JPH0796567B2 - Method for polymerizing α-olefin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for polymerizing α-olefin, and more particularly to a method capable of producing poly α-olefin having excellent stereoregularity with high catalytic activity. More specifically,
The present invention relates to a method for polymerizing α-olefin by using a highly active α-olefin prepolymerization catalyst having excellent stereoregularity, which is capable of achieving higher activation without lowering the stereoregularity.

[Prior Art] A method for producing crystalline polyolefin by polymerizing α-olefin such as propylene or 1-butene in the presence of a stereoregular catalyst is proposed and known in many prior arts.
Among these polymerization methods, from (a) a highly active titanium solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organometallic compound catalyst component and (c) an electron donor catalyst component. Many prior art methods have also been proposed in which a highly stereoregular polymer can be obtained with high catalytic activity by polymerizing α-olefin in the presence of a catalyst to be formed. It has been adopted on an industrial scale as an excellent polymerization method that does not require the removal of catalyst and amorphous polymer from the coalescence. However, even in this technical field, there is a great demand for a rationalization technique, and a further highly activated polymerization technique is required.

On the other hand, the applicant has already disclosed in Japanese Patent Publication No. 57-31726 that the titanium catalyst component and the periodic table No. 1 obtained by treating a magnesium-halogen compound / titanium-halogen compound complex with an organic acid ester and a titanium compound. Proposed is a method of polymerizing α-olefin in the presence of an organometallic compound of Group 3 to Group 3 metal, and Japanese Patent Publication No. 56-45403 discloses a method in which a titanium compound is added in the presence of a magnesium halogen compound / titanium halogen compound complex. A catalyst comprising a solid catalyst component (A) obtained by reacting an organometallic compound of a metal of Group 1 to 3 of the periodic table and an organometallic compound component (B) of a metal of Group 1 to 3 of the periodic table We propose a method to polymerize olefins in the presence. However, all of these methods have low polymerization activity and stereoregularity, and there is a demand for a polymerization method having more excellent performance.

[Problems to be Solved by the Invention] The inventors of the present invention recognize that the technology in the field of polymerization of α-olefin is in the above situation, and have conventionally proposed (a) magnesium, titanium, halogen and A highly active solid titanium catalyst component containing an electron donor as an essential component, (b)
In a method of polymerizing α-olefin in the presence of a catalyst formed from a catalyst component of an organometallic compound and a catalyst component of an electron donor (c), further achieving high activation of the catalyst without reducing stereoregularity. As a result of diligent study on a method capable of producing α-olefin, at least (A) a highly active titanium solid catalyst component, (B) an organometallic compound catalyst component, and (C) an organohalogen compound catalyst component are present in the presence of a catalyst. The inventors have found that the above object can be achieved by polymerizing α-olefin in the presence of a catalyst obtained by prepolymerization, and have reached the present invention.

[Means for Solving Problems] and [Action] According to the present invention, at least (A) a highly active solid titanium catalyst component containing magnesium, titanium and halogen as essential components, (B) Group 1 of the periodic table To a Group 3 metal organometallic compound catalyst component, and (C) organohalogen compound catalyst component, provided that the ratio of the halogen atom X of the component (C) to 1 gram atom of titanium of the component (A) is 0.1 to 10. Characterized in that α-olefin is prepolymerized in the presence of a catalyst formed in the range of gram atoms, and α-olefin is polymerized in the presence of the resulting α-olefin prepolymerization catalyst. A method of polymerizing alpha-olefin is provided.

Hereinafter, the present invention will be described in detail.

In the present invention, the term “polymerization” may be used to include not only homopolymerization but also copolymerization, and the term “polymer” may be used to include not only homopolymer but also copolymer. .

The titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium and halogen as essential components and a specific electron donor described later as an optional component. The titanium catalyst component (A) is compared to a commercially available magnesium halide, containing a small magnesium halide microcrystals, typically, a specific surface area of from about 3m ² / g or more, preferably about 40 to about 1000 m ² / g, more preferably about 80 to about
The composition does not change substantially by washing with hexane at room temperature of about 800 m ² / g. In the titanium catalyst component (A), the halogen / titanium (atomic ratio) is about 5
To about 200, especially about 5 to about 100, and the electron donor / titanium (molar ratio) described below is about 0.1 to about 10, especially about 0.2.
To about 6, and the magnesium / titanium (atomic ratio) is about 2 to about 100, particularly about 4 to about 50. The component (A) may also contain other electron donors, metals, elements, functional groups and the like. It may also contain organic or inorganic diluents such as silicon compounds, aluminum and polyolefin.

Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), optionally an electron donor and a titanium compound,
In some cases, other reaction reagents such as silicon, phosphorus,
Compounds such as aluminum can be used.

As a method for producing such a titanium catalyst component (A),
For example, JP-A-50-108385, 50-126590, 51-
20297, 51-28189, 51-64586, 51-92885
No. 51, No. 51-136625, No. 51-87489, No. 52-100596
No. 52-147688, No. 52-104593, No. 53-2580,
53-40093, 53-43094, 55-135102, 56
-135103, 56-811, 56-11908, 56-1860
No. 6, 58-83006, 58-138705, 58-138706
No. 58, No. 58-138707, No. 58-138708, No. 58-138709
No. 58, No. 58-138710, No. 58-138715, No. 60-23404
No. 61-21109, No. 61-37802, No. 61-37803,
It can be manufactured according to the method disclosed in each publication such as JP-A 55-152710. Some examples of the method for producing the titanium catalyst component (A) will be briefly described below.

(1) An electron donor and / or an organoaluminum compound, which is crushed or not crushed with or without a magnesium compound or a complex compound of a magnesium compound and an electron donor in the presence or absence of an electron donor, a grinding aid, or the like. It is pretreated with a reaction aid such as a halogen-containing silicon compound or is reacted with a titanium compound that forms a liquid phase under the reaction conditions with the solid obtained without pretreatment.

(2) A liquid titanium compound having no reducing ability is reacted with a liquid titanium compound in the presence or absence of an electron donor to precipitate a solid titanium complex.

(3) A titanium compound is reacted with the material obtained in (2).

(4) An electron donor and a titanium compound are reacted with those obtained in (1) and (2).

(5) A magnesium compound or a complex compound of a magnesium compound and an electron donor is ground in the presence or absence of an electron donor, a grinding aid, etc., and in the presence of a titanium compound to obtain an electron donor and / or an organic compound. Pretreatment with a reaction aid such as an aluminum compound or a halogen containing silicon compound, or the solid obtained without pretreatment is treated with halogen or a halogen compound or an aromatic hydrocarbon.

(6) The compound obtained in (1) to (4) above is treated with halogen or a halogen compound or an aromatic hydrocarbon.

Among these preparation methods, it is preferable to use a liquid titanium halide in the catalyst preparation, or to use a halogenated hydrocarbon after or after using the titanium compound.

Examples of the electron donor that can be a constituent of the highly active titanium catalyst component (A) of the present invention include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, Oxygen-containing electron donors such as acid anhydrides, ammonia, amines, nitriles,
Examples thereof include nitrogen-containing electron donors such as isocyanate.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-
C1-C18 alcohols such as ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, C6 which may have alkyl group such as nonylphenol and naphthol
To 25 phenols; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc., having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde, etc., having 2 to 15 carbon atoms Aldehydes of methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di2-di-1,2-cyclohexanedicarboxylate
Ethylhexyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate, Organic acid esters having 2 to 30 carbon atoms, including the following esters, which are preferably contained in titanium catalyst components such as dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; Inorganic acid esters such as ethyl silicate, butyl silicate, vinyltriethoxysilane, phenyltriethoxysilane, and diphenyldiethoxysilane; acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthalic acid dichloride, etc. C2 to C15 acid halides; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether; acetic acid amide, benzoic acid amide, toluyl Acid amides such as acid amides; acid anhydrides such as benzoic anhydride and phthalic anhydride; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine ;
Nitriles such as acetonitrile, benzonitrile, tolunitrile; and the like can be mentioned. Two or more kinds of these electron donors can be used.

The electron donor that is preferably contained in the titanium catalyst component is an ester, and more preferred is a compound represented by the general formula: (Here, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ , R ⁶
Is hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. R ³ and R ⁴ may be connected to each other. the above
The substituted hydrocarbon group represented by R ^{1 to} R ⁶ includes a heteroatom such as N, O and S, and is, for example, C—O—C, COOR, COOH,
It has a group such as OH, SO ₃ H, —C—N—C—, and NH ₂ . And a skeleton represented by

Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms.

Specific examples of preferable polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methyl glutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, isopropyl diethyl malonate. ,
Diethyl butyl malonate, diethyl phenylmalonate,
Diethyl malonate diethyl, allyl malonate diethyl,
Diisobutyl diethyl malonate, Dinormal butyl malonate diethyl, dimethyl maleate, monooctyl maleate, dioctyl maleate, dibutyl maleate,
Dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methyl glutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctyl citraconic acid, aliphatic polycarboxylic acids such as dimethyl citraconic acid Acid ester, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate,
Aliphatic polycarboxylic acid esters such as diethyl tetrahydrophthalate and diethyl nadicuate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, mononormal butyl phthalate, diethyl phthalate, ethyl phthalate Isobutyl, ethyl normal butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-phthalate
Aromatic polyenes such as 2-ethylhexyl, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate. Examples thereof include carboxylic acid esters and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Specific examples of preferable polyhydric hydroxy compound esters include 1,2-diacetoxybenzene and 1-
Examples thereof include methyl-2,3-diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol dipivalate and butanediol pivalate.

Examples of the ester of hydroxy-substituted carboxylic acid include benzoylethyl salicylate, acetylisobutyl salicylate, acetylmethyl salicylate and the like.

Other examples of the polycarboxylic acid ester that can be supported in the titanium catalyst component include diethyl adipate,
Diisobutyl adipate, diisopropyl sebacate,
Examples thereof include long-chain dicarboxylic acid esters such as n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexane sebacate.

Among these polyfunctional esters, those having a skeleton represented by the above-mentioned general formula are preferable, and more preferable are esters of phthalic acid, maleic acid, substituted malonic acid and the like and alcohols having 2 or more carbon atoms. Particularly preferred is a diester of phthalic acid and an alcohol having 2 or more carbon atoms.

Another electron donor component that can be supported on the titanium catalyst component is RCOOR '(R and R'are hydrocarbyl groups which may have a substituent, at least one of which is a branched chain (alicyclic group). Included) or a ring-containing chain-like group). For example the R and / or _{R ', (CH 3) 2} CH-, C 2 H 5 CH (CH 3) -, (CH 3)
_{2 CHCH 2 -, (CH 3} ) 3 C-, C 2 H 5 CH (CH 3) CH 2 -, It may be a group such as. If either R or R'is a group as described above, the other may be a group as described above,
Alternatively, it may be another group, for example, a linear or cyclic group.

Specifically, various monoesters of dimethylacetic acid, trimethylacetic acid, α-methylacetic acid, β-methylbutyric acid, methacrylic acid, benzoylacetic acid, etc., various monocarboxylic acids of alcohols such as isopropanol, isobutyl alcohol, tert-butyl alcohol, etc. An ester can be illustrated.

Carbonates can also be selected as electron donors. Specifically, diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate, etc. can be illustrated.

When carrying these electron donors, it is not always necessary to use them as starting materials, and it is necessary to use compounds that can be changed to these during the preparation process of the titanium catalyst component and convert them into these compounds at the stage of the preparation. Good.

Other electron donors may coexist in the titanium catalyst component, but if they coexist in too large an amount, it will have an adverse effect and should be suppressed to a small amount.

In the present invention, the magnesium compound used for preparing the solid titanium catalyst component (A) is a magnesium compound with or without reducing ability. As an example of the former, a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond, such as dimethylmagnesium,
Diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl Examples include magnesium hydride. These magnesium compounds can also be used in the form of complex compounds with, for example, organic aluminum,
It may be in a liquid state or a solid state. On the other hand, examples of magnesium compounds having no reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; magnesium methoxy chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy. Alkoxy magnesium halides such as magnesium chloride; Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride; Alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium Magnesium; Aryloxymag like phenoxymagnesium, dimethylphenoxymagnesium Siumu; magnesium laurate, and the like can be exemplified carboxylates of magnesium such as magnesium stearate. Further, the magnesium compound having no reducing ability may be derived from the above-mentioned magnesium compound having reducing ability or may be one derived at the time of preparation of the catalyst component. For example, there may be mentioned a method in which a magnesium compound having a reducing ability is brought into contact with a compound such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester or an alcohol to convert it into a magnesium compound having no reducing ability. Further, the magnesium compound may be a complex compound with another metal, a double compound, or a mixture with another metal compound. Further, it may be a mixture of two or more kinds of these compounds. Among these, preferred magnesium compounds are compounds having no reducing ability, and particularly preferred are halogen-containing magnesium compounds, especially magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride.

In the present invention, there are various titanium compounds used for the preparation of the solid titanium catalyst component (A).
gX _{4- g} (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦ 4)
A tetravalent titanium compound represented by is preferable. More specifically, tetrahalogenated titanium such as TiCl ₄ , TiBr ₄ , Til ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , T
Trihalogenated alkoxy titanium such as i (OC ₂ H ₅ ) Br ₃ and Ti (OisoC ₄ H ₉ ) Br ₃ ; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On
_{-C 4 H 9) 2 Cl 2} , Ti (OC 2 H 5) dihalogenated alkoxy titanium such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On-C ₄ H ₉ )
Mono-halogenated trialkoxy titanium such as ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; tetra such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ and Ti (On-C ₄ H ₉ ) ₄ Alkoxy titanium etc. can be illustrated. Of these, preferred are halogen-containing titanium compounds, especially titanium tetrahalides, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be diluted with a hydrocarbon, a halogen hydrocarbon or the like.

In the preparation of the titanium catalyst component (A), a titanium compound,
The amount of the magnesium compound, the electron donor to be supported, and the electron donor that may be optionally used, such as alcohol, phenol, monocarboxylic acid ester, silicon compound, and aluminum compound, depends on the preparation method. Although different and cannot be specified unconditionally, for example, the ratio can be 0.05 to 5 mol of electron donor to be supported and 0.05 to 500 mol of titanium compound per mol of the magnesium compound.

The halogen atom constituting the titanium catalyst component may be fluorine, chlorine, bromine, iodine or a mixture thereof, and chlorine is particularly preferable.

When the titanium solid catalyst component (A) contains an electron donor in the method of the present invention, a polymer having particularly excellent stereoregularity can be obtained by the polymerization method of the present invention.

In the present invention, the titanium solid catalyst component (A) as described above, an organometallic compound catalyst component of a metal of Groups 1 to 3 of the periodic table, such as an organoaluminum compound catalyst component (B) and the after-mentioned (C). Olefin polymerization or copolymerization is carried out using a combination catalyst of the components.

The organometallic compound catalyst component (B) of a metal of Groups 1 to 3 of the Periodic Table includes (i) at least one in the molecule.
An organoaluminum compound having an Al-carbon bond, for example, a general formula R ¹ mAl (OR ² ) nHpXq (wherein R ¹ and R ² are carbon atoms, usually a hydrocarbon group containing 1 to 15, preferably 1 to 4). And may be the same or different from each other.

X is a halogen, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q is a number 0 ≦ q <3, and m +
n + p + q = 3), and (ii) a general formula M ¹ ▲ AlR ¹ ₄ ▼ (wherein M ¹ is Li, Na, K, R ¹ is the same as above) A complex alkylated product of a Group 1 metal and aluminum, (iii) a group represented by the general formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, M ² is Mg, Zn, Cd) Examples thereof include dialkyl compounds of Group 2 metals.

Examples of the organoaluminum compound belonging to (i) above include the following. General formula ▲ R ¹ _m A ▼ l (OR ² ) _3- m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m <3), a general formula R ¹ AlX _3- m (where R ¹ is the same as above, X is a halogen, and m is preferably 0 <m <3), a general formula R ¹ AlH _3- m (where R ¹ is the same as above. M is preferably 2 ≦ m <3), the general formula R ¹ mAl (OR ² ) nXq (wherein R ¹ and R ² are the same as above. X Is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

In the aluminum compound belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum, trialkenyl aluminum such as triisoprenyl aluminum, diethyl aluminum ethoxide, dialkyl aluminum alkoxide such as dibutyl aluminum butoxide, ethylaluminum sesquichloride ethoxide, in addition to alkylaluminum sesqui alkoxides such as butyl sesquichloride _{^{butoxide, ▲ R 1 2 · 5 ▼}} Al partially alkoxylated with an average composition represented by like (OR ²⁾ _{0 · 5} Alkyl aluminum, diethyl aluminum chloride, dibutyl aluminum chloride, dialkyl aluminum halogenide such as diethyl aluminum bromide, ethyl acetate Partial halogenation of alkyl aluminum sesquihalogenides such as minium sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, alkyl aluminum dihalogenides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc. Alkyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydride such as dibutyl aluminum hydride, ethyl aluminum dihydride, partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as propyl aluminum dihydride, ethyl aluminum ethoxy chloride, Butyl Aluminum Butoxy Cyclolide, Ethyl Aluminum Ethoxy Broth De is a partially alkoxylated and halogenated alkylaluminum such as.

Compounds belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiA
Examples of l (C ₇ H ₁₅ ) _{4 and the} like, and examples of the compound belonging to (iii) above include diethylzinc and diethylmagnesium. Alkyl magnesium halides such as ethyl magnesium chloride can also be used. Among these, trialkylaluminum, alkylaluminum halide, and mixtures thereof are particularly preferable.

Examples of the organohalogen compound catalyst component (C) that can be used in the present invention include organohalogen compounds composed of a hydrocarbon group having 1 to 20 carbon atoms and a halogen group such as chlorine, bromine, iodine or fluorine. You can

More specifically, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, propyl fluoride, isopropyl fluoride, n-propyl chloride, isopropyl chloride, n-propyl bromide, odor Isopropyl chloride,
Isopropyl iodide, n-butyl chloride, sec-butyl chloride, isobutyl chloride, tert-butyl chloride, tert-butyl bromide, tert-butyl iodide, n-amyl chloride, activated amyl chloride, isoamyl chloride, tert-amyl chloride , Neopentyl chloride, isoamyl bromide, tert-amyl bromide, n chloride
Alkyl halides such as hexyl, hexyl bromide, heptyl chloride, octyl chloride, decyl chloride, vinyl chloride, vinyl bromide, vinyl iodide, 1-propenyl chloride,
Unsaturated monohalogen derivatives such as isopropenyl chloride and isopropenyl bromide, methylene chloride, methylene bromide, methylene iodide, ethylidene chloride, ethylene chloride, propylidene dichloride, propylene dichloride, isopropylidene dichloride, isopropyl dibromide Saturated dihalogen derivatives such as lidene, 1,2-dichlorobutane, 1,3-dichlorobutane, pentamethylene dichloride, hexamethylene dichloride, vinylidene dichloride, unsaturated dihalogen derivatives such as 1,2-dichloroethylene, other chloroform, Polyhalogen derivatives such as trichloropropane and carbon tetrachloride can be exemplified. Among these organic halogen compounds, chlorides are preferable, and branched-chain hydrocarbon group-containing chlorides are particularly preferable.

In the present invention, (A) a highly active titanium solid catalyst component containing magnesium, titanium and halogen as essential components, (B) an organometallic compound catalyst component of a metal of Groups 1 to 3 of the periodic table, and (C) In addition to the organic halogen compound catalyst component, a catalyst component (D) consisting of an organic silicon compound or amines having large steric hindrance can be optionally used.

Among the catalyst components [D] used in the present invention, the organic silicon compound generally has a Si—O—C or Si—N—C bond and is, for example, an alkoxysilane or an aryloxysilane. As an example of this,
Formula RnSi (OR ¹ ) _4- n (wherein 0 ≦ n ≦ 3, R is a hydrocarbon group,
For example, alkyl group, cycloalkyl group, aryl group, alkenyl group, haloalkyl group, aminoalkyl group, etc.
Or halogen, R ¹ is a hydrocarbon group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkoxyalkyl group, etc., provided that n R and (4-n) OR ¹
The groups may be the same or different. ) And a silicon compound represented by Other examples include siloxanes having an OR ¹ group and silyl esters of carboxylic acids. Another example is a compound in which two or more silicon atoms are bonded to each other via an oxygen or nitrogen atom. The above-mentioned organosilicon compound is converted into a compound having a Si-O-C bond by previously reacting a compound having no Si-O-C bond with a compound having an O-C bond, or by reacting at a polymerization site. You may use it. As such an example, for example, a halogen-containing silane compound or silicon hydride having no Si-O-C bond, an alkoxy group-containing aluminum compound, an alkoxy group-containing magnesium compound, other metal alcoholate, alcohol, formic acid ester, ethylene oxide, etc. A combination can be exemplified. The organosilicon compound may also contain other metals (eg, aluminum, tin, etc.).

More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, Diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o
-Tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane, bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, Methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane. , Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-
Norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,
Examples include trimethylphenoxysilane, methyltriallyloxysilane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, and dimethyltetraethoxydisiloxane, and especially ethyltriethoxysilane and n-propyltriethoxysilane. , T-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyl. Dimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2
-Norbornanemethyldimethoxysilane, diphenyldiethoxysilane, ethyl silicate and the like are preferable.

Further, as the amines having large steric hindrance, 2,2,6,6
-Tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, derivatives thereof, tetramethylmethylenediamine and the like are preferable. The component (D) can also be used in the form of other compounds and addition compounds.

When the catalyst component (D) is used in the polymerization method of the present invention, a polymer having particularly high stereoregularity can be obtained with higher activity from α-olefin having 3 or more carbon atoms such as propylene.

The catalyst used in the method for polymerizing olefin according to the present invention is α-olefin prepolymerization in the presence of a catalyst formed from at least component (A), component (B), component (C) and optionally component (D). And the resulting α-olefin prepolymerization catalyst. In the method of the present invention, the following method can be exemplified as a method for forming the α-olefin prepolymerization catalyst.

[1] A catalyst is formed by previously contacting the component (A), the component (B), the component (C) and optionally the component (D) in an inert medium, and then contacting with α-olefin. Thereby forming an α-olefin prepolymerization catalyst.

[2] Contacting component (A), component (B), component (C) and optionally component (D) in the presence of α-olefin, if necessary in an inert medium or in an α-olefin medium. A method of forming an α-olefin prepolymerization catalyst by

[3] After the component (A), the component (B), the component (C), and optionally the component (D) are contacted with each other in advance to form a catalyst, if necessary, in an inert medium or α- A method of forming an α-olefin prepolymerization catalyst by contacting with α-olefin in an olefin medium.

In the method of the present invention, component (A), component (B),
When the catalyst is formed by contacting the component (C) and optionally the component (D) in the absence of α-olefin, the temperature during the contact treatment is usually -50 to 100 ° C, preferably -20 to The temperature is 30 ° C., and the time required for the contact treatment is usually 1 minute to 10 hours, preferably 5 minutes to 2 hours. The contacting treatment is optionally carried out in the absence of the α-olefin component, in an inert medium, and when contacted in an inert medium, the catalyst is formed in suspension. If the catalyst is formed in suspension, the catalyst suspension can be used as it is for the prepolymerization of α-olefin, and the catalyst formed can be separated from the suspension. It can also be used for prepolymerization of α-olefin.

Further, in the method of the present invention, as described above, the component (A), the component (B), the component (C) and optionally the component (D) are added in the presence of α-olefin as an inert medium, if necessary. By contacting in medium or in α-olefin medium,
The formation of the catalyst and the formation of the α-olefin prepolymerization catalyst can be carried out simultaneously or sequentially.

In the method of the present invention, the component (A), the component (B) during the formation of the catalyst or the α-olefin prepolymerization catalyst,
The ratio of each component of the component (C) and optionally the component (D) is as follows. The ratio of the metal atom M ₁ of the component (B) to 1 gram atom of titanium of the component (A) is usually 1 to 10.
It is in the range of 0 gram atom, preferably 2 to 30 gram atoms, and the ratio of the halogen atom X of the component (C) to 1 gram atom of titanium of the component (A) is usually 0.
It is in the range of 1 to 10 gram atom, preferably 0.3 to 3 gram atom, and the ratio of component (D) to 1 gram atom of titanium of component (A) is usually 0.3 to 30 mol, preferably 0.7 to 5 mol. Is.

In the method of the present invention, the prepolymerization is carried out in an amount of 0.5 to 500 g, preferably 1 to 100 g, and more preferably 2 to 10 g of α-gram per gram of the high activity titanium solid catalyst component (A).
This is done by polymerizing olefins. As the α-olefin used in the prepolymerization, ethylene and α-olefin having 3 to 20 carbon atoms, such as propylene,
Examples thereof include 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and propylene is preferable.

The prepolymerization temperature is in the range of -20 ° C to 70 ° C, preferably -10 ° C to 60 ° C, more preferably 0 ° C to 50 ° C. The time required for prepolymerization is usually 0.5 to 20 hours,
It is preferably 1 to 10 hours.

The prepolymerization may be carried out batchwise or continuously, and may be carried out under normal pressure or under pressure. In the prepolymerization, a molecular weight modifier such as hydrogen may coexist, but the intrinsic viscosity [η] measured in decalin of at least 135 ° C is 0.2 dl / g or more, preferably 0.5 to 20 dl / g It is better to limit the amount to be manufactured.

The prepolymerization is carried out without solvent or in an inert medium. From the viewpoint of operability, prepolymerization in an inert hydrocarbon medium is preferred. As the inert hydrocarbon medium used in the prepolymerization, the above-mentioned solvents can be exemplified.

In the prepolymerization, the concentration of the solid catalyst in the prepolymerization reaction system is usually 10 as the concentration of the transition metal atom in the solid catalyst.
^-6 to 1 gram atom / l, preferably 10 ^-4 to 10 ^-2 gram atom / l.

In the method of the present invention, the formation of the catalyst or the α-
Inert media that may be used in forming the olefin prepolymerization catalyst include ethane, propane, butane, pentane, methylpentane, hexane, heptane,
Octane, decane, gasoline, kerosene, aliphatic hydrocarbons such as light oil, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, benzene, toluene, aromatic hydrocarbons such as xylene can be exemplified. It is also possible to use an inert medium consisting of a mixture of two or more of these. Similarly, as the α-olefin medium, the α-olefin described as the α-olefin for prepolymerization can be similarly exemplified.

In the α-olefin polymerization method of the present invention, the α-olefin prepolymerization catalyst is formed in a suspension state by the above-mentioned prepolymerization. The suspension can be used as it is, or the catalyst produced from the suspension can be separated and used.

The α-olefin prepolymerization catalyst obtained by the above-mentioned prepolymerization exhibits excellent polymerization activity in the polymerization of α-olefin.

The olefins used for polymerization in the method of the present invention include ethylene, propylene, 1-butene, 4-methyl-
1-Pentene, 1-octene and the like, which can be subjected to not only homopolymerization but also random copolymerization or block copolymerization. Upon copolymerization, polyunsaturated compounds such as conjugated dienes and non-conjugated dienes can be selected as the copolymerization component. Among these olefins, homopolymerization of propylene or 1-butene or 4-methyl-1-pentene or a mixed component of these olefins and other olefins containing propylene or 1-butene as a main component (for example, 50 mol) % Or more, preferably 70 mol% or more) It is preferable to apply the method of the present invention to the polymerization or copolymerization of mixed olefins.

In the process of the present invention, the olefin polymerization is carried out in the gas phase or in the liquid phase, for example in the form of a slurry. In the slurry polymerization, an inert hydrocarbon may be used as the solvent, or olefin itself may be used as the solvent.

In the method of the present invention, the polymerization of α-olefin is carried out by the above α
Carried out in the presence of olefin prepolymerization catalysts. In the polymerization reaction, it is possible to use only the above α-olefin prepolymerization catalyst, or in addition to the above α-olefin prepolymerization catalyst, any one of the components (B), (C) and (D) It can be carried out by adding two, three or three components.

In the method of the present invention, the proportion of each catalyst component present in the polymerization reaction system is about 0.001 to about 0.5 milligram atom / l in terms of Ti atom for the catalyst component (A), and particularly about
0.005 to about 0.5 milligram atom / l, and for the catalyst component (B), about 1 gram atom of titanium atom in the catalyst component (A) to about 1 metal atom in the component (B).
To about 2000 gram atoms, preferably about 5 to about 500
The catalyst component (D) has a range of about 0.1 to about 500 mol, preferably about 0.5 to about 500 mol, per 1 gram atom of titanium atom in the catalyst component (A). It is in the range of 100 moles.

When the catalyst component (B) is additionally added to the α-olefin prepolymerization catalyst in the polymerization reaction, the ratio of the component (B) is 1 g atom of titanium atom in the catalyst component (A). In contrast, the metal atom in the component (B) is about 1
To about 2000 gram atoms, preferably in the range of about 10 to about 500 gram atoms. Similarly, when the catalyst component (D) is added and polymerized in addition to the α-olefin prepolymerization catalyst, the addition ratio of the component (D) is 1 gram atom of titanium in the catalyst component (A). About 0 to
It is in the range of 1000 mol, preferably about 0 to about 100 mol.

The olefin polymerization temperature is preferably about 20 to about 200 ° C,
More preferably about 50 to about 180 ° C. or so, the pressure is atmospheric pressure to about 100 kg / cm ^2, preferably carried out preferably from about 2 to about 50 kg / cm ² about pressure conditions, polymerization, batchwise,
It can be carried out by either a semi-continuous method or a continuous method. It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

[Effect of the Invention] In the present invention, a polymer having a high stereoregularity index can be produced with high catalyst efficiency, particularly when applied to stereoregular polymerization of α-olefin having 3 or more carbon atoms. In relation to higher activity, the polymer yield per unit solid catalyst component is superior to the conventional proposals at the level of obtaining a polymer with the same stereoregularity index, so that It is possible to reduce the content of the catalyst residue, particularly the halogen content, and it is possible to omit the catalyst removal operation, and it is possible to significantly suppress the rusting tendency of the mold during molding.

Example Next, an example will be described in more detail.

Example 1 [Preparation of solid Ti catalyst component [A]] Anhydrous magnesium chloride 7.14 g (75 mmol), decane 38 ml and 2-ethylhexyl alcohol 35.1 ml (225 mmol) were added to 1 part.
After heating reaction at 30 ℃ for 2 hours to make a homogeneous solution, 1.7g (11.3mmol) of phthalic anhydride was added to this solution.
The mixture is further stirred and mixed for 1 hour to dissolve phthalic anhydride in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 200m of titanium tetrachloride kept at -20 ° C
A total amount of 1 (1.8 mmol) is added dropwise over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C over 4 hours, and when it reached 110 ° C, diisobutyl phthalate was added.
5.03 ml (18.75 mmol) is added and the mixture is kept at the same temperature for 2 hours with stirring. After the completion of the reaction for 2 hours, the solid portion was collected by heating, the solid portion was resuspended in 275 ml of TiCl ₄ , and then the reaction was carried out by heating again at 110 ° C. for 2 hours. After completion of the reaction, the solid portion is again collected by heating, and the solid portion is thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound is detected in the washing liquid. The catalyst component [A] is stored as a hexane slurry in the solid Ti synthesized by the above manufacturing method, and the slurry concentration of the catalyst is also measured. The composition of the solid Ti catalyst component [A] obtained by drying a part of the above is 2.4% by weight of titanium, 56% by weight of chlorine, and 19% of magnesium.
% By weight and 13.6% by weight of isobutyl phthalate.

[Pretreatment of Ti catalyst component [A]] In a 400 ml four-necked glass reactor equipped with a stirrer, 100 ml of purified hexane, 1.0 mmol of triethylaluminum, 2 mmol of diphenyldimethoxysilane, 0.5 mmol of tert-butyl chloride and the above were added in a nitrogen atmosphere. After adding 2.0 g of solid Ti catalyst component [A], at a temperature of 20 ° C, 3.2 Nl / Hr
Propylene was fed to the reactor at a rate of 1 hour for 1 hour.
When the supply of propylene was completed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removing the supernatant liquid and adding purified hexane was performed twice, and then resuspended in purified hexane to transfer the entire amount to a catalyst bottle. Liquor At this time, the total capacity was measured together with the catalyst slurry concentration.

[Polymerization] 750 ml of purified hexane was charged into an autoclave having an internal volume of 2 l, and 0.75 mmol of triethylaluminum, 0.075 mmol of diphenyldimethoxysilane and 0.075 mmol of diphenyldimethoxysilane in the propylene atmosphere at 60 ° C. and the pretreatment product of the catalyst component [A] were treated with titanium atoms. Converted to 0.0075 mmol (converted to the catalyst component [A] above was 22.8
Equivalent to milligrams) was added. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and propylene polymerization was carried out for 2 hours.
The pressure during the polymerization was kept at 7 kg / cm ² G.

After the completion of the polymerization, the slurry containing the produced polymer was passed through to separate the white powdery polymer and the liquid phase part. The yield of the white powdery polymer after drying was 334.5 g, the extraction residual rate with boiling n-heptane was 98.9%, the MI was 2.7, and the apparent density was 0.44 g / m 2.
It was l. On the other hand, 1.3 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part. Therefore, the activity was 14,100 g-pp / g-catalyst, and II in all polymers was 98.5%.

Comparative Example 1 The same pretreatment operation as in Example 1 was performed except that 1 mmol of titanium tetrachloride was not added in the pretreatment of the Ti catalyst component [A] in Example 1. The polymerization was carried out in the same manner as in Example 1. The polymerization results are shown in Table 1.

Examples 2 to 5 Preliminary contact was performed in the same manner as in Example 1 except that the amount of t-butyl chloride added as shown in Table 1 and the solvent at the time of preliminary contact were changed, and propylene was polymerized. It was The results are shown in Table 1.

Example 6 Except that in Example 1, the feed rate and time of propylene during pre-contact were changed to 8 Nl / Hr and 4 hours, respectively.
Preliminary contact was carried out in the same manner as in Example 1, and propylene was polymerized. The results are shown in Table 1.

Example 7 [Preparation of solid Ti catalyst component [A]] A high-speed stirrer (made by Tokushu Kika Kogyo) having an internal volume of 2 l was sufficiently replaced with N _2, and then 700 ml of refined kerosene, 10 g of commercially available MgCl ₂ and 24.2 g of ethanol and a product 3 g of the name Emazol 320 (Kao Atlas, sorbitan distearate) was added, the system was heated under stirring, and the system was stirred at 120 ° C. at 800 rpm for 30 minutes. 2 liters of refined kerosene 1 pre-cooled to -10 ° C was added using a Teflon tube with an inner diameter of 5 mm under high-speed stirring.
The liquid was transferred to a glass flask (with a stirrer). The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier.

After suspending 7.5 g of the carrier at room temperature in 150 ml of titanium tetrachloride, 33 ml of di-n-octyl cyclohexanedicarboxylate was suspended.
Was added, and the mixture was stirred and mixed at 120 ° C for 1.5 hours, and the supernatant was removed by decantation. Then, the solid portion was suspended again in 150 ml of titanium tetrachloride, and again stirred and mixed at 130 ° C for 1 hour. went. A solid reaction product was collected from the reaction product in excess and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The component was 2.6 wt% titanium, 60 wt% chlorine, and 19 wt% magnesium in terms of atoms.

[Pretreatment of Ti catalyst component [A]] Same as Example 1 except that the Ti catalyst component [A] used in the pretreatment of Example 1 was changed from the Ti catalyst component of Example 1 to the above Ti catalyst component. Pretreatment by various methods,
In addition, propylene was polymerized. The results are shown in Table 2.

Comparative Example 2 In the pretreatment of the Ti catalyst component [A] in Example 7,
Pretreatment was carried out in the same manner as in Example 7 except that 1 mmol of titanium tetrachloride was not added. The polymerization was carried out in the same manner as in Example 7. The polymerization results are shown in Table 2.

Example 8 [Preparation of solid Ti catalyst component [A]] 6 g of flaky Mg metal and 100 ml of n-hexane were added to a 400 ml flask, washed at 68 ° C. for 1 hour, and then dried with nitrogen. Next, 52 g of ethyl silicate was added and the temperature was raised to 65 ° C., then 0.1 ml of a 1 g solution of iodine in 5 ml of methyl iodide was added, and further 50 parts of n-hexane was added.
A solution consisting of 25 g of n-BuCl in ml was added over 1 hour and the temperature of the mixture was kept at 70 ° C for 6 hours. After completion of the reaction, the mixture was washed at 50 ° C. with n-hexane 6 times. 7 g of the solid thus obtained was suspended in 100 ml of TiCl ₄ and 5.5 mmol of diisobutyl phthalate was added, and the mixture was reacted at 120 ° C. for 1 hour. Then, the supernatant liquid was removed by decantation and 100 ml of 100 ml was again added. TiCl ₄ was added and the reaction was carried out at 120 ° C. for 1 hour. After completion of the reaction, the solid Ti catalyst component [A] was thoroughly washed with hexane
Was prepared. The composition of the Ti catalyst component [A] was 2.8 wt% titanium, 60 wt% chlorine, 19 wt% magnesium and 11.3 wt% diisobutyl phthalate.

[Pretreatment of Ti Catalyst Component [A]] Same as Example 1 except that in the pretreatment of Example 1, the Ti catalyst component of Example 1 of the Ti catalyst component [A] used was replaced with the above Ti catalyst component. Pretreatment by various methods,
In addition, propylene was polymerized. The results are shown in Table 2.

Comparative Example 3 In the pretreatment of the Ti catalyst component [A] in Example 8,
Pretreatment was carried out in the same manner as in Example 8 except that 1 mmol of titanium tetrachloride was not added. The polymerization was carried out in the same manner as in Example 8. The polymerization results are shown in Table 2.

Examples 9 to 12 In Example 7, the di-n-octyl cyclohexanedicarboxylate used in the preparation of the Ti catalyst component [A] was replaced with the electron donor shown in Table 3, and the Ti catalyst component [A] was preliminarily prepared. A Ti catalyst component [A] was prepared in the same manner as in Example 7 except that the electron donor shown in Table 3 was used instead of the diphenyldimethoxysilane used for the treatment and the polymerization of propylene. After performing the pretreatment of [A], propylene was polymerized. The results are shown in Table 3.

Comparative Examples 4 to 7 Pretreatment of Ti catalyst component [A] in Examples 9 to 12
Polymerization of propylene was carried out by pretreatment in the same manner as in Examples 9 to 12 except that TiCl ₄ was not added. The results are shown in Table 3.

Examples 13 to 15 The pretreatment was carried out in the same manner as in Example 1 except that 0.5 mmol of tert-butyl chloride added during the pretreatment of the Ti catalyst component [A] in Example 1 was replaced with that in Example 1.
Polymerization of propylene was carried out in the same manner as in. The results are shown in Table 4.

Example 16 (A) Synthesis of organomagnesium compound After a flask having an internal volume of 1 liter equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was replaced with argon, 32.0 g of milled magnesium for Grignard was charged. Add 120 g of n-butyl chloride and 500 m of di-n-butyl ether to the dropping funnel.
About 30 ml was added dropwise to magnesium in the flask to start the reaction. After the reaction was started, dropwise addition was continued at 50 ° C. for 4 hours, and after completion of the dropwise addition, the reaction was continued at 60 ° C. for an additional hour. Then, the reaction solution was cooled to room temperature and solids were separated by filtration.

When n-butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid and back-titrated with 1N aqueous sodium hydroxide solution to determine the concentration (phenolphthalein was used as an indicator), the concentration was 2.2. Mol /
It was l.

(B) Synthesis of solid product After a flask having an internal volume of 500 ml equipped with a stirrer and a dropping funnel was replaced with argon, 300 ml of n-heptane, 4.1 g (12.1 mmol) of tetrabutoxytitanium and 42.9 g of tetraethoxysilane (206 g). Was added to make a uniform solution. Next, the organomagnesium compound synthesized in (A)
100 ml was gradually added dropwise from the dropping funnel over 2 hours while maintaining the temperature in the flask at 5 ° C. After the dropping is completed,
After further stirring at room temperature for 1 hour, solid-liquid separation was performed at room temperature.
-Washing with 300 ml of heptane was repeated three times, followed by drying under reduced pressure to obtain 32.0 g of a brown solid product.

1.7% by weight of trivalent titanium atoms, 18.2% by weight of magnesium atoms, 2.2% by weight of silicon atoms in the solid product,
It contained 0.8% by weight of n-butyl ether, 33.5% by weight of ethoxy groups, and 2.4% by weight of butoxy groups.

In addition, no clear diffraction peak was observed in the wide-angle X-ray diffraction pattern of this solid product by Cu-Kα line, and the solid product had an amorphous structure.

(C) Synthesis of ester-treated solid After replacing a flask having an internal volume of 200 ml with argon,
15 g of the solid product synthesized in (B), monochlorobenzene 9
Add 0 ml and 2.7 ml of diisobutyl phthalate, and add 1 at 80 ℃.
A time reaction was performed.

After the reaction, solid-liquid separation was carried out and washing with 120 ml of n-heptane was carried out three times. The ester-treated solid contained 1.5% by weight of diisobutyl phthalate.

(D) Synthesis of solid catalyst component After completion of washing in (C) above, 90 ml of monochlorobenzene and 5.5 ml of n-butyl ether (32.5 mmol) were placed in a flask.
And add 49.3 ml (450 mmol) of titanium tetrachloride to 80
The reaction was carried out at ℃ for 1 hour. After completion of the reaction, solid-liquid separation was performed at 80 ° C., and then washing with 90 ml of monochlorobenzene at the same temperature was performed twice, and then 120 ml of n-heptane was further added at room temperature.
The washing was repeated 4 times.

The above treatment with the mixture of n-butyl ether and titanium tetrachloride was repeated once more under the same conditions to obtain 13.3 g of an ocher solid catalyst component.

In the solid catalyst component, titanium atom is 1.9% by weight, magnesium atom is 21.2% by weight, silicon atom is 0.2% by weight, butoxy group is 0.1% by weight, ethoxy group is 1.2% by weight, diisobutyl phthalate is 1.6% by weight, n-butyl ether is 2.3
% By weight and 67.0% by weight of chlorine.

[Pretreatment of Ti catalyst component [A]] Same as Example 1 except that the Ti catalyst component [A] used in the pretreatment of Example 1 was changed from the Ti catalyst component of Example 1 to the above Ti catalyst component. Pretreatment by various methods,
Further, propylene was polymerized. The results are shown in Table 6.

Comparative Example 8 In the pretreatment of the Ti catalyst component [A] in Example 16,
Example 16 was repeated except that 0.5 mmol of tert-butyl chloride was not added. Further, the polymerization was carried out in the same manner as in Example 16. The results are shown in Table 6.

Examples 17 and 18, Comparative Example 9 The procedure of Example 1 was repeated, except that the amount of tert-butyl chloride added during the pretreatment of the Ti catalyst component [A] was changed as shown in Table 7. The results are shown in Table 7.

[Brief description of drawings]

FIG. 1 is a flow chart showing an example of a catalyst preparation method in the polymerization method of α-olefin of the present invention.

Claims (1)

[Claims] 1. A highly active titanium solid catalyst component containing at least (A) magnesium, titanium and halogen as essential components, (B) an organometallic compound catalyst component of a metal of Groups 1 to 3 of the Periodic Table, and (C) ) An organohalogen compound catalyst component, provided that the ratio of the halogen atom X of the component (C) converted to 1 gram atom of titanium of the component (A) is in the range of 0.1 to 10 gram atom, in the presence of the catalyst formed from A method for polymerizing an α-olefin, which comprises preliminarily polymerizing the α-olefin with a polymer, and polymerizing the α-olefin in the presence of the resulting α-olefin prepolymerization catalyst.