JP2740503B2 - Method for polymerizing α-olefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the polymerization of .alpha.-olefin.
Poly-α-olefin having excellent stereoregularity
Process that can produce ynes with high catalytic activity
You. More specifically, a high activity α-o with excellent stereoregularity
Polymerizing α-Olefin with Refine Prepolymerization Catalyst
Method without reducing stereoregularity.
And a method by which high activation can be achieved. [0002] 2. Description of the Related Art Alpha-olefins such as propylene and 1-butene
Fin is polymerized in the presence of a stereoregular catalyst to form a crystalline poly
Methods for producing olefins have been proposed in many prior arts.
It is known. Among these polymerization methods, (a) mug
Nesium, titanium, halogen and electron donor
Active titanium solid catalyst component, and (b) organometallic conversion
Formed from compound catalyst component and (C) electron donor catalyst component
Polymerizing α-olefin in the presence of a catalyst
Gives highly stereoregular polymer with high catalytic activity
Methods have also been proposed in many prior arts, and these methods
Removes catalyst and amorphous polymer from polymer after polymerization
Adopted on an industrial scale as an excellent polymerization method without the need for
Have been. However, in the technical field
The demand for advanced technology is remarkable, and
There is a need for integrated technology. On the other hand, the present applicant has already disclosed Japanese Patent Publication No. 57-31.
No. 726 discloses a magnesium halide compound / titanium.
Organic acid ester and titanation of halogen compound complex
The titanium catalyst component obtained by treating with the compound
Existence of organometallic compounds of metals of Groups 1 to 3 of the periodic table
Proposed a method of polymerizing α-olefin in the presence of
No. 56-45403 discloses a magnesium halide compound.
Titanium in the presence of a compound-titanium halide compound complex
Compounds and organometallic compounds of metals of Groups 1 to 3 of the Periodic Table
Solid catalyst component (A) obtained by reacting
From organometallic compound component (B) of Group 1 to Group 3 metal
To polymerize olefins in the presence of different catalysts
ing. However, all of these methods involve polymerization.
Low activity and stereoregularity further enhance these performances
There is a need for an improved polymerization method. [0004] The present inventors have found that α-
Olefin polymerization technology is in the above situation
Recognized and conventionally proposed (a) magnesium,
Titanium, halogen and electron donor as essential components
Active titanium solid catalyst component, (b) organometallic compound catalyst component
And catalyst formed from (c) an electron donor catalyst component
In the polymerization of α-olefin in the presence of
Higher catalyst activation without reducing stereoregularity
Of the methods that can achieve
As a result, at least a highly active titanium solid catalyst component (A), an organic
Metal compound catalyst component (B) and transition metal compound catalyst component
Α-olefin in the presence of a catalyst formed from (C)
Α-olefin obtained by prepolymerizing
Polymerization of α-olefin in the presence of a prepolymerization catalyst
It is found that the above objects can be achieved by
Reached. [0005] Means and Action for Solving the Problems The present invention
According to at least (A) Magnesium, titanium and halogen are essential components
-Active titanium solid catalyst component to be used as component (B) Periodic table
An organometallic compound catalyst component of a Group 1 to Group 3 metal, and
And (C) transition metal compounds soluble in inert organic media
Catalyst component, α-olefin in the presence of a catalyst formed from
Prepolymerizes the resulting α-olefin prepolymer.
Polymerization of α-olefin in the presence of a polymerization catalyst
There is provided a method for polymerizing α-olefin characterized by the following.
You. Hereinafter, the present invention will be described in detail. In the present invention, the term polymerization is used for homopolymerization.
It is sometimes used to mean copolymerization.
The term polymer means not only homopolymer but also copolymer
Sometimes used to include the body. The titanium catalyst component (A) used in the present invention comprises:
With magnesium, titanium and halogen as essential components,
Highly active catalyst containing specified electron donor as optional component
Component. This titanium catalyst component (A) is a commercially available halogen
Compared to magnesium halides, smaller crystal halides
It contains gnesium and usually has a specific surface area of about 3m^Two/ G or less
Above, preferably about 40 to about 1000 m^Two/ G, more preferred
About 80 to about 800m^Two/ G and at room temperature
Hexane washing changes its composition substantially.
And not. In the titanium catalyst component (A), a halogen may be used.
/ Titanium (atomic ratio) is about 5 to about 200, especially about 5
To about 100, and the electron donor / titanium (molar ratio) is about
0.1 to about 10, especially about 0.2 to about 6,
About 2 to about 100, especially in the case of asium / titanium (atomic ratio)
Is preferably about 4 to about 50. The component
(A) also includes other electron donors, metals, elements, and functional groups.
Any may be included. Organic or inorganic diluents, eg
For example, silicon compounds, aluminum, polyolefin, etc.
It may be contained. Such a titanium catalyst component (A) is, for example,
Magnesium compound (or magnesium metal)
The contact between the electron donor and the titanium compound.
Or, in some cases, other reactants such as silica
Compounds such as nitrogen, phosphorus and aluminum
it can. A method for producing such a titanium catalyst component (A)
As the method, for example, JP-A-50-108385,
Nos. 50-126590, 51-20297, 51
-28189, 51-64586, 51-92
No. 885, No. 51-136625, No. 51-8748
No. 9, No. 52-100576, No. 52-147688
No. 52-104593, No. 53-2580, No.
53-40093, 53-43094, 55-
No. 135102, No. 56-135103, No. 56-8
No. 11, 56-11908, 56-18606
No. 58-83006, No. 58-138705,
No. 58-138706, No. 58-138707, No.
Nos. 58-138708, 58-138709, 5
8-138710, 58-138715, 60
No. 23404, No. 61-21109, No. 61-37
No. 802, No. 61-37803, No. 55-15271
No. 0, etc.
Can be. The method for producing these titanium catalyst components (A)
A few examples are briefly described below. (1) Magnesium compound or mug
A complex compound of a nesium compound and an electron donor
Grinding or grinding in the presence or absence of body, grinding aid, etc.
Electron donor and / or organoaluminum without
Reaction aids such as compounds and halogen-containing silicon compounds
Solids obtained with or without pretreatment and reaction conditions
To a titanium compound which forms a liquid phase. (2) Magnesification without reducing ability
The liquid titanium compound and the liquid titanium compound in the presence of an electron donor.
Reaction in the presence or absence of a solid titanium complex
Precipitate. (3) Titanium compound is reacted with the compound obtained in (2)
Let it. (4) To those obtained in (1) and (2)
The electron donor and the titanium compound are reacted. (5) Magnesium compound or mug
A complex compound of a nesium compound and an electron donor
Body, in the presence or absence of grinding aid, etc., and titanium compound
Crushed in the presence of material, electron donor and / or organic aluminum
Reactions such as silicon compounds and halogen-containing silicon compounds
The solid obtained with or without pretreatment with the auxiliary
Treatment with benzene or halogen compounds or aromatic hydrocarbons
You. (6) The compound obtained in the above (1) to (4)
Compounds are halogens or halogen compounds or aromatic hydrocarbons
To process. [0016] Among these preparation methods, catalyst preparation
Using liquid titanium halide or titanium
Halogenated carbon after or during use
Those using hydrogen are preferred. The structure of the highly active titanium catalyst component (A) of the present invention
Alcohols that can be a component include alcohol
, Phenols, ketones, aldehydes, carvone
Acids, esters of organic or inorganic acids, ethers, acid acids
Oxygen-containing electron donors such as
Donation of nitrogen-containing electrons such as min, nitrile and isocyanate
A body or the like can be exemplified. More specifically, methanol, ethanol
, Propanol, pentanol, hexanol, octane
Tanol, 2-ethylhexanol, dodecanol, e
Kutadecyl alcohol, benzyl alcohol, phenyl
Ethyl alcohol, cumyl alcohol, isopropyl alcohol
C1-C18 alcohol such as benzyl alcohol
Phenols, cresol, xylenol, ethyl
Phenol, propyl phenol, cumyl phenol,
Has an alkyl group such as nonylphenol or naphthol
C6 to C25 phenols which may be used; acetone,
Methyl ethyl ketone, methyl isobutyl ketone, aceto
C3 to C15 such as phenone and benzophenone
Ketones; acetaldehyde, propionaldehyde,
Octylaldehyde, benzaldehyde, tolaldehyde
Al, C2 to C15 aldol such as naphthaldehyde
Dehydes; methyl formate, ethyl acetate, vinyl acetate, acetic acid
Propyl, octyl acetate, cyclohexyl acetate, propyl acetate
Ethyl onate, methyl butyrate, ethyl valerate, stearin
Ethyl acetate, methyl chloroacetate, ethyl dichloroacetate,
Methyl acrylate, ethyl crotonate, dibu maleate
Chill, diethyl butylmalonate, dibutylmalonate
Chill, ethyl cyclohexanecarboxylate, 1,2-cycle
Diethyl rohexanedicarboxylate, 1,2-cyclohexyl
Di-2-ethylhexyl sandicarboxylate, methyl benzoate
, Ethyl benzoate, propyl benzoate, butyrate butyl
Octyl benzoate, cyclohexyl benzoate, benzoate
Phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, amyl toluate, ethylbenzoic acid
Ethyl, methyl anisate, ethyl anisate, ethoxy ammonium
Ethyl benzoate, dimethyl phthalate, diethyl phthalate,
Dibutyl phthalate, dioctyl phthalate, γ-butyrol
Couton, δ-valerolactone, coumarin, phthalide, charcoal
Is expected to be contained in titanium catalyst components such as ethylene acid
Organic acids having 2 to 30 carbon atoms including esters
Esters; ethyl silicate, butyl silicate, vinyl tri
Ethoxysilane, phenyltriethoxysilane, diphen
Inorganic acid esters such as nildiethoxysilane; acetyl
Luchloride, benzoyl chloride, toluic acid chloride
Carbon such as chloride, anisic chloride and phthalic dichloride
Acid halides of the formulas 2 to 15; methyl ether, ethyl
Ether, isopropyl ether, butyl ether,
Amyl ether, tetrahydrofuran, anisole, di
C2-C20 ethers such as phenyl ether
Acetic acid, benzoic acid amide, toluic acid amide
Which acid amides; acids such as benzoic anhydride and phthalic anhydride
Anhydride; methylamine, ethylamine, diethylamido
, Tributylamine, piperidine, tribenzylamine
, Aniline, pyridine, picoline, tetramethylethyl
Amines such as diamine; acetonitrile, benzo
Nitriles such as nitrile and tolunitrile; and the like.
Can be Use two or more of these electron donors
Can be It is desirable that the titanium catalyst component contains
Electron donors are esters, more preferably
Is the general formula [0020] Embedded image (Where R¹Is a substituted or unsubstituted hydrocarbon
Group, R^Two, R^Five, R⁶Is hydrogen or substituted or unsubstituted hydrocarbon
Base group, R^Three, R^FourIs hydrogen or substituted or unsubstituted carbonized
A hydrogen group, preferably at least one of which is substituted or
Is an unsubstituted hydrocarbon group. Also R^ThreeAnd R^FourAre connected to each other
It may be. R above¹~ R⁶With a substituted hydrocarbon group
For example, those containing foreign atoms such as N, O, and S, for example,
COC, COOR, COOH, OH, SO_ThreeH,-
C—N—C—, NH_TwoAnd the like. )so
Those having the represented skeleton can be exemplified. Among them, particularly preferred is R¹, R^Twoof
At least one of which is an alkyl group having 2 or more carbon atoms;
It is a diester of carboxylic acid. Preferred as the polyvalent carboxylic acid ester
Specific examples of are: diethyl succinate, dib succinate
Chill, diethyl methylsuccinate, α-methylglutaric acid
Diisobutyl, dibutylmethyl malonate, dienomalonate
Chill, diethyl ethylmalonate, isopropylmalonic acid
Diethyl, diethyl butylmalonate, phenylmalonic acid
Diethyl, diethyl malonate diethyl, allyl malonic acid
Diethyl, diethyl diisobutylmalonate, dinormal
Diethyl butylmalonate, dimethyl maleate, male
Monooctyl phosphate, dioctyl maleate, maleic acid
Dibutyl, dibutyl butyl maleate, butyl maleic
Diethyl phosphate, diisopropyl β-methylglutarate,
Diallyl succinate, di-2-ethylhexyl fumarate
, Diethyl itaconate, dibutyl itaconate, citrus
Aliphatic such as dioctylconate and dimethyl citrate
Polycarboxylic acid ester, 1,2-cyclohexanecal
Diethyl borate, 1,2-cyclohexanecarboxylic acid di
Isobutyl, diethyl tetrahydrophthalate, nadic
Alicyclic polycarboxylates such as diethyl phosphate;
Monoethyl talate, dimethyl phthalate, methyl phthalate
Ethyl, monoisobutyl phthalate, mononorma phthalate
Rubutyl, diethyl phthalate, ethyl phthalate
, Ethyl n-butyl phthalate, di-n-phthal phthalate
Ropyl, diisopropyl phthalate, di-n-butyl phthalate
, Diisobutyl phthalate, di-n-heptyl phthalate,
Di-2-ethylhexyl phthalate, di-n-octyl phthalate
Chill, dineopentyl phthalate, didecyl phthalate, phthalate
Benzyl butyl talate, diphenyl phthalate, naphthali
Diethyl dicarboxylate, dibu naphthalene dicarboxylate
Chill, triethyl trimellitate, dib trimellitate
Aromatic polycarboxylic acid esters such as tyl
Heterocyclic polycarboxylic acid esters such as landicarboxylic acid
And the like. Further, as a polyvalent hydroxy compound ester
Preferred specific examples include 1,2-diacetoxy.
Benzene, 1-methyl-2,3-diacetoxybenze
2,3-diacetoxynaphthalene, ethylene glyco
Diol pivalate, butanediol pivalate, etc.
I can do it. Examples of esters of hydroxy-substituted carboxylic acids
Benzoylethyl salicylate, acetyl
Sobutyl salicylate, acetyl methyl salicylate
And the like. The catalyst can be supported on a titanium catalyst component.
Another example of a polycarboxylic acid ester is adipine
Diethyl acetate, diisobutyl adipate, diyl sebacate
Sopropyl, di-n-butyl sebacate, di-n-sebacate
Octyl, di-2-ethylhexyl sebacate, etc.
Esters of chain dicarboxylic acids can be mentioned. Preferred among these polyfunctional esters
Are those having the skeleton of the general formula described above,
More preferably, phthalic acid, maleic acid, substituted malonic acid, etc.
And esters of alcohols having 2 or more carbon atoms,
Preferably, phthalic acid and an alcohol having 2 or more carbon atoms
Is a diester of It can be supported on a titanium catalyst component.
Other electron donor components include RCOOR '(R and R' are substituted
A hydrocarbyl group which may have
Are either branched (including alicyclic) or ring-containing
A monocarboxylic acid ester represented by
You. For example, as R and / or R ' [0029] Embedded imageAnd the like. R or R '
If one of them is the above group, the other is the above group.
Or other groups, such as linear or cyclic groups
May be used. Specifically, dimethyl acetic acid, trimethyl vinegar
Acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid,
Various monoesters such as benzoyl acetic acid, isopropanol
, Isobutyl alcohol, tert-butyl alcohol,
Examples of various monocarboxylic acid esters of alcohols such as
can do. Carbonate was also selected as the electron donor.
You can choose. Specifically, diethyl carbonate
G, ethylene carbonate, diisopropyl carbonate
G, phenylethyl carbonate, diphenylcarbonate
For example. In carrying these electron donors,
It is not necessary to use these as starting materials,
These can be changed during the preparation of titanium catalyst components
The compounds are converted to these compounds during the preparation step.
May be. In the titanium catalyst component, another electron donor is used.
May coexist, but if too much coexist, adverse effect
Should be kept small. In the present invention, (A) the solid titanium catalyst
Magnesium compounds used in the preparation of components have a reducing ability
It is a magnesium compound having or not having. Former
Examples include magnesium-carbon bonds and magnesium-hydrogen
Magnesium compound having a bond, such as dimethylmag
Nesium, diethylmagnesium, dipropylmagnesi
, Dibutylmagnesium, diamylmagnesium,
Dihexylmagnesium, didecylmagnesium, ethi
Magnesium chloride, propyl magnesium chloride, spot
Magnesium chloride, hexyl magnesium chloride,
Magnesium chloride, butylethoxymagnesium,
Butylmagnesium, butylmagnesium hydra
Id and the like. These magnesium compounds are
For example, it can be used in the form of a complex compound with organoaluminum, etc.
It can be in liquid or solid state
No. On the other hand, as a magnesium compound without reducing ability
Is magnesium chloride, magnesium bromide, magnesium iodide
Magnesium, magnesium fluoride such as magnesium fluoride
Methoxymagnesium chloride, ethoxymagnesium chloride
, Magnesium isopropoxy chloride, butoxy chloride
Magnesium and octoxymagnesium chloride
Lucoxy magnesium halide; phenoxy chloride magne
Such as sodium and methylphenoxymagnesium chloride.
Riloxy magnesium halide; ethoxy magnesium
System, isopropoxy magnesium, butoxy magnesium
, N-octoxymagnesium, 2-ethylhexoxy
Alkoxymagnesium, such as cimagnesium; Hue
Nonoxymagnesium, dimethylphenoxymagnesium
Allyloxymagnesium, such as magnesium laurate
, Magnesium such as magnesium stearate
And the like. Also,
These magnesium compounds having no reducing ability are described above.
Derived from magnesium compounds having reducing ability
Or may have been derived during the preparation of the catalyst component.
No. For example, a magnesium compound having a reducing ability and a policy
Loxane compound, halogen-containing silane compound, halogen
Conversion of contained aluminum compounds, esters, alcohols, etc.
Magnesium that does not have reducing ability by contact with compound
For example, a method of converting the compound into a compound of formula (II). Also,
Magnesium compounds are complex compounds and complex compounds with other metals
Alternatively, it may be a mixture with another metal compound. Sa
Further, a mixture of two or more of these compounds may be used.
No. Among these, preferred magnesium compounds have a reducing ability.
Is a compound having no halogen, particularly preferably containing halogen.
Magnesium compounds, especially magnesium chloride, al
Magnesium oxychloride, allyloxymagnesium chloride
It is. In the present invention, the solid titanium catalyst component (A)
There are various titanium compounds used for the preparation of
Normal Ti (OR)_gX_4-g(R is a hydrocarbon group, X is a halogen,
A tetravalent titanium compound represented by 0 ≦ g ≦ 4) is preferable.
You. More specifically, TiCl_Four, TiBr_Four, TiI_FourSuch as
Titanium tetrahalide; Ti (OCH_Three) Cl_Three, Ti (OC
_TwoH_Five) Cl_Three, Ti (O_n-C_FourH₉) Cl_Three, Ti (OC_TwoH_Five) B
r_Three, Ti (OisoC_FourH₉) Br_ThreeTrihalogenated alcohols such as
Xtitanium; Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl_Two,
Ti (O_n-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoBr_TwoSuch as
Halogenated alkoxytitanium; Ti (OCH_Three)_ThreeCl, Ti
(OC_TwoH_Five)_ThreeCl, Ti (O_n-C_FourH₉)_ThreeCl, Ti (OC
_TwoH_Five)_ThreeMonohalogenated trialkoxy titers such as Br
N; Ti (OCH_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (O_n-C
_FourH₉)_FourSuch as tetraalkoxy titanium
Can be. Of these, preferred are halogen-containing
Titanium compounds, especially titanium tetrahalides,
Particularly preferred is titanium tetrachloride. These titanium
The compounds may be used alone or in the form of a mixture.
No. Or diluted into hydrocarbons or halogenated hydrocarbons
May be used. In the preparation of the titanium catalyst component (A),
Compound, magnesium compound and electron donation to be carried
Body, and electron donation that may be used as needed
Body, such as alcohol, phenol, monocarboxylic acid
Such as silicon compounds, aluminum compounds, etc.
The amount used depends on the preparation method and cannot be specified unconditionally
Is, for example, the amount of electricity to be carried per mole of magnesium compound.
0.05 to 5 moles for children, 0.05 for titanium compound
The ratio can be about 500 moles. A halogen atom constituting the titanium catalyst component and
Fluorine, chlorine, bromine, iodine or a mixture thereof
Can be mentioned, and chlorine is particularly preferred. In the method of the present invention, the titanium solid catalyst component
When (A) contains an electron donor, the polymerization method of the present invention
A polymer having particularly excellent stereoregularity is obtained. In the present invention, the titanium solid as described above
Having a catalyst component (A) and a metal of Groups 1 to 3 of the periodic table
Metal compound catalyst components, such as organoaluminum compounds
Product catalyst component (B) and the combination catalyst of component (C) described later
To polymerize or copolymerize olefins. Organic gold of metals of Groups 1 to 3 of the Periodic Table
(I) at least a molecule
Having one Al-carbon bond therein
Compound, for example, general formula R¹ _mAl (OR^Two)_nH_pX_q (Where R¹And R^TwoIs a carbon atom, usually 1 to 15
, Preferably 1 to 4 hydrocarbon radicals
They may be the same or different. X is halogen, m is 0 <m ≦
3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦ q <3.
And m + n + p + q = 3)
Aluminum compound, (ii) general formula M¹AlR¹ _Four (Where M¹Is Li, Na, K, and R¹Is the same as above)
Complex alkylation of Group 1 metals with aluminum
Object, (iii) general formula R¹R^TwoM^Two (Where R¹And R^TwoIs the same as above. M^TwoIs Mg, Zn, C
d) is a dialkyl compound of a Group 2 metal represented by
And so on. Organoaluminumization belonging to the above (i)
The following can be exemplified as the compound. General formula R¹ _mAl (OR^Two)_3-m (Where R¹And R^TwoIs the same as above. m is preferably 1.
5 ≦ m <3), General formula R¹AlX_3-m (Where R¹Is the same as above. X is halogen, m is preferred
Is 0 <m <3), General formula R¹AlH_3-m (Where R¹Is the same as above. m is preferably 2 ≦ m <3
), General formula R¹ _mAl (OR^Two)_nX_q (Where R¹And R^TwoIs the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
) Can be exemplified. In the aluminum compound belonging to (i)
And more specifically triethyl aluminum, tributyl
Trialkyl aluminum such as aluminum
Trialkenyl alky such as isoprenyl aluminum
Minium, diethylaluminum ethoxide, dibutyl
Dialkyl aluminum such as aluminum butoxide
Alkoxide, ethyl aluminum sesquiethoxide,
Alkyls such as butyl aluminum sesquibutoxide
In addition to the luminium sesquialkoxide, R¹ _2.5Al (OR^Two)
₀._FivePartially having an average composition represented by
Alkylated aluminum, diethylaluminum
Umum chloride, dibutylaluminum chloride, diethyl
Dialkylaluminum such as aluminum bromide
Muhalogenide, ethyl aluminum sesquichloride,
Chill aluminum sesquichloride, ethyl aluminum
Alkyl aluminum sesquiha such as sesquibromide
Logenide, ethyl aluminum dichloride, propyl alcohol
Luminium dichloride, butyl aluminum dibromide
Such as alkylaluminum dihalogenides
Partially halogenated alkyl aluminum, die
Chill aluminum hydride, dibutyl aluminum hydride
Dialkylaluminum hydrides such as
Luminium dihydride, propyl aluminum dihydride
Alkyl aluminum dihydride
Alkyl aluminum, ethyl aluminum
Umethoxycyclolide, butyl aluminum butoxy
Parts such as chloride, ethyl aluminum ethoxy bromide
Partially alkoxylated and halogenated alkyl groups
Luminium. The compound belonging to the above (ii) includes Li
Al (C_TwoH_Five)_Four, LiAl (C₇H_Fifteen)_FourEtc., and in (iii) above
Compounds belonging to diethyl zinc, diethyl magnesium
For example. Also ethyl magnesium chloride
Alkali magnesium halides like
You. Among these, especially trialkyl aluminum,
Uses alkyl aluminum halides and their mixtures
Is preferred. The transition metal compound catalyst component (C) is inert.
It is a transition metal compound that is soluble in organic media.
Of metals of group IVB of the periodic table such as ruconium and hafnium
For inert media of compounds, vanadium, chromium and other metals
Soluble compounds such as chlorides, bromides, iodides
Which halide, methoxide, ethoxide, propoxy
Alkoxides such as sides, etc.
You. As these transition metal compounds, specifically, usually T
i (OR)_gX_4-g(R is a hydrocarbon group, X is a halogen, 0 ≦ g
≦ 4) are preferred. Yo
More specifically, TiCl_Four, TiBr_Four, TiI_FourSuch as tetra
Titanium halide; Ti (OCH_Three) Cl_Three, Ti (OC_TwoH_Five)
Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (OC_TwoH_Five) Br_Three, Ti
(OisoC_FourH₉) Br_ThreeTrihalogenated alkoxythio
Tan; Ti (OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl_Two, Ti
(On-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoBr_TwoDihalo
Alkoxy titanium genide; Ti (OCH_Three)_ThreeCl, Ti (OC
_TwoH_Five)_ThreeCl, Ti (O_n-C_FourH₉)_ThreeCl, Ti (OC_TwoH_Five)_ThreeBr
Monohalogenated trialkoxytitanium such as Ti; OC (OC
H_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (O_n-C_FourH₉)_FourSuch as Tet
Laalkoxy titanium or aluminum compound
Products, mixtures with other metal compounds such as silicon compounds
can do. Of these, preferred is halogen
Containing titanium compounds, especially titanium tetrahalides
Yes, particularly preferred is titanium tetrachloride. The transition metal compound catalyst component vanadium
Specifically, the VOCl_Three, VCl_Four, VO
(OCH_Three) Cl_Two, VO (OC_TwoH_Five) Cl_Two, VO (OC
_TwoH_Five)₁._FiveCl₁._Five, VO (OCH_Three)_TwoCl, VO (OC_TwoH_Five)_Three
And the like. In the present invention, (A) magnesium
Active titanium containing titanium, titanium and halogen as essential components
Solid catalyst component, (B) Periodic Table Groups 1 to 3
Metal organometallic compound catalyst component and (C) inert
In addition to the transition metal compound catalyst component soluble in organic media,
(D) organosilicon compound or sterically hindered
Catalyst components composed of amines can be used. [D] Catalyst component used in the present invention
Of these, organosilicon compounds are generally Si-OC or
It has a Si-NC bond, and for example, alkoxysilane,
For example, aryloxysilane. This
As an example, the formula R_nSi (OR¹)_4-n(Where 0 ≦ n ≦ 3,
R is a hydrocarbon group such as an alkyl group, cycloalkyl
Group, aryl group, alkenyl group, haloalkyl group,
A non-alkyl group, or halogen, R¹Is a hydrocarbon group,
For example, an alkyl group, a cycloalkyl group, an aryl group,
Alkenyl group, alkoxyalkyl group, etc., provided that n
R, (4-n) ORs¹The groups can be the same or different. )
And a silicon compound represented by the following formula: or,
Another example is OR¹Group-containing siloxanes, carbo
And the like. or,
In another example, two or more silicon atoms are oxygen or nitrogen
Compounds that are connected to each other through an atom
Can be The above organosilicon compound is Si-O-
A compound having no C bond and a compound having an OC bond
React in advance or react in a polymerization
It may be used after being converted into a compound having an i-O-C bond.
No. As such an example, for example, a Si-OC bond is used.
Halogen-containing silane compounds or silicon hydra
And alkoxy group-containing aluminum compounds, alcohols
Xy group-containing magnesium compounds, other metal alcoholers
, Alcohol, formate, ethylene oxide, etc.
Can be exemplified. Organosilicon compound
Containing other metals (e.g., aluminum, tin, etc.)
It may be something. More specifically, trimethylmethoxysila
, Trimethylethoxysilane, dimethyldimethoxysilane
Orchid, dimethyldiethoxysilane, diisopropyldimene
Toxisilane, t-butylmethyldimethoxysilane, t-
Butylmethyldiethoxysilane, t-amylmethyldie
Toxisilane, diphenyldimethoxysilane, phenyl
Methyldimethoxysilane, diphenyldiethoxysila
, Bis o-tolyldimethoxysilane, bis m-tolyldi
Methoxysilane, bis p-tolyldimethoxysilane,
Sp-tolyldiethoxysilane, bisethylphenyldi
Methoxysilane, dicyclohexyldimethoxysilane,
Cyclohexylmethyldimethoxysilane, cyclohexyl
Methyldiethoxysilane, ethyltrimethoxysila
, Ethyltriethoxysilane, vinyltrimethoxysilane
Orchid, methyltrimethoxysilane, n-propyltriet
Xysilane, decyltrimethoxysilane, decyltrier
Toxisilane, phenyltrimethoxysilane, γ-chloro
Lepropyl trimethoxy silane, methyl triethoxy
Orchid, ethyltriethoxysilane, vinyltriethoxy
Silane, t-butyltriethoxysilane, n-butyltri
Ethoxysilane, iso-butyltriethoxysilane,
Enyltriethoxysilane, γ-aminopropyltrie
Toxoxysilane, chlorotriethoxysilane, ethyltri
Isopropoxy silane, vinyl tributoxy silane,
Clohexyltrimethoxysilane, cyclohexyltri
Ethoxysilane, 2-norbornanetrimethoxysila
2-norbornanetriethoxysilane, 2-norbo
Lunan methyl dimethoxysilane, ethyl silicate, silicic acid
Butyl, trimethylphenoxysilane, methyltriaryl
Roxy (allyloxy) silane, vinyl tris (β-methoxy
Ethoxysilane), vinyltriacetoxysilane,
Such as tyltetraethoxydisiloxane, especially
Ethyltriethoxysilane, n-propyltriethoxy
Silane, t-butyltriethoxysilane, vinyltrie
Toxysilane, phenyltriethoxysilane, vinyl
Riboxysilane, diphenyldimethoxysilane, phen
Nylmethyldimethoxysilane, bis-p-tolyldimethoxy
Sisilane, p-tolylmethyldimethoxysilane, dicycl
Rohexyldimethoxysilane, cyclohexylmethyldi
Methoxysilane, 2-nonebornanetriethoxysila
, 2-norbornanemethyldimethoxysilane, diphen
Preferred are nildiethoxysilane, ethyl silicate and the like. As the amines having a large steric hindrance,
Is 2,2,6,6-tetramethylpiperidine, 2,2,5,
5-tetramethylpyrrolidine or derivatives thereof
And tetramethylmethylenediamine are preferred.
The component (D) is formed in the form of an adduct with another compound.
Can also be used. In the polymerization method of the present invention, the catalyst component
When (D) is used, α- such as propylene having 3 or more carbon atoms
More polymers with excellent stereoregularity from olefins
It can be obtained with high activity. The olefin used in the polymerization method of the present invention is used.
At least the components (A), (B), (C) and
And optionally in the presence of a catalyst formed from component (D).
Olefin prepolymerization and the resulting α-olefin
In-prepolymerization catalyst. In the method of the present invention, α-
The following methods are used to form the olefin prepolymerization catalyst.
The method can be illustrated. [1] In an inert medium, (A)
The components (B), (C) and optionally (D)
After the formation of the catalyst by the
Contact to form an α-olefin prepolymerized catalyst.
How to do it. [2] The components (A), (B), (C) and
And optionally (D) component in the presence of α-olefin
Depending on whether it is in an inert medium or in an α-olefin medium,
Contact to form the α-olefin prepolymerized catalyst.
How to do it. [3] Component (A), component (B), component (C)
By contacting the component and optionally component (D).
After formation, optionally in an inert medium or α
-Contact with α-olefin in an olefin medium;
To form an α-olefin prepolymerization catalyst by
Law. In the method of the present invention, the component (A)
Component (B), component (C) and optionally component (D)
Formation of catalyst by contact in the absence of in
In some cases, the temperature during the contact treatment is usually -50 to 1
00 ° C., preferably -20 to 30 ° C.
Usually takes 1 minute to 10 hours, preferably
Is 5 minutes to 2 hours. The contact treatment is α-olefin
Conducted in an inert medium, if necessary, in the absence of any
Catalyst when in contact with an inert medium
It is formed in the state of Catalyst formed in suspension
If necessary, the catalyst suspension can be used as is in α-olefin
Can be used for the prepolymerization of
Of α-olefin by separating the catalyst formed from
It can also be used for Also, in the method of the present invention,
Thus, in the presence of α-olefin, the components (A) and (B)
Component (C) and optionally component (D) may be added, if necessary, to an inert medium.
By contact in the body or in an α-olefin medium
Of the catalyst and the form of the α-olefin prepolymerized catalyst
Can be performed simultaneously or sequentially. In the process of the present invention, the formation of a catalyst or
Component (A) during the formation of the α-olefin prepolymerization catalyst,
Component (B), component (C) and optionally component (D)
Is as follows: 1 g atom of titanium of component (A)
On the other hand, the metal atom M of the component (B)₁Is usually between 1 and
100 gram atoms, preferably 2 to 30 gram atoms
In the range of the element, and per gram atom of titanium of the component (A).
Transition metal atom M of component (C)_TwoIs usually not 0.1
10 gram atoms, preferably 0.4 to 3 gram atoms
In the range of the element, and per gram atom of titanium of the component (A).
The proportion of component (D) is usually 0.3 to 30 mol, preferably
Or from 0.7 to 5 moles. In the method of the present invention, the prepolymerization is
0.5 to 0.5 g per gram of neutral titanium solid catalyst component (A)
500 g, preferably 1 to 100 g, more preferably
By polymerizing 2 to 10 g of α-olefin.
It is done. Α-olefin used for prepolymerization
Is ethylene and α-olefin having 3 to 20 carbon atoms.
Propylene, 1-butene, 4-methyl-1
-Pentene, 1-hexene, 1-octene, 1-decene
, 1-dodecene, 1-tetradecene, etc.
But propylene is preferred. The prepolymerization temperature is from -20 ° C to 70 ° C, preferably
Preferably -10 ° C to 60 ° C, more preferably 0 ° C
It is in the range of 50 ° C. The time required for prepolymerization is usually
Is 0.5 to 20 hours, preferably 1 to 10 hours
It is. The prepolymerization can be carried out batchwise or continuously.
Can be adopted, and can be used under normal pressure or pressure.
You can do that. Hydrogen in prepolymerization
Such a molecular weight regulator may be used in combination with at least 13
Intrinsic viscosity [η] measured in decalin at 5 ° C is 0.2 dl / g
As described above, preferably, the prepolymer of 0.5 to 20 dl / g is used.
It is better to keep down to the amount that can be manufactured. The prepolymerization is carried out without solvent or in an inert medium.
Be done. Spare in inert hydrocarbon media in terms of operability
Polymerization is preferred. Inert hydrocarbon used for the prepolymerization
As the raw medium, the above-mentioned solvents can be exemplified. Solids in the prepolymerization reaction system in the prepolymerization
Usually, the concentration of the transition metal atom in the solid catalyst is
10 as concentration^-6To 1 gram atom / l, preferably
10^-FourOr 10^-2It is in the range of gram atoms / l. In the method of the present invention, the formation of the catalyst
Or in the formation of the α-olefin prepolymerization catalyst.
Inert media that may be used include ethane, pro
Bread, butane, pentane, methylpentane, hexane,
Heptane, octane, decane, gasoline, kerosene, light oil
Which aliphatic hydrocarbons, cyclohexane, methylcyclo
Alicyclic hydrocarbons such as hexane, benzene, and toluene
And aromatic hydrocarbons such as xylene.
And an inert medium comprising a mixture of two or more of these.
The body can also be used. Similarly, α-olefin
Α-Olefin for prepolymerization
Α-Olefin described above can be similarly exemplified. In the process for the polymerization of α-olefin of the present invention
The α-olefin prepolymerization catalyst by the above prepolymerization.
Are formed in suspension. Put the suspension as it is
The suspension can be used in the form
The medium can be used separately. The α-ole obtained by the above prepolymerization
The fin prepolymerization catalyst is superior in the polymerization of α-olefin.
Shows the polymerization activity obtained. Olefin used for polymerization in the method of the present invention
As the ethylene, propylene, 1-butene, 4
-Methyl-1-pentene, 1-octene, etc.
These are not only homopolymers but also random copolymers or
Tsuku copolymerization can be performed. In copolymerization,
Polyunsaturated compounds such as diene and non-conjugated diene
It can be selected as a combined component. Of these olefins
Is propylene or 1-butene or 4-methyl-1
-Homopolymerization of pentene or their olefins and other
Propylene or 1-
Butene as a main component (for example, 50 mol% or more, preferably
Or 70 mol% or more).
It is preferred to apply the method of the invention to the polymerization. In the process of the present invention, the polymerization of olefin
Is carried out in the gas phase or in the liquid phase, for example in the form of a slurry.
You. In slurry polymerization, an inert hydrocarbon is used as a solvent.
Or olefin itself can be used as the solvent.
You. In the method of the present invention, α-olefin
Polymerization was carried out in the presence of the α-olefin prepolymerization catalyst
Is done. In the polymerization reaction, the above-mentioned α-olefin
The combined catalyst alone can be used, or the α-olefin
In addition to the pre-polymerization catalyst, components (B) and (C)
And any one, two or three components of component (D)
Can be added. In the method of the present invention, the compound is present in the polymerization reaction system.
The ratio of each catalyst component is T
About 0.001 to about 0.5 milligrams in terms of i atom
Atom / l, especially about 0.005 to about 0.5 milligram
Atom / l, and the catalyst component (B)
For each gram atom of titanium in the medium component (A), (B)
About 1 to about 2000 gram atoms of metal atoms in the component;
Preferably in the range of about 5 to about 500 gram atoms
As for the catalyst component (D), the catalyst component (A)
The component (D) is about 0.1 per gram atom of titanium atom.
To about 500 moles, preferably about 0.5 to 100
Range of moles. In the polymerization reaction, the α-olefin
The polymerization is carried out by adding the catalyst component (B) in addition to the polymerization catalyst.
In this case, the ratio of the component (B) is determined by the amount of the catalyst in the catalyst component (A).
Metal atom in component (B) per gram atom of tan atom
Is from about 1 to about 2000 gram atoms, preferably
It ranges from about 10 to about 500 gram atoms. Likewise
In addition to the α-olefin prepolymerization catalyst, the catalyst component
When polymerization is carried out by adding (D), additional component (D) is added.
In the case where the amount of titanium is 1 gram atom in the catalyst component (A),
About 0 to 1000 mol, preferably about 0 to about 10
It is in the range of 0 mol. The olefin polymerization temperature is preferably about 20.
About 200 ° C., more preferably about 50 to about 180
℃, pressure from normal pressure to about 100kg / cm^Two, Preferably
Is about 2 to about 50 kg / cm^TwoUnder a moderate pressure condition
Is preferred. Polymerization can be batch, semi-continuous, or continuous
The method can also be performed in the method described above. React further polymerization
It is also possible to perform it in two or more stages under different conditions.
You. [0073] According to the present invention, in particular, the number of carbon atoms is 3 or more.
When applied to the stereoregular polymerization of α-olefin of
Producing polymers with high stereoregularity index with high catalytic efficiency
Can be. In connection with being more active, the unit
Polymer yield per solid catalyst component is the same
Better than previous proposals in the number of polymers obtained
Catalyst residue in the polymer, especially containing halogen
The amount can be reduced and the catalyst removal operation can be omitted.
Not to mention the tendency of the mold to rust during molding.
It can be suppressed significantly. [0074] Next, the present invention will be described in more detail with reference to examples. [0075]referenceExample 1 [0076] [Preparation of solid Ti catalyst component [A]] Anhydrous magnesium chloride
7.14 g (75 mmol), 38 ml of decane and 2-ethyl
35.1 ml (225 mmol) of xyl alcohol at 130 ° C.
After performing a heating reaction for 2 hours to make a homogeneous solution,
1.7 g (11.3 mmol) of phthalic anhydride are added and
And further stir and mix for 1 hour to remove phthalic anhydride
Dissolve in solution. The homogeneous solution obtained in this way is
After cooling to a temperature, titanium tetrachloride 2 kept at -20 ° C
Charge 100 ml (1.8 mol) dropwise over 1 hour
You. After completion of the charging, the temperature of the mixture was raised to 11 over 4 hours.
The temperature was raised to 0 ° C, and when it reached 110 ° C, diisobutyl
5.03 ml (18.75 mmol) of phthalate are added and this is
For 2 hours at the same temperature with stirring. After 2 hours reaction
A solid portion was collected by hot filtration, and this solid portion was 275 ml of T
iCl_FourAnd re-suspended at 110 ° C for 2 hours.
Perform a thermal reaction. After completion of the reaction, the solid portion was collected again by hot filtration.
Take it and release it in the washing solution at 110 ° C with decane and hexane
Wash thoroughly until no titanium compound is detected. Less than
The catalyst component [A] is added to the solid Ti synthesized by the above production method.
The catalyst slurry is stored at the same time as the hexane slurry.
-Measure the concentration. Some of these were obtained by drying
The composition of the solid Ti catalyst component [A] is titanium 2.4% by weight, chlorine
56% by weight, 19% by weight of magnesium and diisobuty
It was 13.6% by weight of luphthalate. [0077] [Pretreatment of Ti catalyst component [A]] 400 ml with a stirrer
Purified hexane 100 under nitrogen atmosphere in a neck glass reactor
ml, triethylaluminum 1.0 mmol, diphenyl
Rudimethoxysilane 2 mmol, the above solid Ti catalyst component
[A] 2.0 g and 1 mmol of titanium tetrachloride were added.
After that, propylene was added at a temperature of 20 ° C. at a rate of 3.2 Nl / Hr.
Was fed to the reactor for 1 hour. Propylene supply
When the reaction was completed, the inside of the reactor was replaced with nitrogen, and the supernatant was
Two washing operations consisting of removal and addition of purified hexane
After reconstitution, resuspend in purified hexane and transfer
Liquid. In addition, at this time, the measurement of the whole capacity is also performed.
In both cases, the slurry concentration of the catalyst was also measured. [0078] [Polymerization] Purified hexane 7 in an autoclave with an internal volume of 2 l
Charge 50 ml, and trie in propylene atmosphere at 60 ° C.
0.75 mmol of chilled aluminum, diphenyldimethoxy
0.075 mmol of silane and the reserve of the catalyst component [A]
The treated product was 0.0075 mmol in terms of titanium atom (the catalyst
(Equivalent to 10.9 milligrams in terms of component [A])
Was. After introducing 200 ml of hydrogen, the temperature was raised to 70 ° C. and 2 hours
During the propylene polymerization. The pressure during polymerization is 7kg / cm
^TwoG was kept. After completion of the polymerization, the slurry containing the produced polymer is washed.
After filtration, the mixture was separated into a white powdery polymer and a liquid phase. After drying
The yield of the white powdery polymer was 232.3 g, which was boiled.
The extraction residual ratio with n-heptane is 98.5%, and the MI is 5.5.
1. Its apparent density was 0.44 g / ml. On the other hand, the liquid phase
By concentrating the parts, 1.3 g of a solvent-soluble polymer was obtained. Accordingly
The activity is 17,300 g-pp / g-catalyst,
II was 98.0%. ComparisonreferenceExample 1reference In the pretreatment of the Ti catalyst component [A] in Example 1,
Except that 1 mmol of titanium tetrachloride was not addedthree
ConsiderationThe same pre-processing operation as in Example 1 was performed. The polymerization isreference
The procedure was the same as in Example 1. Table 1 shows the polymerization results. [0081]referenceExamples 2-5 TiCl as shown in Table 1₄Amount of pre-contact
Except for the solventreferencePreparatory contact by the same operation as in Example 1.
And propylene polymerization was carried out. The result
The results are shown in Table 1. [0082]referenceExample 6reference In Example 1, the propylene feed rate and
And time were changed to 8 Nl / Hr and 4 hours, respectively.
Other thanreferencePreliminary contact is performed in the same manner as in Example 1,
In addition, propylene was polymerized. The results are shown in Table 1. Example1 [0084] [Preparation of solid Ti catalyst component [A]] High-speed stirring of 2 l internal volume
Equipment (manufactured by Tokushu Kika Kogyo)_TwoAfter replacement, refined lamp
700ml oil, commercial MgCl_Two10g, ethanol 24.2g
And trade name EMAZOL 320 (manufactured by Kao Atlas Co., Ltd.
3 g of (vitandistearate) and heat the system with stirring
Then, the mixture was stirred at 120 rpm at 800 rpm for 30 minutes. High speed stirring
Under stirring, use a Teflon tube with an inner diameter of 5 mm.
First, 1 liter of refined kerosene cooled to -10 ° C
The solution was transferred to a 2 l glass flask (with a stirrer). Generation
The body is collected by filtration, washed thoroughly with hexane, and
I got a body. 7.5 g of the carrier was added at room temperature to 150 ml of titanium tetrachloride.
After suspending in cyclohexane, the cyclohexanedicarboxylic acid
Add 33 ml of n-octyl and stir at 120 ° C for 1.5 hours
After mixing, the supernatant was removed by decantation,
The body was suspended again in 150 ml of titanium tetrachloride and
The mixture was stirred and mixed at 30 ° C. for 1 hour. Reaction from the reactants
The solid matter is collected by filtration, and with a sufficient amount of purified hexane.
The solid catalyst component [A] was obtained by washing. The ingredient is raw
2.6% by weight of titanium, 60% by weight of chlorine,
It was 19% by weight of calcium. [0086] [Pretreatment of Ti catalyst component [A]]referencePreliminary treatment of Example 1
In the above, the used Ti catalyst component [A]referenceT of Example 1
Except for replacing the i catalyst component with the above Ti catalyst componentreferenceAn example
Preliminary treatment is carried out in the same manner as
Polymerization was performed. The results are shown in Table 2. Comparative Example1 Example1In the preliminary treatment of the Ti catalyst component [A]
Except that 1 mmol of titanium tetrachloride was not added
Is an example1Preliminary treatment was performed in the same manner as described above. or
Example of polymerization1Was performed in the same manner as described above. The polymerization results are shown in Table 2.
did. Example2 [0089] [Preparation of solid Ti catalyst component [A]] In a 400 ml flask
Add 6 g of flaked Mg metal and 100 ml of n-hexane.
After washing at 68 ° C. for 1 hour, it was dried with nitrogen. Then
After adding 52 g of ethyl iate and heating to 65 ° C., 5 ml of methyl iodide
Add 0.1 ml of a solution of 1 g of iodine, and further add 50 ml of n-hexane.
A solution consisting of 25 g of n-BuCl in medium was added over 1 hour.
The temperature of the mixture was maintained at 70 ° C. for 6 hours. After reaction 50
Washed 6 times using n-hexane at ℃. Obtained in this way
7 g of the solid obtained are mixed with 100 ml of TiCl._FourPhthalic acid after suspended in
Add 5.5 mmol of diisobutyl and react at 120 ° C for 1 hour.
After the reaction, remove the supernatant with decantation and repeat
100 ml TiCl_FourAt 120 ° C for 1 hour
Got it. After the reaction is complete, wash thoroughly using hexane.
Thus, a solid Ti catalyst component [A] was prepared. The Ti catalyst component
The composition of [A] is titanium 2.8% by weight, chlorine 60% by weight,
19% by weight of gnesium and diisobutyl phthalate 1
1.3% by weight. [0090] [Pretreatment of Ti catalyst component [A]]referencePreliminary treatment of Example 1
In the above, the used Ti catalyst component [A]referenceT of Example 1
Except for replacing the i catalyst component with the above Ti catalyst componentreferenceAn example
Preliminary treatment is carried out in the same manner as
Polymerization was performed. The results are shown in Table 2. Comparative Example2 Example2In the preliminary treatment of the Ti catalyst component [A]
Except that 1 mmol of titanium tetrachloride was not added.
Is an example2Preliminary treatment was performed in the same manner as described above. or
Example of polymerization2Went as well. The polymerization results are shown in Table 2.
did. Example3-6 Example1Used in the preparation of the Ti catalyst component [A]
Table 3 shows di-n-octyl cyclohexanedicarboxylate.
Of the Ti catalyst component [A] instead of the electron donor
Diphenyl dimethate used for pretreatment and polymerization of propylene
Except that xysilane was replaced by the electron donor shown in Table-3
Example1Preparation of Ti catalyst component [A] was carried out in the same manner as described above.
Then, the pretreatment of the Ti catalyst component [A] was performed.
Thereafter, propylene was polymerized. Table 3 shows the results. Comparative Example3-6 Example3-6In the preliminary treatment of the Ti catalyst component [A]
TiCl₄Example except that no was added3-6
Pretreatment is performed in the same manner as in
Natsuta Table 3 shows the results. [0094] [Table 1] [0095] [Table 2][0096] [Table 3]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flowchart showing one example of a catalyst preparation method in the method for polymerizing α-olefin of the present invention.

Claims (1)

(57) [Claims] (A) A magnesium compound is pretreated with an alcohol and / or halogen-containing silicon compound having less than 8 carbon atoms and reacted with a tetravalent titanium compound which forms a liquid phase under the reaction conditions to obtain a polycarboxylic acid. magnesium obtained by reacting ester and tetravalent titanium compounds, titanium, high activity titanium solid catalyst component for the halogen and polycarboxylic acid ester as必<br/> Sunari component, (B) the periodic table group 1 (C) Ti (OR) _g X which is soluble in an inert organic medium
_4-g (R is a hydrocarbon group, X is a halogen, 0 ≦ g ≦ 4)
And a tetravalent titanium compound represented by the formula (D): R _n Si (OR ¹ ) _4-n (wherein R and R
¹ is an alkyl group, cycloalkyl group, aryl group or alkenyl group, 0 ≦ n ≦ 3, provided that n R and (4-n) OR ¹ groups may be the same or different. Α-olefin is prepolymerized in the presence of a catalyst formed from the silicon compound represented by the formula (1), and α-olefin is polymerized in the presence of the resulting α-olefin prepolymerized catalyst. -Method for polymerizing olefins.