JP2000026522A - Olefin polymerization catalyst and polymerization of olefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a catalyst capable of producing highly stereoregular polyolefins with wide molecular weight distribution and good moldability in high polymerization activity. SOLUTION: This catalyst is composed of [A] a solid titanium catalytic component comprising magnesium, titanium, a halogen and an electron donor, wherein the titanium is not substantially lost even by washing with hexane at room temperature and the reduction in the titanium content is <15 wt.% when washed with o-dichlorobenzene at 90 deg.C, [B] an organoaluminum compound, and [C] an organosilicon compound having cyclic amino group and at least one 1-10C alkoxy group. The other objective method for polymerizing an olefin comprises using the above catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a catalyst for olefin polymerization capable of producing a polyolefin and a method for polymerizing olefin. The present invention relates to a method for producing propylene and a propylene-based copolymer.

2. Description of the Related Art Conventionally, Ziegler-Natta catalysts comprising a titanium catalyst component and an organoaluminum compound have been widely used as catalysts for producing polyolefins. In particular, a carrier-supported solid titanium catalyst component has been used as the titanium catalyst component. The catalyst exhibits high polymerization activity. Among such solid titanium catalyst components, a catalyst using a magnesium chloride-supported titanium catalyst component exhibits high polymerization activity and, when olefins such as propylene and butene are polymerized, polyolefins having high stereoregularity are produced. Can be manufactured. A novel olefin polymerization catalyst such as a solid titanium catalyst component supported on magnesium chloride and an electron donating compound (electron donor) as a third component together with an organoaluminum compound, aiming at a catalyst capable of producing a polyolefin having higher stereoregularity. ) Has been proposed. Such a solid titanium catalyst component is prepared by contacting a titanium compound, a magnesium compound, an electron donor, and the like, and the solid titanium catalyst thus prepared has active points having different performances from each other. It is considered that there exist active sites which exist as different active sites and by-produce the low stereoregular polyolefin. In order to reduce the number of active sites that by-produce such low stereoregularity polyolefins, for example, JP-A-59-124909 discloses that a titanium compound with an aromatic hydrocarbon such as toluene,
A method for washing a solid titanium catalyst component obtained by bringing a magnesium compound and an electron donor into contact with each other has also been proposed.

As described above, in the method using the electron donor alone or the method for washing the solid titanium catalyst component with an aromatic hydrocarbon, the activity causing the by-product of a low stereoregular polyolefin is obtained. Either to remove the points or to remove the active donors as well as to remove the electron donor even if they can be removed, the amount of low stereoregular polyolefin in the resulting polyolefin is further reduced, and at the same time the high stereoregular polyolefin is removed. A method that can obtain higher activity has been desired. In particular, it is possible to produce a polyolefin having a low molecular weight distribution with a low content of a low stereoregular polyolefin with high activity so that a polyolefin having improved moldability, for example, a fluidity (eg, MFR value) upon melting can be increased. There has been a desire for a catalyst for olefin polymerization and a production method that can be produced. The present invention has been made in view of the prior art as described above, and has a low by-product amount of a low stereoregular polyolefin, and has a solid form capable of producing a high stereoregular polyolefin with high activity. An object of the present invention is to provide a method for polymerizing an olefin using a titanium catalyst, a prepolymerization catalyst containing the solid titanium catalyst, and a catalyst for olefin polymerization. It is another object of the present invention to provide a method for producing propylene polymerization or copolymer.

[Means for Solving the Problems]

SUMMARY OF THE INVENTION The olefin polymerization catalyst according to the present invention contains magnesium, titanium, halogen and an electron donor, and (1) has a titanium content of 2.5% by weight or less;
(2) the total content of magnesium and halogen is 65% by weight or more and less than 92% by weight, (3) the electron donor content is 8 to 30% by weight, and (4) the electron donor / titanium (weight (Ratio) is 7-40, (5) titanium is not substantially desorbed by hexane washing at room temperature, and 90 ° C.
Solid titanium catalyst component having a reduction rate of titanium content of less than 15% by weight when washed with o-dichlorobenzene
[A], [B] an organoaluminum compound component and [C] an organosilicon compound having a cyclic amino group and at least one alkoxy group having 1 to 10 carbon atoms. The above-mentioned olefin polymerization catalyst is a preferable polymerization catalyst particularly for polymerization using propylene. Also,
Prepolymerization catalyst for olefin polymerization according to the present invention,
The catalyst component comprising [A] a solid titanium catalyst component, [B] an organoaluminum compound component, and [C] an organosilicon compound contains an olefin having 2 or more carbon atoms in an amount of 0.1 to 1 g per [A] solid titanium catalyst component. It is characterized by being prepolymerized in an amount of from 01 to 2000 g. The method for polymerizing olefins according to the present invention is characterized in that olefins are polymerized or copolymerized in the presence of the olefin polymerization catalyst, and olefins can be polymerized with high activity.
It is possible to produce a highly stereoregular polyolefin having a low generation of low stereoregular components and a wide molecular weight distribution and excellent moldability. Especially in the presence of an olefin polymerization catalyst,
A method for producing a propylene-based random copolymer in which propylene is copolymerized with at least one olefin selected from ethylene and an olefin having 4 to 20 carbon atoms can be suitably produced.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the solid titanium according to the present invention will be described.
Method for producing catalyst component, solid titanium catalyst component and
Prepolymerization catalyst containing solid titanium catalyst component, olefin
A polymerization catalyst and a method for polymerizing an olefin will be described.
In the present invention, the term "polymerization" refers only to homopolymerization.
Is sometimes used to mean not only copolymerization but also
The term “polymer” is used not only for homopolymers but also for copolymers.
It is sometimes used in a sense that includes polymers. FIG.
Next, a process for preparing a solid titanium catalyst component, this solid titanium
Example of the preparation process of an olefin polymerization catalyst containing a catalyst component
Show. [A] Method for producing solid titanium catalyst component In the method for producing a solid titanium catalyst component according to the present invention,
Contains gnesium, titanium, halogen and electron donor
And desorption of titanium by washing with hexane at room temperature
Solid titanium (i) without
The polar compound (ii) which is 0.50 to 4.00 Debye is mixed with 40
C. or higher, and contains titanium in the solid titanium (i).
The amount of the electron donor / titanium
Produces solid titanium catalyst component (weight ratio) is 7 or more
are doing. The above solid titanium (i) is converted to magnesium
Compounds, titanium compounds and electron donors by various methods
Can be prepared by contacting
Although the preparation method is not limited, in the present invention, (a) liquid state
Magnesium compound and (b) a titanium compound in a liquid state
And (c) contact with an electron donor to obtain solid titanium (i).
Preferably, all solids are produced. First solid
For each component method used for the preparation of glassy titanium (i)
Show physically. (A) Magnesium compound In the present invention, when preparing solid titanium (i),
Gnesium compounds are preferably used in liquid form
No. This liquid state magnesium compound is magnesium
The compound itself may be in a liquid state.
Or a solid magnesium compound.
Was formed in the magnesium compound solution by the solvent
It may be something. With such a magnesium compound
A magnesium compound having a reducing ability
Magnesium compounds that have no function
You. As a magnesium compound having a reducing ability, for example,
For example, an organomagnesium compound represented by the following formula is given.
be able to. R_2-nMgX_n In the formula, n is 0 ≦ n <2, and R is hydrogen or carbon atom 1
An alkyl group having from 20 to 20; an aryl group having from 6 to 21 carbon atoms;
Is a cycloalkyl group having 5 to 20 carbon atoms, n is 0 and
In some cases, the two Rs may be the same or different. X is
Halogen. Organic magne with such reducing ability
Specific examples of the calcium compound include dimethylmagnesium.
, Diethylmagnesium, dipropylmagnesium
, Dibutyl magnesium, diamyl magnesium, di
Hexyl magnesium, Didecyl magnesium, Octi
Rubutylmagnesium, ethylbutylmagnesium, etc.
Dialkylmagnesium compound, ethyl chloride magnesium
, Propyl magnesium chloride, butyl magnesium chloride
, Hexyl magnesium chloride, amyl chloride
Alkyl magnesium halides such as um, butyl eth
Magnesium xium, ethyl butoxymagnesium, octane
Alkyl magnesium, such as tilbutoxy magnesium
Alkoxide, other butylmagnesium hydride
And the like. Magnesium compounds without reducing ability
Specific items include magnesium chloride and magnesium bromide.
C, magnesium iodide, magnesium fluoride, etc.
Magnesium logenide, methoxymagnesium chloride, d
Magnesium oxychloride, Magnesium isopropoxy chloride
Um, butoxymagnesium chloride, octoxymagnesium chloride
Alkoxy magnesium halides such as nesium
Magnesium chloride, methylphenoxy chloride
Allyloxymagnesium halides such as arsenic, ethoxy
Simmagnesium, isopropoxymagnesium, butoki
Simagnesium, n-octoxymagnesium, 2-ethyl
Alkoxy magnesium such as hexoxy magnesium
System, phenoxymagnesium, dimethylphenoxymag
Allyloxymagnesium such as nesium, laurate
Magnesium such as gnesium and magnesium stearate
And the like. Other
Use of magnesium metal and magnesium hydride
it can. Magnesium compounds without these reducing ability
Is derived from the above-mentioned magnesium compound having a reducing ability.
Derived compounds or compounds induced during the preparation of catalyst components
It may be a compound. Magnesification without reducing ability
Compound is derived from a magnesium compound having a reducing ability.
For example, a magnesium compound having a reducing ability
With a polysiloxane compound and a halogen-containing silane compound.
Substances, halogen-containing aluminum compounds, esters, al
Coal, halogen-containing compounds, or OH groups or active
What is necessary is just to contact with the compound which has a carbon-oxygen bond. What
Magnesium compound having the above reducing ability and reduction
Non-functional magnesium compounds are the organic metals described below.
Compounds such as aluminum, zinc, boron, beryli
Complexed with other metals such as um, sodium and potassium
Compounds, complex compounds, or other metals
It may be a mixture with a compound. In addition, magnesium
May be used alone, and two or more of the above compounds may be used.
You may combine above. Used for the preparation of solid titanium (i)
Magnesium compounds that can be used
Gnesium compounds can be used, but the final solid
In body titanium (i), halogen-containing magnesium
It is preferably present in the form of a compound,
When using a magnesium compound that does not contain
During the reaction, it is preferable to carry out a contact reaction with a halogen-containing compound.
Good. Among these, magnesium which does not have reduction ability
Compounds, particularly halogenated magnesium compounds
Are preferred, and among these, magnesium chloride
System, alkoxy magnesium chloride, allyloxy chloride mug
Nesium is preferred. Magnesium compounds as above
If the magnesium compound is a solid,
It can be made into a liquid state by using a child donor (c-i).
As the electron donor (c-i), as the electron donor (c),
Alcohols, phenols, ketones as described below
, Aldehydes, ethers, amines, pyridines
Etc. can be used. Also tetraethoxytita
, Tetra-n-propoxytitanium, tetra-i-propoxy
Titanium, tetrabutoxytitanium, tetrahexoxytita
, Tetrabutoxyzirconium, tetraethoxydyl
Metal acid esters such as conium can also be used.
Wear. Of these, alcohols and metal acid esters
Are particularly preferably used. Solid magnesium
The solubilization reaction of the compound with the electron donor (c-i)
Contact the gonium compound with the electron donor (c-i)
A method of heating as necessary is generally used. This contact
Usually 0 to 200 ° C, preferably 20 to 180 ° C
Or at a temperature of 50 to 150 ° C. Also the above solubilization
In the reaction, a hydrocarbon solvent (d) may coexist.
Specific examples of such a hydrocarbon solvent include pentane,
Hexane, heptane, octane, decane, dodecane, te
Aliphatic hydrocarbons such as Toradecan and kerosene, cyclopen
Tan, methylcyclopentane, cyclohexane, methyl
Like cyclohexane, cyclooctane and cyclohexene
Unalicyclic hydrocarbons, dichloroethane, dichloropro
Halo such as bread, trichloroethylene, chlorobenzene
Genated hydrocarbons, benzene, toluene, xylene, etc.
Aromatic hydrocarbons and the like are used. (b) Titanium compound In the present invention, the titanium compound (b) in a liquid state is
A tetravalent titanium compound is preferably used. like this
As the tetravalent titanium compound, a compound represented by the following formula:
Can be mentioned. Ti (OR)_g X_4-g In the formula, R is a hydrocarbon group having 1 to 15 carbon atoms, and X is
A logen atom, and 0 ≦ g ≦ 4. Such a compound
As a product, specifically, TiCl_Four, TiBr_Four, TiI_Four 
Such as titanium tetrahalide, Ti (OCH_Three) Cl_Three, T
i (OC_TwoH_Five) Cl_Three, Ti (On-C_FourH₉) Cl_Three, Ti (OC
_TwoH_Five) Br_Three, Ti (O-iso-C_FourH₉) Br_ThreeSuch as trihalogen
Alkoxy titanium, Ti (OCH_Three)_TwoCl_Two, Ti (OC_Two
H_Five)_TwoCl_Two, Ti (On-C_FourH₉)_TwoCl_Two, Ti (OC_TwoH _Five)_TwoBr
_TwoDialkoxytitanium dihalides such as Ti (OC
H_Three)_ThreeCl, Ti (OC_TwoH_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeCl,
Ti (OC_TwoH_Five)_ThreeMonohalogenated trialkoxy such as Br
Shitanita, Ti (OCH_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (On-
C_FourH₉)_Four, Ti (O-iso-C_FourH₉)_Four, Ti (O-2-ethylhex
Sill)_FourSuch as tetraalkoxy titanium
You. Of these, titanium tetrahalide is preferred.
And titanium tetrachloride is particularly preferred. These titanium compounds
Objects can be used in combination of two or more. Above
Tan compounds are hydrocarbons, halogenated hydrocarbons, aromatic carbons
It may be used after diluting with hydrogen chloride. (c) electron donor electron donor (c) used in the preparation of solid titanium (i)
Alcohols, phenols, ketones,
Dehydration, carboxylic acid, organic acid halide, organic acid or none
Ester, ether, acid amide, acid anhydride,
Monia, amine, nitrile, isocyanate, nitrogen-containing ring
Compounds, oxygen-containing cyclic compounds and the like. More
Physically, methanol, ethanol, propanol,
Tanol, pentanol, hexanol, 2-ethylhexyl
Sanol, octanol, dodecanol, octadecyl
Alcohol, oleyl alcohol, benzyl alcohol
Phenylethyl alcohol, cumyl alcohol,
Sopropyl alcohol, isopropyl benzyl alcohol
Alcohols having 1 to 18 carbon atoms, such as
Tanol, trichloroethanol, trichlorohexano
Alcohol containing 1 to 18 carbon atoms such as alcohol
, Phenol, cresol, xylenol, ethylphenol
Phenol, nonylphenol, phenol
Has a lower alkyl group such as milfnol and naphthol
Phenols having 6 to 20 carbon atoms, acetone,
Tyl ethyl ketone, methyl isobutyl ketone, acetoph
3 carbon atoms such as enone, benzophenone, benzoquinone
~ 15 ketones, acetaldehyde, propional
Aldehyde, octyl aldehyde, benzaldehyde, tol
Aldehyde, naphthaldehyde, etc.
Aldehydes, methyl formate, methyl acetate, ethyl acetate,
Vinyl acetate, propyl acetate, octyl acetate, cycloacetate
Hexyl, ethyl propionate, methyl butyrate, valeric acid
Chill, methyl chloroacetate, ethyl dichloroacetate, methac
Methyl lylate, ethyl crotonate, cyclohexanecal
Ethyl bonate, methyl benzoate, ethyl benzoate, benzoate
Propyl perfate, butyl benzoate, octyl benzoate,
Cyclohexyl benzoate, phenyl benzoate, benzoate
Undil, methyl toluate, ethyl toluate, toluy
Amyl luate, ethyl ethyl benzoate, methyl anisate,
Ethyl anisate, ethyl ethoxybenzoate, γ-butyro
Lactone, δ-valerolactone, coumarin, phthalide,
Organic having 2 to 30 carbon atoms such as dimethyl carbonate and ethyl carbonate
Acid esters, acetyl chloride, benzoyl chloride
, Toluic acid chloride, anisic acid chloride, etc.
Acid halides of the formulas 2 to 15, methyl ether, ethyl ether
-Tel, isopropyl ether, butyl ether, amine
Charcoal such as ruether, anisole and diphenyl ether
Ethers of prime numbers 2 to 20, acetic acid N, N-dimethylamide,
Benzoic acid N, N-diethylamide, toluic acid N, N-dimethyl
Acid amides such as amides, methylamine, ethylamido
Dimethylamine, diethylamine, trimethylamine
, Triethylamine, tributylamine, tribenzy
Luamine, tetramethylenediamine, hexamethylenedi
Amines such as amines, acetonitrile, benzonitrile
Nitriles such as toluene and tolunitrile, acetic anhydride,
Acid anhydrides such as tallic acid and benzoic anhydride, pyrrole, methyl
Pyrroles such as lupyrrole and dimethylpyrrole;
Phosphorus; pyrrolidine; indole; pyridine, methylpyri
Gin, ethylpyridine, propylpyridine, dimethylpi
Lysine, ethylmethylpyridine, trimethylpyridine,
Phenylpyridine, benzylpyridine, pyridine chloride
Which pyridines, piperidines, quinolines, isoquino
Nitrogen-containing cyclic compounds such as phosphorus, tetrahydrofuran,
1,4-cineole, 1,8-cineole, pinolfuran,
Chilfuran, dimethylfuran, diphenylfuran, ben
Zofuran, coumaran, phthalane, tetrahydropyran,
Cyclic oxygenated compounds such as pyran and dihydropyran
No. In addition, as the electron donor (c), 1-methoxyethyl
Tanol, 2-methoxyethanol, 4-methoxybutanol
Polyhydroxy compounds such as toluene and 2-butoxyethanol
Ethers can be mentioned as particularly preferred examples.
Further, as the above organic acid ester, represented by the following general formula
Carboxylic acid esters having a skeleton having a
Examples can be given.

Embedded image In the above formula, R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are 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. It is a hydrogen group. R ³ and R ⁴ may be connected to each other to form a cyclic structure. The hydrocarbon groups R ^{1 to} R ⁶ generally have 1 to 15 carbon atoms, and when these are substituted, the substituents include heteroatoms such as N, O, S, and, for example, C- OC, COOR, CO
It has groups such as OH, OH, SO ₃ H, —C—N—C—, and NH ₂ . As such polycarboxylic acid esters, specifically, diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, Diethyl butylmalonate, diethylphenylmalonate, diethyldiethylmalonate, diethyldibutylmalonate, monooctylmaleate, dioctylmaleate, dibutylmaleate, dibutylbutylmaleate, diethylbutylbutylmaleate, diisopropylβ-methylglutarate, Diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acids such as aliphatic polycarboxylic acid esters such as diethyl itaconate and dioctyl citraconic acid, diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate Ester, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate , Di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate,
Aromatic polycarboxylic acid esters such as diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, dibutyl trimellitate, and 3,4-furandicarboxylic acid and, for example, ethanol, n-butanol, i-butanol And heterocyclic polycarboxylic acid esters such as esters with 2-ethylhexanol and the like. Other examples of polycarboxylic acid esters include diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, di-2 sebacate.
And esters of long-chain dicarboxylic acids such as -ethylhexyl. In the present invention, the electron donor
As (c), a polyether compound having two or more ether bonds existing through a plurality of atoms can also be used. Examples of the polyether include carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur, and compounds in which two or more kinds of atoms are present between ether bonds. Of these, a relatively bulky substituent is bonded to the atom between the ether bonds, and 2
Compounds in which a plurality of carbon atoms are contained in atoms existing between two or more ether bonds are preferable, and for example, a polyether represented by the following formula is preferable.

Embedded image(Wherein, n is an integer of 2 ≦ n ≦ 10;¹~ R²⁶Is
Carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, borane
Contains at least one element selected from silicon and silicon
And any R¹~ R²⁶, Preferably R¹~
R²ⁿMay together form a ring other than the benzene ring
In addition, atoms other than carbon may be contained in the main chain. Of these, 1,3-diethers are preferably used,
In particular, 2,2-diisobutyl-1,3-dimethoxypropane, 2-a
Sopropyl-2-isobutyl-1,3-dimethoxypropane, 2-
Isopropyl-2-isopentyl-1,3-dimethoxypropa
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxyprop
Lopan, 2-cyclohexyl-2-isopropyl-1,3-dimethoate
Xipropane, 2-isopropyl-2-s-butyl-1,3-dimethoate
Xypropane, 2,2-diphenyl-1,3-dimethoxypropa
2-cyclopentyl-2-isopropyl-1,3-dimethoxy
Propane or the like is preferably used. And this child
As the donor (c), an organosilicon compound as described below
[C], water, or anionic, cationic, nonionic
A system surfactant can also be used. In the present invention
Is a carboxylic acid among the above as an electron donor (c)
It is preferable to use an ester, especially a polycarboxylic acid.
Esters, polyhydroxy compound esters, especially
Phthalates, aliphatic polyhydroxy compounds A
It is preferred to use ters and acid anhydrides. These
Two or more types of the children (c) can be used in combination. Preparation of Solid Titanium (i) In the present invention, the magnesium compound in a liquid state as described above is used.
(A), titanium compound (b) in liquid state, and electron donation
Preparation of solid titanium (i) by contact with body (c)
it can. When bringing these components into contact with each other,
Using the tan compound (b) once to produce a solid (1)
This solid (1) may be further converted to a liquid state titanium
The compound (b) may be contacted to form a solid (2).
No. Also, a solid is prepared by contacting the components (a) to (c).
At the time of preparation of the magnesium compound (a) in a liquid state.
Use a hydrocarbon solvent (d) as described
Can be. In the present invention, these (a) to (c) are
The solid (1) or (2) is
Is in contact with a polar compound (ii) whose is 0.50 to 4.00 Debye
Can be used directly as solid titanium (i)
Converts the solid (1) or (2) into carbon if necessary.
It is possible to prepare solid titanium (i) by washing with hydrogen solvent.
preferable. When preparing solid titanium (i),
In addition to these compounds, as carriers and reaction aids
Organic containing silicon, phosphorus, aluminum, etc. used
A compound or an inorganic compound may be used. This
As a carrier, Al_TwoO_Three , SiO_Two , B_TwoO_Three , Mg
O, CaO, TiO _Two , ZnO, SnO_Two , BaO, ThO,
Resins such as styrene-divinylbenzene copolymer
No. Among them, TiO_Two , Al_TwoO_Three ,
SiO_Two , A styrene-divinylbenzene copolymer is preferred.
It is used well. From the above components, a solid (1) or
(2) Those who prepare (or directly solid titanium (i))
Examples of the method include the following methods
Can be. The method for preparing solids shown below is in the liquid state.
Preparing a magnesium compound (a)
You. Further, in the following method, an organoaluminum compound
As described later as an organometallic compound [B]
An organic aluminum compound is used. (1) Magnesium
Compound, the above electron donor (c-i) and a hydrocarbon solvent
The liquid magnesium compound (a) consisting of
Contact reaction with a luminium compound to precipitate a solid
After, or while depositing the titanium compound in liquid state (b)
And contact reaction. In this process, the electron donor (c)
Is contacted with the contact product at least once. (2) Contact between the inorganic carrier and the liquid organomagnesium compound (a)
Titanium compound (b) in liquid state and electron donor
(c) is contact-reacted. At this time, the inorganic carrier and the liquid
Halogenated in contact with organic magnesium compound (a)
Reaction with compound and / or organoaluminum compound
May be. (3) Magnesium compound, electron donor (c-i),
Is a liquid state magnet composed of a hydrocarbon solvent.
Mixing of the compound (a) with an inorganic or organic carrier
From the material, the inorganic or inorganic
And then prepare the liquid titanium compound
(b) is contacted. In this process, the electron donor (c)
 Is contacted with the contact product at least once. (4) Magnesium compound, titanium compound in liquid state (b)
 , If necessary, electron donor (c-i) and / or carbonization
A solution containing a hydrogen solvent, an inorganic or organic carrier,
Bring into contact with child (c). (5) Liquid state organomagnesium compound (a) and liquid state
After contacting the titanium compound (b) with the electron donor (c).
 Contact. (6) Liquid halogenated organomagnesium compound (a)
After contact reaction with the containing compound, the titanium compound in the liquid state
The object (b) is brought into contact. In this process, the electron donor
Use (c) at least once. (7) The alkoxy-containing magnesium compound (a) is
Reaction with Titanium Compound (b) and Electron Donor (c)
Let it. (8) Consists of a magnesium compound and an electron donor (c-i)
Complex hydrocarbon solution (magnesium compound in liquid state)
(a)), a titanium compound (b) in a liquid state, an electron donor
(c) and contact reaction. (9) Magnesium compounds and electrons
Liquid complex consisting of donor (c-i) (magnesium in liquid state)
Compound (a)) with an organoaluminum compound
After that, contact reaction with the titanium compound (b) in a liquid state
You. In this process, at least one electron donor (c) is used.
Contact with the contact product. (10) Liquid magnesium compound (a) having no reducing ability and
The titanium compound (b) in a liquid state is reacted with the electron donor (c).
The contact is made in the presence or absence. In this process
Contact the electron donor (c) with the contact product at least once
Let it. (11) The reaction product (solid matter) obtained in (1) to (10)
(1)) was further contacted with the titanium compound (b) in a liquid state.
Touch. (12) The reaction products (solids) obtained in (1) to (10)
(1)), the electron donor (c) and the liquid
The tan compound (b) is brought into contact. The contact of each component as described above is usually performed at -70 ° C to + 200C.
° C, preferably -50 ° C to + 150 ° C, more preferably-
It is performed at a temperature of 30 to + 130 ° C. Solid titanium (i)
The amount of each component used in the preparation of
Can not be specified unconditionally, for example, magnesium
The amount of the electron donor is preferably 0.01 to 10 mol per mol of the compound.
Preferably in an amount of 0.1 to 5 moles, the titanium compound is 0.01
To 1000 mol, preferably 0.1 to 200 mol
Can be. In the present invention, the contact
Forming the solid (1) by the method (8)
Solid by contact method (11) or (12) including method (8)
It is preferable to produce the product (2), especially the contact method
It is preferable to produce solid (1) by (8).
No. Olefin polymerization catalysts containing solids (1)
Because of its high activity in the homopolymerization of pyrene,
Producing a random copolymer of propylene with a low can-soluble content
To give, solid (1) is preferred. More like this
Method, a magnesium compound and an electron donor (c-
i) a liquid state magnesium compound prepared from (a)
And contact the titanium compound (b) in a liquid state,
When contacting the electron donor (c), as the electron donor (c)
Polycarboxylic acid esters and / or polyhydric hydroxy
It is preferable to use a compound ether. In the present invention
Is the solid (1) or (2) thus obtained.
Can be used as it is as solid titanium (i)
Wash this solid with a hydrocarbon solvent at 0-150 ° C.
Preferably. Such hydrocarbon solvents include, for example,
Hexane, heptane, octane, nonane, decane,
Aliphatic hydrocarbon solvents such as tan, toluene, xylene,
Non-halogenated aromatic hydrocarbon solvents such as benzene,
Halogen-containing aromatic hydrocarbon solvents as described below
Is used. Of these, aliphatic hydrocarbon solvents or
Is preferably a halogen-free aromatic hydrocarbon solvent
Can be. When washing solids, the hydrocarbon solvent is
Usually 10 to 500 ml, preferably 2 to 1 g of solid matter
Used in an amount of 0-100 ml. Obtained in this way
Solid titanium (i) is magnesium, titanium, halo
Gen and electron donors. This solid titanium
In (i), when the electron donor / titanium (weight ratio) is 6 or less,
Preferably, there is. This solid titanium (i)
There is no desorption of titanium by washing with hexane. Contact treatment with polar compound (ii) In the present invention, the solid titanium (i) and the dipole
The polar compound (i.
i) to prepare a solid titanium catalyst component [A]
ing. Dipole used for contact with solid titanium (i)
Polar compound having a moment of 0.50 to 4.00 Debye
(ii) (also referred to simply as a polar compound)
Chlorobenzene, o-dichlorobenzene, m-dichloroben
Zen, trichlorobenzene, dichlorotoluene, α, α,
α-trichlorotoluene, o-chlorotoluene, chloride
Halogen-containing fragrances such as benzyl and 2-chlorobenzyl chloride
Group hydrocarbons, 1,2-dichloroethane, 1,1,2,2-tetrachloro
Loethane, 1-chloropropane, 2-chloropropane, 1,2-
Dichloropropane, 1-chlorobutane, 2-chlorobutane,
1-chloro-2-methylpropane, 2-chloro-2-methylpropa
And halogen-containing aliphatic hydrocarbons such as 1-chloropentane
Element, diphenyldichlorosilane, methyltrichlorosila
Halogen-containing Si compounds such as
You. Of these, O-dichlorobenzene, 2,4 di
Halogen-containing aromatic hydrocarbons such as chlorotoluene are preferred.
New Contact between the solid titanium (i) and the polar compound (ii),
Usually 40 to 200 ° C, preferably 50 to 180 ° C
Or at a temperature of 60 to 160 ° C for 1 minute to 10 hours.
Or 10 minutes to 5 hours. In this contact, the polarity
Compound (ii) is usually 1 to 1 g of solid titanium (i).
10,000ml, preferably more than 5-5000ml
Or 10 to 1000 ml. Solid titanium
(I) and the polar compound (ii) under an inert gas atmosphere,
The contact is preferably performed with stirring. For example,
In a glass flask with a stirrer
The slurry of titanium (i) and polar compound (ii) is heated at the above temperature.
The stirrer is operated at 100 to 1000 rpm, preferably 200 to 1000 rpm.
The mixture was stirred at the rotation speed of 800 rpm for the above-mentioned time to form a solid chip.
It is desirable to contact the tan (i) with the polar compound (ii).
No. The solid titanium (i) and the polar compound (ii) after the contact,
It can be separated by filtration. Such a solid chip
The contact between tan (i) and polar compound (ii) results in solid titanium
Solid titanium with reduced titanium content compared to titanium (i)
A medium component is obtained. Specifically, the titanium content is solid
25% by weight or more of titanium (i), preferably 30 to 9%
5% by weight, preferably 40-90% by weight less solid
The titanium catalyst component [A] is obtained. Get as above
The solid titanium catalyst component [A] according to the present invention is
Contains gnesium, titanium, halogen and electron donor
And satisfies the following (1) to (5). (1) Titanium content of this solid titanium catalyst component [A]
Is less than 2.5% by weight, preferably 2.2 to 0.1% by weight.
More preferably 2.0 to 0.2% by weight, particularly preferably 1.8%.
~ 0.3% by weight, most preferably 1.4 ~ 0.4% by weight.
You. (2) The total content of magnesium and halogen is 65 times
% Or more and less than 92% by weight. (3) The content of the electron donor is 8 to 30% by weight. (4) The electron donor / titanium (weight ratio) is preferably 7 or more.
Is more preferably 7.5 to 35, more preferably 8 to 30 and particularly preferably
8.5 to 25. (5) The solid titanium catalyst component [A] is hexane at room temperature.
The titanium is not substantially desorbed by the washing.
The washing of the solid titanium catalyst component with hexane means
Usually 10 to 500 ml is preferable for 1 g of titanium catalyst component.
Or 20 to 100 ml of hexane for 5 minutes
Means Room temperature is 15-25 ° C. Again
The solid titanium catalyst component [A] according to the present invention has a temperature of 90 ° C.
Reduced titanium content when washed with chlorobenzene
Less than 15% by weight, preferably less than 10% by weight.
You. O-Dichlorobenzene of solid titanium catalyst component [A]
The washing is carried out specifically using the solid titanium catalyst component [A] 0.5.
g in 100 ml of o-dichlorobenzene at 90 ° C for 1 hour.
Touching. Where magnesium, halogen
The amounts of titanium, titanium and electron donor were
Weight% per unit weight of the tan catalyst component [A],
Magnesium, halogen and titanium are plasma emission components
By electron analysis (ICP method), the electron donor was gas chromatograph.
Quantified by chromatography. According to the present invention as described above.
Solid titanium catalyst component [A] is a catalyst for olefin polymerization.
When used as a medium component, olefins are polymerized with high activity
Polyolefin with low stereoregularity
Polyolefin with low stereochemistry and high stereoregularity
Can be manufactured. [B] Organometallic compound In the present invention, when forming a catalyst for olefin polymerization,
Together with the solid titanium catalyst component [A] as described above
Organometallic compounds are used. This organometallic compound
Include metals selected from Groups I to III of the periodic table.
Preferably, an organic aluminum compound is used.
Compounds, complex alkyl compounds of Group I metals with aluminum,
Group II metal organometallic compounds and the like can be mentioned.
You. Such organoaluminum compounds are, for example,
It is shown by the notation. R^a _n AlX_3-n (Where R^a Is a hydrocarbon group having 1 to 12 carbon atoms, and X
Is halogen or hydrogen, and n is 1 to 3. ) R^a Is a hydrocarbon group having 1 to 12 carbon atoms such as alkyl
Group, cycloalkyl group or aryl group,
Typically, methyl, ethyl, n-propyl, isopropyl
Pill, isobutyl, pentyl, hexyl, octyl
Tyl, cyclopentyl, cyclohexyl, phenyl
And a tolyl group. Such organic aluminum
As the compound, specifically, trimethylaluminum
Aluminum, triethyl aluminum, triisopropyl aluminum
, Triisobutylaluminum, trioctylurea
Luminium, tri-2-ethylhexyl aluminum, etc.
Trialkyl aluminum, isoprenyl aluminum, etc.
Which alkenyl aluminum, dimethyl aluminum
Chloride, diethylaluminum chloride, diisopropyl
Aluminum chloride, diisobutyl aluminum chloride
Dialkis such as chloride and dimethylaluminum bromide
Aluminum halide, methyl aluminum sesquik
Loride, ethyl aluminum sesquichloride, isopro
Pill aluminum sesquichloride, butyl aluminum
Sesquichloride, ethyl aluminum sesquibromide
Which alkyl aluminum sesquihalide, methyl al
Minium dichloride, ethyl aluminum dichloride,
Isopropylaluminum dichloride, ethylaluminum
Alkali aluminum dihalides such as um dibromide
, Diethyl aluminum hydride, diisobutyl
Alkyl aluminum such as aluminum hydride
Hydride and the like. Also organic aluminum
As the compound, a compound represented by the following formula may also be mentioned.
it can. R^a _nAlY_3-n In the above formula, R^a Is the same as above, and Y is -OR
^b Base_,-OSiR^c _Three Group, -OAlR^d _Two Group, -NR^e _Two 
Group, -SiR^f _Three Group or -N (R^g ) AlR^h _Two In the base
And n is 1-2, R^b , R^c , R^d And R^h Is
Methyl group, ethyl group, isopropyl group, isobutyl group,
A cyclohexyl group or a phenyl group; ^e Is water
Element, methyl group, ethyl group, isopropyl group, phenyl
Group, trimethylsilyl group, etc.^f And R^g Is
Examples include a methyl group and an ethyl group. Such organic aluminum
Specifically, the following compounds may be used as the nickel compound.
Things. (i) R^a _n Al (OR^b)_3-n Dimethyl aluminum methoxide, diethyl aluminum
Muethoxide, diisotyl aluminum methoxide
And (ii) R^a _n Al (OSiR^c)_3-n Et_TwoAl (OSiMe_Three), (Iso-Bu)_TwoAl (OSiM
e_Three), (Iso-Bu)_TwoAl (OSiEt_Three), Etc. (iii) R^a _n Al (OAlR^d _Two)_3-n Et_TwoAlOAlEt_Two, (Iso-Bu)_TwoAlOAl (iso-Bu)_Two
 (Iv) R^a _n Al (NR^e _Two)_3-n Me_TwoAlNEt_Two, Et_TwoAlNHMe, Me_TwoAlNHEt, Et
_TwoAlN (Me_ThreeSi)_Two, (Iso-Bu)_TwoAlN (Me_ThreeSi)_Two 
Etc., (v) R^a _n Al (SiR^f _Three)_3-n (Iso-Bu)_TwoAlSiMe_Three(Vi) R^a _n Al [N (R_g ) -AlR^h _Two ]_3-n Et_TwoAlN (Me) -AlEt_Two, (Iso-Bu)_TwoAlN (Et)
Al (iso-Bu)_Two Such. Further similar compounds,
For example, two or more aluminum atoms through an oxygen atom and a nitrogen atom
May be mentioned as well.
it can. More specifically, (C_TwoH_Five)_TwoAlOAl (C_TwoH
_Five)_Two, (C_FourH₉)_TwoAlOAl (C_FourH₉)_Two, (C_TwoH_Five)
_TwoAlN (C_TwoH_Five) Al (C_TwoH_Five)_Two, And more
List aluminoxanes such as rualuminoxane
Can be. Of the above organoaluminum compounds
But R^a _ThreeAl, R^a _n Al (OR^b )_3-n , R^a _n Al
(OAlR^d _Two )_3-nOrganic aluminum compound represented by
Is preferably used. Group I metals and aluminum
The complex alkylated product is represented by the following general formula. M¹AlR^j _Four (M¹ Is Li, Na, K, and R^j Has 1 to 15 carbon atoms
Specifically, LiAl (C_TwoH_Five)
_Four , LiAl (C₇H_Fifteen)_Four And the like. Group II gold
The organometallic compounds of the genus are represented by the following general formula. R^k R^l M^Two (R^k , R^l Is a hydrocarbon group having 1 to 15 carbon atoms or ha
And are the same or different from each other,
Except when all are halogen. M^Two Is Mg, Z
n, Cd) Specifically, diethyl zinc, diethyl magnesium,
Chill ethyl magnesium, ethyl magnesium chloride
And butylmagnesium chloride. This
These compounds may be used in combination of two or more. [C] Organosilicon Compound The component [C] of the present invention has a cyclic amino group,
Organic having at least one alkoxy group having a prime number of 1 to 10
Silicon compounds are used. Preferred cyclic amino groups
Some are derived from secondary cyclic amine compounds.
I can do it. As the secondary cyclic amine compound, pyrrolidi
Compound, pyrrole compound, pyrroline compound, piperidi
Compounds, pyridine compounds, indoline compounds, India
Compounds, quinoline compounds, isoquinoline compounds,
Rubazole compounds, ethyleneimine compounds, etc.
It is. As specific examples of the secondary cyclic amine compound, the following formula
The compound of.

Embedded image

Embedded image

Embedded image

Embedded image Particularly preferably, the secondary cyclic amino compound is

Embedded image Is mentioned. The component [C] of the present invention can be obtained by reacting a secondary cyclic amine compound with a silicon halide compound. Alternatively, it can be obtained by reacting an alkali metal salt or an alkaline earth metal salt of a secondary cyclic amine compound with tetraalkoxysilane. As the silicon halide compound, Si (OMe) ₂ Cl ₂ , Si (OMe) ₂ Br ₂ , Si (OEt) ₂ Cl
_2, Jiha LOGIS alkoxysilanes such as Si (OEt) ₂ Br ₂ can be exemplified. Examples of the alkali metal salt or alkaline earth metal salt of the secondary cyclic amine compound include a lithium salt and a magnesium salt of the secondary cyclic amine compound. As the tetraalkoxysilane, Si (O
Me) ₄ , Si (OEt) _{4 and the} like. Preferred examples of the organosilicon compound [C] include those represented by the following general formula. R ¹ _m R ² _n Si (OR ³ ) _4-mn (wherein, R ¹ is a cyclic amino group, R ² is a hydrocarbon group having 1 to 18 carbon atoms, and R ³ is a carbon group having 1 to 10 carbon atoms. M and n are integers satisfying 0 <m <4, 0 ≦ n <3, and 0 <m + n <4.) As R ¹ , Those derived from higher cyclic amine compounds can be used. When m ≧ 2, a plurality of R ¹ bonded to a silicon atom may be the same cyclic amino group or an organosilicon compound in which a plurality of R ¹ are different cyclic amino groups. . R ² is an unsaturated or saturated aliphatic hydrocarbon group having 1 to 18 carbon atoms or an aromatic hydrocarbon group, preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 12 carbon atoms. Specifically, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, t- butyl group, a pentyl group, a hexyl group, thexyl group (-C (CH _3)
2 CH (CH ₃ ) ₂ ), octyl, cyclopentyl, cyclohexyl, norbornyl, phenyl, tolyl and the like. A cyclopentyl group, a cyclohexyl group, a phenyl group and the like may have a substituent. Among them, an isopropyl group, a t-butyl group, a texyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, and a norbornyl group are exemplified. R ³ has 1 to 10 carbon atoms
And particularly preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, texyl
_{(-C (CH 3) 2 CH} (CH 3) 2), an octyl group, a cyclopentyl group,
Examples include a cyclohexyl group, a norbornyl group, a phenyl group, and a tolyl group. A cyclopentyl group, a cyclohexyl group, a phenyl group and the like may have a substituent. Among them, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a cyclohexyl group are exemplified. m + n <3, that is, dialkoxy and trialkoxy compounds having a plurality of alkoxy groups are preferred. In this case, those alkoxy groups may be the same or different. It is particularly preferred that the plurality of alkoxy groups are the same as in the compounds specifically shown below.

Embedded image At this time, R ¹ is most preferably any ^one of the following cyclic amino groups.

Embedded imageThese organosilicon compounds [C] may be used in combination of two or more.
Can also be. Olefin according to the present invention
Catalysts for polymerization of magnesium, magnesium, titanium, halogen, etc.
(1) Titanium content is 2.5% by weight
(2) The total content of magnesium and halogen
(5) the weight is 65% by weight or more and less than 92% by weight;
(4) an electron donor having a donor content of 8 to 30% by weight;
/ Titanium (weight ratio) is 7 to 40, and (5)
Titanium is substantially desorbed by xanse washing
No, and washed with o-dichlorobenzene at 90 ° C
[A] whose reduction rate of titanium content is less than 15% by weight
A solid titanium catalyst component, [B] an organometallic compound,
[C] an alcohol having a cyclic amino group and further having 1 to 10 carbon atoms
Organosilicon compounds having at least one xyl group,
Formed from In the present invention, each of these components [A],
When forming an olefin polymerization catalyst from [B] and [C]
Other ingredients can be used as needed,
For example, the aforementioned polyether compound, 2,6-substituted piperidine
, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmeth
Tylenediamine, N, N, N ', N'-tetraethylmethylenedia
Substituted methylene diamines such as
Midazolidine, 1,3-dibenzyl-2-phenylimidazoli
Nitrogen-containing electron donation for substituted imidazolidines such as gin
Body, triethyl phosphite, tri-n-propyl phospha
Site, triisopropyl phosphite, tri-n-butyl phosphate
Sphite, triisobutyl phosphite, diethyl n-
Butyl phosphite, diethyl phenyl phosphite
Phosphorus-containing electron donors such as phosphites, 2,6-
Substituted tetrahydropyrans, 2,5-substituted tetrahydropyrans
Oxygen-containing electron donors such as
Two or more of these can be used in combination. Also in the present invention
Is the formation of a prepolymerization catalyst from each of the above components
May be. The prepolymerized catalyst is a solid titanium catalyst as described above.
Component [A] organometallic compound [B] and optionally
Olefins etc. in the presence of organic silicon compound [C]
It is formed by preliminary (co) polymerization. Prepolymerization
Olefins sometimes used include, for example,
Ren, propylene, 1-butene, 1-pentene, 1-hexene
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl
1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-he
Xene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
1-hexadecene, 1-octadecene, 1-eicosene, etc.
Α-olefins having 2 or more carbon atoms are exemplified. Also described later
Pre-weight other vinyl and polyene compounds
It can be used at the same time. These can be used in combination of two or more.
Is also good. The α-olefin used in the prepolymerization will be described later.
The same as the α-olefin used in the main polymerization,
May also be different. In the present invention, preliminary polymerization is performed.
There is no particular limitation on the method.
The reaction can be performed in a state where the compound is in a liquid state,
The reaction can be carried out in the presence of an inert solvent.
It is also possible to perform under the circumstances. Of these, the inert solvent
In the presence of olefins and each catalyst component in the inert solvent
In addition, it is preferable to carry out prepolymerization under relatively mild conditions.
New At this time, the formed prepolymer dissolves in the polymerization medium.
Under conditions that do not dissolve
However, it is preferable to perform under conditions that do not dissolve.
No. The prepolymerization is usually carried out at about -20 to + 100 ° C, preferably
About -20 to + 80 ° C, more preferably -10 to + 40 ° C
It is desirable to perform at. The prepolymerization is a batch type,
Can be performed in both semi-continuous and continuous systems
You. In the prepolymerization, the concentration of the catalyst in the system in the main polymerization is
Even higher concentrations of catalyst can be used. Pre-polymerization
The concentration of the catalyst component depends on the catalyst component used.
Although the concentration of the solid titanium catalyst component [A] is different,
Normally, about 1 atom of polymerization volume, in terms of titanium atom,
0.001 to 5000 mmol, preferably about 0.01 to 1
000 mmol, particularly preferably 0.1 to 500 mmol
It is desirable that The organometallic compound [B] is a solid
0.01 to 2000 g per 1 g of the titanium catalyst component [A]
Preferably from 0.03 to 1000 g, more preferably 0.0
In an amount such that 5-200 g of the preliminary (co) polymer is formed.
Used in the solid titanium catalyst component [A].
Usually, about 0.1 to 1000 moles, preferably about 0.1
5 to 500 mol, preferably 1 to 100 mol
Can be. At the time of pre-polymerization, the organosilicon compound
[C] is replaced by a titanium atom in the solid titanium catalyst component [A].
Usually 0.01 to 50 moles, preferably 0.05 to 5 moles per mole.
30 mol, more preferably 0.1 to 10 mol
It can be used according to. In the prepolymerization
Can also use a molecular weight regulator such as hydrogen. Up
When the prepolymerized catalyst is obtained in a suspended state as described above
In the next step (main) polymerization, the preliminary polymerization catalyst is
It can be used as a suspension,
The pre-polymerized catalyst thus formed can be used separately. Up
The prepolymerized catalyst as described above is usually an organometallic compound.
[B], an organosilicon compound [C] and olefin
A mixed catalyst is formed, but only the prepolymerized catalyst is
In some cases, it can be used as a combined catalyst. Extra weight
When the organosilicon compound [C] is not used
Is an organosilicon compound together with the prepolymerization catalyst during the main polymerization.
[C] may be used to form an olefin polymerization catalyst.
No. Incidentally, the olefin polymerization catalyst according to the present invention, the above-mentioned
In addition to such components, other useful for the polymerization of olefins
Components can be included. Olefin polymerization method In the olefin polymerization method according to the present invention, as described above
Solid titanium catalyst component [A], organometallic compound [B] and
For the polymerization of olefins consisting of olefins and organosilicon compounds [C]
In the presence of a catalyst, including a catalyst or a prepolymerization catalyst,
Fins are polymerized or copolymerized. Such me
Fins specifically used in prepolymerization
It is possible to use the same α-olefin having 2 or more carbon atoms as in
And cyclopentene, cycloheptene, norbo
Runene, 5-ethyl-2-norbornene, tetracyclodode
Sene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Cycloolefins such as octahydronaphthalene, styrene
Len, dimethylstyrene, allylnaphthalene, allylno
Lebornane, vinyl naphthalene, allyl toluene, ant
Benzene, vinylcyclopentane, vinylcyclohexene
Sun, vinylcycloheptane, allyltrialkylsila
Vinyl compounds such as compounds can also be used. This
Among them, ethylene, propylene, 1-butene, 3-methyl
1-butene, 3-methyl-1-pentene, 4-methyl-1-pen
Ten, vinylcyclohexane, dimethylstyrene, ant
Lutrimethylsilane, allylnaphthalene, etc. are preferred
Used. In addition, a small amount of a diene compound is added to the olefin.
It can also be polymerized. Such a diene compound
Specifically, specifically, 1,3-butadiene, 1,3-pentadiene,
1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene
1,5-hexadiene, 4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 6-methyl-1,6-octadie
7-methyl-1,6-octadiene, 6-ethyl-1,6-octa
Diene, 6-propyl-1,6-octadiene, 6-butyl-1,6-
Octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,
6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,
6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,
6-decadiene, 6-methyl-1,6-undecadiene, 1,7-o
Kutadiene, 1,9-decadiene, isoprene, butadier
, Ethylidene norbornene, vinyl norbornene and
And dicyclopentadiene. They are,
Two or more kinds may be used in combination. In the present invention, the polymerization is
Liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization
It can be carried out in any of the methods. Polymerization is slur
When adopting the reaction mode of Lee polymerization, the reaction solvent
The inert organic solvent described above can be used, and the reaction temperature
In the above, a liquid olefin may be used. polymerization
In this case, the solid titanium catalyst component [A] or the preliminary weight
The combined catalyst was converted to titanium atoms per liter of polymerization volume.
And usually about 0.001 to 100 mmol, preferably
It is used in an amount of about 0.005-20 mmol. Organic gold
In the genus compound [B], the metal atom in the compound [B] is polymerized.
Usually about 1 to 2000 moles per mole of titanium atom in the system
Preferably in an amount of about 2 to 500 moles.
It is. Organosilicon compounds [C] are organometallic compounds
Usually about 0.001 mol per 1 mol of the metal atom of [B]
Used in an amount of from 10 mol to 10 mol, preferably from 0.01 mol to 5 mol.
Can be If a prepolymerization catalyst is used during this polymerization,
Metal compound [B] and organosilicon compound [C]
Sometimes it is not necessary. Along with the prepolymerization catalyst, the components
Contact for olefin polymerization from [B] and / or [C]
When a medium is formed, each of these components [B] and [C]
Can be used in the amounts described above. Hydrogen during polymerization
Can control the molecular weight of the resulting polymer.
As a result, a polymer having a high melt flow rate can be obtained.
In the olefin polymerization method according to the present invention, the olefin species
Type, the type of polymerization, etc.
Temperature of about 20-300 ° C, preferably about 50-150 ° C
At normal pressure ~ 100kg / cm^Two Preferably about 2 to 50 kg
/cm^Two It is carried out under a pressure of In the polymerization method of the present invention
The polymerization can be performed in batch, semi-continuous, or continuous
The method can also be performed. Further polymerization, anti-
The reaction can be performed in two or more stages by changing the reaction conditions. Book
In the invention, an olefin homopolymer may be produced,
Also, a random copolymer or a copolymer of two or more olefins
A block copolymer or the like may be manufactured. The method of the present invention
Is the production of highly stereoregular propylene homopolymer, and
And propylene and ethylene and / or C4-20
Copolymerization of Olefin with Olefin with Low Decane Soluble Content
Particularly suitable for the manufacture of the body. Smell of random copolymer
The amount of comonomer to be reacted with propylene
0 to 500 g of ethylene, preferably 1 kg of propylene
Is 0.5 to 100 g, more preferably 5 to 10 g, carbon
0 to 2000 g, preferably 10 olefins of several or more
１０００1000 g, more preferably 50-500 g.
The obtained copolymer has a propylene unit content of 85 mol% or less.
Above, preferably 90 mol% or more, more preferably 93 mol%
% Or more. Propylene and ethylene and
And / or ethylene of α-olefin copolymer having 4 to 20 carbon atoms
Len content or α-olefin containing 4 to 20 carbon atoms
The amount can be measured as follows. Ethylene content
Amount of ethylene refers to isolated ethylene. Isolated etch
Rene is a series of three or more ethylene units in the polymer chain
Means the ethylene unit of the polymerized part and is isolated
Ethylene content (C_Two ) Is measured as follows
You. That is, Toho Press Seisakusho, Ltd.
Using a pressure molding machine, heat for 2 minutes and 30 seconds,
After performing the punching operation, press at 80 atm for 10 seconds.
You. Subsequently, using a hydraulic forming machine in which cooling water was circulated,
Press at 00 atm for 1 minute to obtain a film. This and
So that the thickness of the resulting film is about 0.3 mm
Use an iron spacer. About the obtained film
And DS-701G type diffraction grating infrared spectrophotometer
800-650cm using a total^-1Infrared absorption spectrum
The vector is measured by transmittance. 760 of the chart obtained
cm^-1Near and 700cm^-1The common tangent of the local maximum point
Pull and set as baseline. 733cm^-1Minimum absorption point
And the transmittance (T%) of 733 cm^-1Waves from the absorption minimum point
Draw a perpendicular to the number line and intersect the perpendicular with the baseline.
Point transmittance (T₀ %), 733 cm^-1Absorbance of
Degree (D₇₃₃ = Log (T₀ / T)). Next, the fox
Vertical ethylene content (C_Two ) Is 733cm^-1Absorbance (D
_{73 Three} ) And the thickness of the film used for the measurement (L (mm))
From the following equation. Isolated ethylene content (%) = 6.17 × (D₇₃₃ / L) C_Four~ C₂₀1-butene as a representative of the α-olefin content of
Content (C_Four ) Can be measured as follows
it can. That is, from 0.5 g of the sample,
Get the film. At this time, the thickness of the obtained film is
An iron spacer is used so as to be about 0.3 mm.
About the obtained film, A-302 type
800-700 cm using a folded grating infrared spectrophotometer^-1Territory
The infrared absorption spectrum of the region is measured by transmittance. Obtained
775 cm of the chart^-1Near and 750cm^-1Nearby
A common tangent to the local maximum is drawn and used as the baseline. 765
cm ^-1The transmittance (T%) of the absorption minimum point of 765 cm^-1
Draw a perpendicular to the wavenumber line from the absorption minimum point of
The transmittance at the intersection with the baseline (T₀ %)
765cm^-1Absorbance (D₇₆₅ = Log (T₀ / T))
calculate. Next, the 1-butene content (C_Four ) Is 733cm
^-1Absorbance (D₇₆₅ ) And the thickness of the film used for the measurement
(L (mm)) is determined by the following equation. 1-butene content (%) = 7.77 × (D₇₆₅ / L)

As described above, when the olefin polymerization catalyst containing the solid titanium catalyst component according to the present invention is used, the amount of polyolefin having low stereoregularity is small, the stereoregularity is high, and the molecular weight distribution is wide. A polyolefin having good moldability can be produced with extremely high polymerization activity.

BEST MODE FOR CARRYING OUT THE INVENTION

EXAMPLES Next, the present invention will be described specifically with reference to examples, but it goes without saying that the present invention is not limited to these examples.

Example 1 [Preparation of solid titanium catalyst component (A)] <Preparation of solid titanium (i)> 7.14 g of anhydrous magnesium chloride
(75 mmol), 37.5 ml of decane and 35.1 ml (225 mmol) of 2-ethylhexyl alcohol were mixed and heated at 130 ° C. for 2 hours to obtain a homogeneous solution. Thereafter, 1.67 g (11.5 mmol) of phthalic anhydride was added to this solution, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature,
200 ml of titanium tetrachloride (TiCl ₄ ) maintained at 20 ° C.
(1.8 mol) over 1 hour. After the dropwise addition, the temperature of the resulting solution was raised to 110 ° C over 4 hours, and when the temperature reached 110 ° C, 5.03 ml (18.8 mmol) of diisobutyl phthalate was added. Stir at the above temperature for another 2 hours. After completion of the reaction for 2 hours, a solid (1) was collected by hot filtration, and the solid
After resuspending in 1 l of TiCl _{4, the} mixture was heated again at 110 ° C. for 2 hours. After the completion of the reaction, the solid part (2) was collected by hot filtration, and washed with toluene and hexane at 100 ° C. The solid part (2) is suspended in 100 ml of hexane,
After stirring with a spatula for about 30 seconds, the mixture was filtered. This operation was repeated until no titanium compound was detected in the filtrate. Solid titanium (i) obtained as described above
Was obtained as a hexane slurry. A part of the solid titanium (i) was collected, dried and analyzed for its composition. The solid titanium (i) contained 2.4% by weight of titanium, 60% by weight of chlorine, 20% by weight of magnesium, and 13% by weight of diisobutyl phthalate. <Contact with o-dichlorobenzene> Next, 100 ml of o-dichlorobenzene was put into a 200 ml glass reactor which was sufficiently purged with nitrogen, and the solid titanium (i) obtained above was converted into 1 titanium atom. 0.0 mmol was charged. 1 inside the reactor
The mixture was kept at 00 ° C. and stirred for 1 hour at a rotation speed of 400 rpm using a stirring blade. After the completion of the heating and stirring, a solid portion was collected by filtration and washed three times with hexane to obtain a solid titanium catalyst component (A). After a part of the solid titanium catalyst component (A) obtained as described above was collected and dried, its composition was analyzed. Solid titanium catalyst component (A)
Contained 1.1% by weight of titanium, 60.0% by weight of chlorine, 20.5% by weight of magnesium and 11.4% by weight of diisobutyl phthalate. Accordingly, the ratio of electron donor / titanium (weight ratio) was 10.36, and the titanium content was 54.2% by weight lower than before contact (solid titanium (i)). [90 ° C. o-dichlorobenzene washing of solid titanium catalyst component (A)] The solid titanium catalyst component (A) obtained above was
0.5 g was collected, placed in a 200 ml glass reactor which was sufficiently purged with nitrogen, and 100 ml of o-dichlorobenzene was added. The temperature inside the reactor was maintained at 90 ° C.
Stirred at rpm for 1 hour. After the stirring, the solid portion was collected by filtration, washed twice with hexane, and dried under reduced pressure. The titanium content of the solid titanium catalyst component (A) after washing was 1.1% by weight. Therefore, the reduction rate of titanium content by washing with o-dichlorobenzene at 90 ° C. was 0% by weight. [Preparation of Preliminary Polymerization Catalyst (I)] 200 ml purged with nitrogen
50 ml of purified hexane was charged into 0.75 mmol of triethylaluminum, and 0.25 mmol of the solid titanium catalyst component (A) obtained above in terms of titanium atom was charged into the glass reactor. Propylene was fed for 1 hour at a rate of 47 liters / hour. After the supply of propylene was completed, the solid part obtained by filtration was washed twice with purified hexane, resuspended in decane, and transferred to a catalyst bottle in its entirety to obtain a prepolymerized catalyst (I). [Main polymerization] 400 ml of purified heptane was charged into an autoclave having an inner volume of 1 liter, and the autoclave was heated to 60 ° C in a propylene atmosphere.
After charging 0.004 mmol of triethylaluminum, 0.4 mmol of bis (perhydroquinolino) -dimethoxysilane, and 0.008 mmol of the prepolymerized catalyst (I) obtained above in terms of titanium atom, After adding 100 ml, the temperature was raised to 70 ° C., and this was maintained for 1 hour to polymerize propylene. During the polymerization, the pressure was kept at 5 kg / cm ² · G. After completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer and a liquid phase. The yield of the white powder polymer after drying was 97.9 g, and 0.2 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 12,240 g-PP / mmol-Ti, 2,810 g-PP / g-catalyst. Table 1 shows the results.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the contact with o-dichlorobenzene and the washing with o-dichlorobenzene were not carried out. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer.

Comparative Example 2 The procedure of Example 1 was repeated except that the organosilicon compound in the main polymerization of Example 1 was changed from bis (perhydroquinolino) -dimethoxysilane to dicyclopentyldimethoxysilane. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer.

Example 2 The procedure of Example 1 was repeated except that the organosilicon compound in the main polymerization of Example 1 was changed from bis (perhydroquinolino) -dimethoxysilane to cyclopentylperhydroquinolinodimethoxysilane. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer.

Example 3 The procedure of Example 1 was repeated except that the organosilicon compound in the main polymerization of Example 1 was changed from bis (perhydroquinolino) -dimethoxysilane to cyclohexylperhydroquinolinodimethoxysilane. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer.

Example 4 The organosilicon compound in the main polymerization of Example 1 was converted from bis (perhydroquinolino) -dimethoxysilane to 2-
The procedure was carried out in the same manner as in Example 1 except that norbornyl perhydroquinolinodimethoxysilane was used. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer.

Example 5 The procedure of Example 1 was repeated, except that the organosilicon compound used in the main polymerization of Example 1 was changed from bis (perhydroquinolino) -dimethoxysilane to perhydroquinolinotrimethoxysilane. Table 1 shows the measurement results of the polymerization activity and the physical properties of the obtained polymer. The decane-soluble component amount of the polymer was measured as follows. A 1-liter flask was charged with 3 g of the sample, 20 mg of 2,6-di-tert-butyl-4-methylphenol, and 500 ml of n-decane, and heated and dissolved at 145 ° C. After dissolution, the mixture was cooled to 23 ° C. over 8 hours and maintained at 23 ° C. for 8 hours. The precipitated solid and an n-decane solution containing the dissolved polymer were separated by filtration through a glass filter. The liquid phase was dried under reduced pressure at 150 ° C. until a constant weight was obtained, and its weight was measured. The amount of polymer dissolved was calculated as a percentage of the weight of the sample. The molecular weight distribution (Mw / Mn) of the polymer was determined by gel permeation chromatography using a TSK mixed polystyrene gel column (G3000-G7000) at 140 ° C.
It was eluted with dichlorobenzene and measured. Bulk specific gravity is JIS
It was measured according to K-6721.

[Table 1]

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[Brief description of the drawings]

FIG. 1 is a solid catalyst according to the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J028 AA01A AB01A AC03A BA02B BB01B BC15B BC16B BC19B BC24B BC27B BC28B BC29B BC30B BC39B DA01 DA02 DA03 DA04 DA05 EB02 EB03 EB04 EB05 EB07 EB08 A04 A02P02A AA09P AA15P AA16P AA17P AA18P AA21P AB00P AB01P AB04P AR03P AR04P AR09P AR11P

Claims (4)

[Claims] 1. The composition contains magnesium, titanium, halogen and an electron donor, (1) the content of titanium is 2.5% by weight or less, and (2) the total content of magnesium and halogen is 65% by weight or more and 92% by weight or less. (3) electron donor content is 8 to 30% by weight, (4) electron donor / titanium (weight ratio) is 7 to 40, and (5) hexane washing at room temperature. Titanium is not substantially desorbed by
And a solid titanium catalyst component [A], [B] an organoaluminum compound component and a titanium content reduction ratio of less than 15% by weight when washed with o-dichlorobenzene at 90 ° C., and
[C] an organosilicon compound having a cyclic amino group and further having at least one alkoxy group having 1 to 10 carbon atoms, the catalyst for olefin polymerization comprising: 2. A catalyst for propylene polymerization comprising [A] a solid titanium catalyst component according to claim 1, [B] an organoaluminum compound component, and [C] an organosilicon compound. 3. The solid titanium catalyst component according to claim 1,
The catalyst component comprising [B] an organoaluminum compound component and [C] an organosilicon compound contains 0.01 to 2000 g of an olefin having 2 or more carbon atoms per 1 g of the [A] solid titanium catalyst component.
Prepolymerization catalyst for olefin polymerization characterized by being prepolymerized in a quantity of 4. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to claim 1 or 3.