compound, the organosilicon compound and the ester compound is preferable from the viewpoint of catalytic activity.

The titanium compound, organosilicon compound and ester compound are preferably dissolved or diluted in a suitable solvent before use. As such a solvent, hexane,
Aliphatic hydrocarbons such as heptane, octane and decane, aromatic hydrocarbons such as toluene and xylene, cyclohexane,
Alicyclic hydrocarbons such as methylcyclohexane and decalin,
Ether compounds such as diethyl ether, dibutyl ether, diisoamyl ether, tetrahydrofuran and the like can be mentioned.

The reduction reaction temperature is -50 to 70 ° C, preferably -30 to 50 ° C, particularly preferably -25 to 35 ° C.
Temperature range. If the reduction reaction temperature is too high, the catalytic activity will decrease. Further, when the solid product is synthesized by the reduction reaction, it is also possible to allow a porous material such as an inorganic oxide or an organic polymer to coexist and impregnate the porous product with the solid product. Such a porous material has a pore radius of 20 to 2
It is preferable that the pore volume at 00 nm is 0.3 ml / g or more and the average particle diameter is 5 to 300 μm.

As the porous inorganic oxide, SiO ₂ , A
l ₂ O ₃ , MgO, TiO ₂ , ZrO ₂ , SiO ₂ · A
_l 〓O ₃ composite oxide, MgO · Al ₂ O ₃ composite oxide,
Examples thereof include MgO / SiO ₂ / Al ₂ O ₃ composite oxide. As the porous polymer, polystyrene, styrene-divinylbenzene copolymer, styrene-n, n'-alkylenedimethacrylamide copolymer,
Styrene-ethylene glycol methyl methacrylate copolymer, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer Coalescence, polyethylene glycol methyl dimethacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methyl acrylate copolymer Examples thereof include polystyrene-based polymers such as polypropylene, polyacrylic acid ester-based polymers, polyacrylonitrile-based polymers, polyvinyl chloride-based polymers, and polyolefin-based polymers. Of these porous materials, SiO ₂ ,
Al ₂ O ₃ and a styrene-divinylbenzene copolymer are preferably used. The dropping time is not particularly limited, but is usually about 30 minutes to 12 hours. After completion of the reduction reaction, a post reaction may be further carried out at a temperature of 20 to 120 ° C.

The amount of the organosilicon compound used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound, Si /
Ti = 1 to 50, preferably 3 to 30, and particularly preferably 5 to 25. Further, the amount of the ester compound used is a molar ratio of the ester compound to the titanium atom of the titanium compound, the ester compound / Ti = 0.05 to 10,
The range is preferably 0.1 to 6, and particularly preferably 0.2 to 3. Further, the amount of the organomagnesium compound used is Ti + Si / Mg = 0.1 to 10, preferably 0.2 to 5.0, and particularly preferably, in terms of the sum of titanium atoms and silicon atoms and the atomic ratio of magnesium atoms. 0.5-2.0
Range. The solid product obtained by the reduction reaction is subjected to solid-liquid separation, and washed with an inert hydrocarbon solvent such as hexane and heptane several times. The solid product thus obtained is
It contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of catalytic performance, an amorphous structure is particularly preferable.

Next, the solid product obtained by the above method is
Treatment with ester compound. The amount of the ester compound used is 0.1 to 1 mol of titanium atom in the solid product.
The amount is 50 mol, more preferably 0.3 to 20 mol, and particularly preferably 0.5 to 10 mol. The amount of the ester compound used is 0.01 to 1.0 mol, preferably 0.03 to 1 mol, per 1 mol of magnesium atom in the solid product.
It is 0.5 mol. If the amount of the ester compound used is too large, the particles will disintegrate. The treatment of the solid product with the ester compound may be carried out by any known method such as a slurry method or a mechanical milling means such as a ball mill capable of bringing them into contact with each other, but mechanical milling produces fine powder in the solid catalyst component. It is generated in a large amount and the particle size distribution becomes wide, which is not preferable from an industrial viewpoint, and it is preferable to bring them into contact with each other in the presence of a diluent. Examples of diluents include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cyclopentane, 1,2-dichloroethane and monochloro. Halogenated hydrocarbons such as benzene can be used. Among these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable. The amount of the diluent used is 0.1 to 1000 ml per 1 g of the solid product.
And preferably 1 to 100 ml. The treatment temperature is −50 to 150 ° C., preferably 0 to 120 ° C.
Is. The treatment time is 5 minutes or more, preferably 1
5 minutes to 3 hours. After completion of the treatment, the mixture is left to stand, solid-liquid separated, and then washed with an inert hydrocarbon solvent several times to obtain an ester-treated solid.

Next, the ester-treated solid is treated with a mixture of an ether compound and titanium tetrachloride. This treatment is preferably performed in a slurry state. Examples of the solvent used for forming a slurry include pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene,
Aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, dichloroethane, trichloroethylene, monochlorobenzene,
Examples thereof include halogens and hydrocarbons such as dichlorobenzene and trichlorobenzene, and of these, halogenated hydrocarbons and aromatic hydrocarbons are preferable. The slurry concentration is
0.05-0.7 g solid / ml solvent, especially 0.1-0.
5 g solids / ml solvent are preferred. The reaction temperature is 30 to 1
50 ° C., preferably 45-135 ° C., particularly preferably 6
It is 0 to 120 ° C. The reaction time is not particularly limited, but usually 30 minutes to 6 hours is suitable.

The ester-treated solid, the ether compound and titanium tetrachloride can be supplied by adding the ether compound and titanium tetrachloride to the ester-treated solid, and conversely, the ester-treated solid in a solution of the ether compound and titanium tetrachloride. Any method of adding may be used. In the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, the method of adding titanium tetrachloride after adding the ether compound, or the method of simultaneously adding the ether compound and titanium tetrachloride is preferable, and particularly to the ester-treated solid. A method of adding a mixture of a previously prepared ether compound and titanium tetrachloride is preferable. The reaction of the ester-treated solid with the ether compound and titanium tetrachloride may be repeated twice or more. From the viewpoint of catalytic activity and stereoregularity, it is preferable to repeat the reaction with the mixture of the ether compound and titanium tetrachloride at least twice.

The amount of the ether compound used is 0.1 to 100 with respect to 1 mol of titanium atom contained in the solid product.
Mol, preferably 0.5 to 50 mol, particularly preferably 1
~ 20 moles. The amount of titanium tetrachloride added is 1 to 100 with respect to 1 mol of titanium atoms contained in the solid product.
0 mol, preferably 3 to 500 mol, particularly preferably 1
It is 0 to 300 mol. The addition amount of titanium tetrachloride to 1 mol of the ether compound is 1 to 100 mol, preferably 1.5 to 75 mol, and particularly preferably 2 to 50 mol. Further, when the ester-treated solid is treated with the mixture of the ether compound and titanium tetrachloride, the ester compound may coexist. In that case, the amount of the ester compound used is 30 mol or less, preferably 15 mol or less, and particularly preferably 5 mol or less, relative to 1 mol of the titanium atom contained in the solid product.

Next, the above solid is treated with the organic transition metal compound (1) having a cyclopentadienyl group. As the solvent used for this treatment, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene,
Aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, dichloroethane, trichloroethylene, monochlorobenzene,
Examples thereof include halogens and hydrocarbons such as dichlorobenzene and trichlorobenzene, and of these, halogenated hydrocarbons and aromatic hydrocarbons are preferable. The treatment concentration is 0.001 to 100 mmol of the organic transition metal compound (1) having a cyclopentadienyl group per 1 g of the solid, and the treatment temperature is 20 to 200 ° C. The treatment time is not particularly limited, but normally 30 minutes to 6 hours is suitable.

The trivalent titanium compound-containing solid catalyst obtained by treating with the organometallic compound (1) is solid-liquid separated, washed several times with an inert hydrocarbon solvent such as hexane or heptane, and then polymerized. Used for. After solid-liquid separation, wash with a large amount of a halogenated hydrocarbon solvent such as monochlorobenzene or an aromatic hydrocarbon solvent such as toluene at a temperature of 50 to 120 ° C one or more times, and further wash with an aliphatic hydrocarbon solvent such as hexane. It is preferable to repeat washing twice and then use for polymerization in terms of catalytic activity and stereoregularity.

(B) Organoaluminum Compound The organoaluminum compound used in the present invention has at least one Al-carbon bond in the molecule.
A typical one is shown below by a general formula. _{^{R 11 γAlY 3- γ R 12 R}} 13 Al-O-AlR 14 R 15 (R 11 ~R 15 has 1-20 hydrocarbon group having carbon atoms, Y represents halogen, hydrogen or an alkoxy group, gamma is 2 ≦ γ
It is a number represented by ≦ 3. ) Specific examples of the organic aluminum compound include trialkylaluminum, triisobutylaluminum, trialkylaluminums such as trihexylaluminum, diethylaluminum hydride, dialkylaluminum hydrides such as diisobutylaluminum hydride, and dialkylaluminum halides such as diethylaluminum chloride.
Examples thereof include a mixture of trialkylaluminum and dialkylaluminum halide such as a mixture of triethylaluminum and diethylaluminum chloride, and alkylalumoxane such as tetraethyldialumoxane and tetrabutyldialumoxane. Of these organoaluminum compounds, trialkylaluminums, mixtures of trialkylaluminums and dialkylaluminum halides, alkylalumoxanes are preferred, especially triethylaluminum, triisobutylaluminum,
A mixture of triethylaluminum and diethylaluminium chloride and tetraethyldialumoxane are preferred. The amount of the organoaluminum compound to be used can be selected in a wide range such as 0.5 to 1000 mol per 1 mol of titanium atom in the solid catalyst, but the range of 1 to 600 mol is particularly preferable.

(C) Electron-donating compound As the electron-donating compound used in the polymerization in the present invention, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, Examples thereof include oxygen-containing electron donors such as acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonias, amines, nitriles and isocyanates. Of these electron donors, inorganic acid esters and ethers are preferably used.

The inorganic acid ester is preferably one
General formula R¹⁶ _nSi (OR¹⁷)_4-n(R ¹⁶Has 1 to 20 carbon atoms
Hydrocarbon group or hydrogen atom, R¹⁷Has 1 to 20 carbon atoms
R is a hydrocarbon group¹⁶, R¹⁷Are in the same molecule
May have different substituents, and n is 0 ≦ n <4
A silicon compound represented by
it can. Specific examples include tetramethoxysilane and tet
Laethoxysilane, tetrabutoxysilane, tetrafe
Noxysilane, Methyltrimethoxysilane, Ethyltri
Methoxysilane, butyltrimethoxysilane, isobutyl
Rutrimethoxysilane, tert-butyltrimethoxy
Silane, isopropyltrimethoxysilane, cyclohex
Syltrimethoxysilane, phenyltrimethoxysila
Amine, vinyltrimethoxysilane, dimethyldimethoxysilane
Orchid, diethyldimethoxysilane, dipropyldimethoxy
Sisilane, propylmethyldimethoxysilane, diisop
Ropyldimethoxysilane, dibutyldimethoxysilane,
Diisobutyldimethoxysilane, di-t-butyldimethoxy
Silane, butylmethyldimethoxysilane, butylethyl
Dimethoxysilane, tert-butylmethyldimethoxy
Silane, isobutylisopropyldimethoxysilane, t
ert-Butylisopropyldimethoxysilane, hex
Lumethyldimethoxysilane, hexylethyldimethoxy
Silane, dodecylmethyldimethoxysilane, dicyclope
Methyl dimethoxysilane, cyclopentyl methyl dimetho
Xysilane, cyclopentylethyldimethoxysilane,
Cyclopentyl isopropyldimethoxysilane, cyclo
Pentyl isobutyldimethoxysilane, cyclopentyl
-Tert-butyldimethoxysilane, dicyclohexyl
Ludimethoxysilane, cyclohexylmethyldimethoxy
Silane, cyclohexylethyldimethoxysilane, shik
Rohexyl isopropyldimethoxysilane, cyclohexyl
Sylisobutyldimethoxysilane, cyclohexyl-t
ert-Butyldimethoxysilane, cyclohexyl
Lopentyldimethoxysilane, cyclohexylphenyl
Dimethoxysilane, diphenyldimethoxysilane,
Nylmethyldimethoxysilane, phenylisopropyldi
Methoxysilane, phenylisobutyldimethoxysila
Phenyl-tert-butyldimethoxysilane, fluorine
Phenylcyclopentyldimethoxysilane, vinylmethyl
Dimethoxysilane, methyltriethoxysilane, ethyl
Triethoxysilane, butyltriethoxysilane, iso
Butyltriethoxysilane, tert-butyltrieth
Xysilane, isopropyltriethoxysilane, cyclo
Hexyltriethoxysilane, phenyltriethoxysilane
Orchid, vinyltriethoxysilane, dimethyldiethoxy
Silane, diethyldiethoxysilane, dipropyldieto
Xysilane, propylmethyldiethoxysilane, diiso
Propyldiethoxysilane, dibutyldiethoxysilane
Amine, diisobutyldiethoxysilane, di-tert-butane
Tyldiethoxysilane, butylmethyldiethoxysila
Amine, butylethyldiethoxysilane, tert-butyl
Methyldiethoxysilane, hexylmethyldiethoxysilane
Orchid, hexylethyldiethoxysilane, dodecylmethy
Ludiethoxysilane, dicyclopentyldiethoxysila
Amine, dicyclohexyldiethoxysilane, cyclohexyl
Lumethyldiethoxysilane, cyclohexylethyldiene
Toxysilane, diphenyldiethoxysilane, phenyl
Methyldiethoxysilane, vinylmethyldiethoxysilane
, Ethyltriisopropoxysilane, vinyltributo
Xysilane, phenyltri-tert-butoxysila
2-norbornanetrimethoxysilane, 2-norbo
Lunantriethoxysilane, 2-norbornanemethyldi
Methoxysilane, trimethylphenoxysilane, methyl
Examples thereof include triaryloxysilane.

Further, the ethers are preferably dialkyl ethers, general formulas (R ^{18 to} R ²¹ are linear or branched alkyl, alicyclic, aryl, alkylaryl, arylalkyl groups having 1 to 20 carbon atoms, and R ¹⁸ or R ¹⁹ may be hydrogen). Mention may be made of the diether compounds as represented. Specific examples include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dineopentyl ether, dihexyl ether, dioctyl ether, methyl butyl ether, methyl isoamyl ether, ethyl isobutyl 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-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-
2-cyclohexyl-1,3-dimethoxypropane, 2
-Isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,
3-dimethoxypropane etc. can be mentioned.

Of these electron-donating compounds, the general formula R
An organic silicon compound represented by ²² R ²³ Si (OR ²⁴ ) ₂ is particularly preferably used. Here, in the formula, R ²² is a hydrocarbon group having 3 to 20 carbon atoms in which carbon adjacent to Si is secondary or tertiary, specifically, isopropyl group, se
a branched alkyl group such as c-butyl group, tert-butyl group, tert-amyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, cycloalkenyl group such as cyclopentenyl group, phenyl group, tolyl group, etc. Examples thereof include an aryl group. Further, in the formula, R ²³ is a hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group,
Linear alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, isopropyl group, sec-butyl group, t
Examples include branched chain alkyl groups such as ert-butyl group, tert-amyl group, cyclopentyl group, cycloalkyl groups such as cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, aryl groups such as phenyl group and tolyl group. To be Further, in the formula, R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.

Specific examples of the organosilicon compound used as the electron donating compound include diisopropyldimethoxysilane, diisobutyldimethoxysilane,
Ditbutyldimethoxysilane, tert-butylmethyldimethoxysilane, isobutylisopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyltbutyldimethoxysilane, dicyclohexyldimethoxysilane, Cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxy Orchids, phenylmethyl dimethoxysilane, phenyl dimethoxysilane, phenyl isobutyl dimethoxysilane, phenyl -tert-
Butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethyl Examples thereof include ethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

(I) Olefin Polymerization Method The α-olefin applicable to the present invention is an α-olefin having 3 or more carbon atoms, and specific examples of the α-olefin that can be used are propylene, butene-1, and pentene-1. ,
Hexene-1, Heptene-1, Octene-1, Decene-
1, linear monoolefins such as 3-methylbutene-1,3-methylpentene-1,4-methylpentene-
1 and the like, branched monoolefins, vinylcyclohexane and the like. One type of these α-olefins may be used, or two or more types may be used in combination. Of these α-olefins,
It is preferable to carry out homopolymerization with propylene or butene-1, or to carry out copolymerization with a mixed olefin containing propylene or butene-1 as a main component, and to carry out homopolymerization with propylene, or propylene. It is particularly preferable to carry out the copolymerization using a mixed olefin containing as a main component. Further, in the copolymerization in the present invention, two kinds or more kinds of olefins selected from ethylene and the above α-olefins can be mixed and used. Further, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used for the copolymerization. And, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out. As a method of supplying each catalyst component to the polymerization tank,
There are no particular conditions to be restricted except that the gas is supplied in an inert gas such as nitrogen or argon without water. The solid catalyst component (A), the organoaluminum compound (B), and the electron-donating compound (C) may be separately supplied, or any two of them may be contacted in advance and supplied.

In the present invention, the olefin can be polymerized in the presence of the above-mentioned catalyst, but the following pre-polymerization may be carried out before such polymerization (main polymerization). The prepolymerization is carried out in the presence of the solid catalyst component (A) and the organoaluminum compound (B) by supplying a small amount of olefin, and is preferably carried out in a slurry state. Examples of the solvent used for forming a slurry include propane, butane, isobutane, pentane, isopentane,
Inert hydrocarbons such as hexane, heptane, octane, cyclohexane, benzene, toluene can be mentioned. Further, when making a slurry, a liquid olefin can be used in place of part or all of the inert hydrocarbon solvent.

The amount of the organoaluminum compound used in the prepolymerization is 1 mol of titanium atom in the solid catalyst component,
Although it can be selected in a wide range such as 0.5 to 700 mol, 0.8 to 500 mol is preferable, and 1 to 200 mol is particularly preferable. The amount of the olefin to be prepolymerized is 0.01 to 1000 g, preferably 0.05 to 500 g, and particularly preferably 0.1 to 1 g per 1 g of the solid catalyst component.
It is 200 g.

The concentration of the slurry during the prepolymerization is 1 to
500 g-solid catalyst component / l-solvent is preferred, especially 3
~ 300 g-solid catalyst component / l-solvent is preferred. The prepolymerization temperature is preferably −20 to 100 ° C., especially 0 to 8
0 ° C is preferred. The partial pressure of the olefin in the gas phase portion in the prepolymerization is preferably 0.01~20kg / cm ^2, especially 0.1 to 10 / cm ² is preferred, the pressure in the prepolymerization, in liquid at a temperature This is not the case with certain olefins. Further, the prepolymerization time is not particularly limited, but usually 2 minutes to 15 hours is suitable.

When carrying out the prepolymerization, the solid catalyst component (A), the organoaluminum compound (B) and the olefin can be supplied by contacting the solid catalyst component (A) with the organoaluminum compound (B). Any of a method of supplying an olefin and a method of supplying the organoaluminum compound (B) after contacting the solid catalyst component (A) with the olefin may be used. Further, as the olefin supply method, either a method of sequentially supplying olefin while maintaining the inside of the polymerization tank at a predetermined pressure or a method of initially supplying all of a predetermined amount of olefin may be used. good. It is also possible to add a chain transfer agent such as hydrogen in order to adjust the molecular weight of the obtained polymer. Furthermore, when preliminarily polymerizing the solid catalyst component (A) with a small amount of olefin in the presence of the organoaluminum compound (B), an electron donating compound (C) may coexist as necessary. The electron donating compound used is a part of the above electron donating compound (C) or
It's all. The amount used is 0.01 to 400 mol, preferably 0.02 to 200 mol, and particularly preferably 0.03 to 100 mol, based on 1 mol of the titanium atom contained in the solid catalyst component (A). , 0.003 to 5 mol, preferably 0.005 to 3 mol, and particularly preferably 0.01 to 2 mol with respect to the organoaluminum compound (B).

There are no particular restrictions on the method of supplying the electron-donating compound (C) during the prepolymerization, and it may be supplied separately from the organoaluminum compound (A) or may be supplied in contact with it in advance. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization. After performing the prepolymerization as described above,
Alternatively, without prepolymerization, in the presence of the catalyst for α-olefin polymerization consisting of the solid catalyst component (A), the organoaluminum compound (B) and the electron-donating compound (C), the α-olefin main component Polymerization can be carried out.

The amount of the organoaluminum compound used during the main polymerization can be selected within a wide range, such as 1 to 1000 mol, per 1 mol of the titanium atom in the solid catalyst component (A), but is particularly within the range of 5 to 600 mol. Is preferred. The electron-donating compound (C) used in the main polymerization is based on 1 mol of titanium atom contained in the solid catalyst component (A).
0.1 to 2000 mol, preferably 0.3 to 1000 mol, particularly preferably 0.5 to 800 mol, and 0.001 to 5 mol, preferably 0.005 to 3 mol, based on the organoaluminum compound. , Particularly preferably 0.01 to
It is 1 mol.

The main polymerization can be carried out up to -30 to 300 ° C, preferably 20 to 180 ° C. There is no particular limitation on the polymerization pressure, but in general, it is from atmospheric pressure to 100 kg / in terms of being industrial and economical.
A pressure of about cm ² , preferably about ² to 50 kg / cm ² , is adopted. The polymerization system may be either batch system or continuous system. Further, slurry polymerization or solution polymerization with an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, bulk polymerization or gas phase polymerization using a liquid olefin as a medium at the polymerization temperature is also possible. During the main polymerization, it is possible to add a chain transfer agent such as hydrogen in order to control the molecular weight of the polymer.

[0051]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not particularly limited to the following Examples. In the examples, evaluation methods for various physical properties of the polymer are as follows. (1) 20 ° C. xylene-soluble part wt% (hereinafter abbreviated as CXS): polypropylene 5 g, boiling xylene 500 ml
After being completely dissolved in the solution, the temperature is lowered to 20 ° C. and left for 4 hours or more. Then, this was separated by filtration into an extrudate and a solution, and the filtrate was dried and dried at 70 ° C. under reduced pressure. 200 ml of 1 g of polymer powder whose content was determined by measuring its weight
After being dissolved in boiling xylene, slowly cool to 50 ° C, then soak in ice water and cool to 20 ° C with stirring,
After standing for 3 hours, the precipitated polymer is filtered off.
The xylene was evaporated from the filtrate and dried under reduced pressure at 60 ° C to 2
A polymer soluble in xylene at 0 ° C was recovered. (2) Intrinsic viscosity dl / g (hereinafter abbreviated as [η]): Measurement was carried out in 135 ° C. tetralin using an Ubbelohde viscometer. (3) Molecular weight distribution (hereinafter abbreviated as Mw / Mn): By gel permeation chromatography (GPC),
The measurement was performed under the following conditions. The calibration curve was prepared using standard polystyrene. Model Millipore Waters 150 CV type column Shodex M / S 80 Measurement temperature 145 C °, solvent orthodichlorobenzene Sample concentration 5 mg / 8 ml Under these conditions, nbs (National Bure)
Standard of au of Standards)
Reference Material706 (M
w / Mn = 2.1 polystyrene) was measured,
A molecular weight distribution (Mw / Mn) of 2.1 was obtained. (4) Melt flow rate g / 10 minutes (hereinafter abbreviated as MFR): According to JIS K7210, polypropylene was measured by the method of condition-14.

Example 1 (a) Synthesis of organomagnesium compound 10 equipped with stirrer, reflux condenser, dropping funnel and thermometer
After replacing the 00 ml flask with argon, 32.0 g of ground magnesium for Grignard was added. Add 120 g of butyl chloride and 5 parts of dibutyl ether to the dropping funnel.
Charge 00 ml and add about 30 to the magnesium in the flask.
ml was added dropwise to start the reaction. After the reaction was started, the dropping was continued at 50 ° C. for 4 hours, and after the dropping was completed, the reaction was continued at 60 ° C.
The reaction continued for an hour. Then, the reaction solution was cooled to room temperature,
The solid was filtered off. The butylmagnesium chloride in the sampled reaction solution was hydrolyzed with 1N sulfuric acid to give 1
When the concentration was determined by back titration with a normal sodium hydroxide aqueous solution (phenolphthalein was used as an indicator), the concentration was 2.1 mol / liter. (B) Synthesis of solid product After replacing a 500 ml flask equipped with a stirrer and a dropping funnel with argon, 300 ml of hexane, 9.3 ml of tetrabutoxytitanium (9.3 g, 27 mmol) and 91.4 ml of tetraethoxysilane. (85.4g, 4
(10 mmol) was added to make a uniform solution. next,
209 m of the organomagnesium compound solution synthesized in (a)
1 was gradually added dropwise from the dropping funnel over 5 hours while maintaining the temperature in the flask at 20 ° C. After completion of the dropping, the mixture was further stirred at room temperature for 1 hour, then solid-liquid separated at room temperature, washed three times with 270 ml of toluene and once with 98 ml, and then 170 ml of toluene was added. (C) Synthesis of ester-treated solid After replacing a 200 ml flask equipped with a stirrer, a dropping funnel, and a thermometer with argon, the whole amount of the slurry containing the solid product obtained in (b) above was charged, and the supernatant was further collected. Drain the liquid and diisobutyl phthalate 42.4 ml (15
8 mmol) was added and the reaction was carried out at 93 ° C. for 30 minutes. After the reaction, solid-liquid separation was performed, and once with 270 ml of toluene, 122
It was washed once with ml. (D) Synthesis of solid catalyst component (activation treatment) After completion of washing in (c) above, toluene was added to the flask.
2 ml, diisobutyl phthalate 3.06 ml (11.4
Mmol), 5.9 ml (47 mmol) of butyl ether, and 113 ml (1.031 mol) of titanium tetrachloride, and the reaction was carried out at 105 ° C. for 3 hours. After completion of the reaction, solid-liquid separation was performed at the same temperature and then toluene 270 was added at the same temperature.
It was washed twice with ml and once with 122 ml. Then
Toluene 12.0 ml, butyl ether 5.9 ml (4
7 mmol), and 56.8 ml of titanium tetrachloride (0.
518 mol) was added and the reaction was carried out at 105 ° C. for 1 hour.
After completion of the reaction, solid-liquid separation was performed at the same temperature, and then 270 ml of toluene was washed 3 times at the same temperature, and then hexane 245 was used.
It was washed 3 times with ml and once with 86 ml, and dried under reduced pressure to obtain 45.9 g of a solid catalyst component. The solid catalyst component contained 1.3% by weight of titanium atom, 9.6% by weight of phthalic acid ester, 0.6% by weight of ethoxy group, and 0.4% by weight of butoxy group. When the solid catalyst component was observed with a stereoscopic microscope, it had good particle properties without fine powder. (E) Treatment of solid catalyst component with dicyclopentadienyl titanium dichloride dicyclopentadienyl titanium dichloride 0.25
140 ml of toluene was added to g to prepare a uniform solution. Subsequently, 17.4 ml of toluene and 3.48 g of the solid catalyst component obtained in (d) above were added to the flask, and then the toluene solution of dicyclopentadienyltitanium dichloride was added in total, and the temperature was raised to 95 ° C. 95 more
It was heated for 1 hour while maintaining the temperature. Then, heat filtration,
The solid catalyst component 3. was washed with 18 ml of toluene 3 times and with 18 ml of hexane 3 times at 95 ° C., and further dried under reduced pressure.
29 g were obtained. In the solid catalyst component, titanium atoms are 1.
The content was 93% by weight, phthalic acid ester was 8.7% by weight, ethoxy group was 0.46% by weight, and butoxy group was 0.27% by weight. (F) Polymerization of Propylene A 3 liter stirring type autoclave made of stainless steel was replaced with argon, 2.6 mmol of triethylaluminum, 0.26 mmol of cyclohexylethyldimethoxysilane and 10.1 mg of a solid catalyst component synthesized in (e).
Was charged, and hydrogen corresponding to a partial pressure of 2.0 kg / cm ² was added. Next, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C, and polymerization was carried out at 80 ° C for 1 hour. After the polymerization was completed, unreacted monomers were purged. The resulting polymer was dried under reduced pressure at 60 ° C. for 2 hours,
4 g of polypropylene powder was obtained. Therefore, the yield of polypropylene per 1 g of the solid catalyst component (hereinafter referred to as PP
/ Cat) is PP / Cat = 15,200 (g
/ G). Further, the ratio of the components soluble in 20 ° C. xylene to the total polymer yield is CXS = 1.0 (wt%), the intrinsic viscosity of the polymer is [η] = 2.18 dl / g,
Mw / Mn = 10.4, powder bulk density is 0.449
It was g / cm ³ .

Comparative Example 1 In the polymerization of propylene of Example 1 (f), 12.6 mg of the solid catalyst component obtained in (d) above was used and 0.3
Polymerization of propylene was carried out in the same manner except that hydrogen corresponding to a partial pressure of 3 kg / cm ² was added. The polymerization result is PP
/ Cat = 31,800 (g / g), CXS = 1.20
(Wt%), [η] = 1.80 dl / g, Mw / Mn =
The powder had a bulk density of 0.452 g / cm ³ . This comparative example has a narrower molecular weight distribution than the present invention because the solid catalyst component of the present invention was not polymerized.

[0054]

According to the present invention, an α-olefin polymer having a wide molecular weight distribution and high stereoregularity is provided.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding 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.

Claims (3)

[Claims] By treatment with claim 1] (A) a trivalent titanium compound-containing solid catalyst component organic transition metal compound having a cyclopentadienyl group represented by the following formula (1), the resulting solid catalyst component Cp _m MX _n R _p (1) (wherein Cp represents a substituted or unsubstituted cyclopentadienyl group, M represents a Group 4 transition metal, X represents a halogen atom, R represents an alkyl group, aryl) Group or O, N,
An alkyl group and an aryl group containing S and P atoms are shown. Further, m, n, and p are integers that satisfy the following formula.
1 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 ≦ p ≦ 3, m + n + p =
4), (B) an organoaluminum compound, and (C) an electron-donating compound. 2. A trivalent titanium compound-containing solid catalyst component,
In the presence of an organosilicon compound having a Si—O bond, the general formula Ti (OR ¹ ) _a X _4-a (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is 0 <a. The solid product obtained by reducing the titanium compound represented by ≤4) with an organomagnesium compound is treated with an ester compound, and then a mixture of an ether compound and titanium tetrachloride or an ether compound and a tetrachloride. The catalyst system for α-olefin polymerization according to claim 1, which is a trivalent titanium compound-containing solid catalyst component obtained by treating with a mixture of titanium chloride and an ester compound. 3. A method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using the catalyst system for α-olefin polymerization according to claim 1 or 2.