JPH06184228A - Catalyst for polymerizing olefin and production of ethylene-alpha-olefinic copolymer using the same catalyst - Google Patents

Abstract

PURPOSE:To obtain the subject new catalyst, composed of a specific solid catalyst component and an organoaluminum compound containing Al-O bond, having a sufficiently high activity based on both the solid catalyst and a transition metal and capable of providing a copolymer, good in powder properties and having a narrow compositional distribution. CONSTITUTION:This catalyst is composed of (A) a solid catalyst component obtained by reacting a reactional mixture of (i) a zirconium compound of formula I [(C5R<2>n) is (substituted)cyclopentadienyl; R<2> is H or 1-20C hydrocarbon; R<1> is 1-4C alkylene which is a group connecting the two groups (C5R<2>n); R<3> and R<4> are 1-20C hydrocarbon, halogen, etc.; (m) is O or 1; (n) is 5 when (m) is 0 and 4 when (m) is 1] with (ii) an organosilicon compound containing Si-O bond with (iii) an organomagnesium compound and then bringing the resultant reactional product into contact with (iv) an organoaluminum halide compound of formula II [R<5> is 1-20C hydrocarbon; X is halogen; (c) is 0-3] and (B) an organoaluniinum compound containing Al-O bond.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst. It also relates to a method for producing an ethylene-α-olefin copolymer using the catalyst. More specifically, a solid catalyst component having sufficiently high catalytic activity per solid catalyst and transition metal is used so that the removal of the catalyst residue is unnecessary in various polymerization processes (slurry polymerization, gas phase polymerization, etc.), and the composition distribution is The present invention relates to a method for producing an ethylene-α-olefin copolymer having a narrow particle size and good powder properties.

[0002]

2. Description of the Related Art In recent years, copolymers of ethylene and α-olefins have been produced by various polymerization methods, and may be linear low density polyethylene (hereinafter sometimes referred to as "LLDPE") or low density polyethylene (hereinafter referred to as "LDDPE"). Sometimes referred to as "LDPE"), and is widely used as a soft resin or an elastomer. Among these, linear low-density polyethylene and soft resins are mainly obtained by using a Ziegler-based catalyst typified by titanium trichloride or Ti / Mg composite system by a gas phase method,
It is manufactured by a slurry method, a solution method, a high-pressure ionic polymerization method, or the like. These composition distributions are generally wide, and there are problems such as poor transparency due to the presence of highly crystalline components, and tackiness and stickiness of molded products due to low crystalline or amorphous components. .

On the other hand, as a new Ziegler type olefin polymerization catalyst, a catalyst composed of a zirconium compound and an aluminoxane has been recently proposed. For example, a catalyst system composed of a biscyclopentadienyl zirconium compound and an aluminoxane (Japanese Patent Publication No. 4-12283), a catalyst system composed of a metallocene compound containing two or more different IVb, Vb and VIb metals and an alumoxane (special Kaisho 60
No. 35006, JP-A-60-35008), and a catalyst system composed of alumoxane and a metallocene compound having a cyclopentadiene having a substituent as a ligand (JP-A-60-35007). With these catalyst systems, the catalytic activity is remarkably high, and although a copolymer having a narrow composition distribution can be obtained, these catalyst systems are soluble in the polymerization system, and the bulk specific gravity of the copolymer, powder properties, etc.
From an industrial point of view, it is still insufficient.

Many attempts have been made to improve the above problems by using a catalyst in which a metallocene compound and / or aluminoxane is supported on a porous compound such as silica or alumina. For example, a catalyst system formed by reacting an aluminum trialkyl with an inorganic substance containing a metallocene compound and water (JP-A-61-31404), a reaction product of a metallocene compound and alumoxane is supported on an inorganic oxide. Catalyst system (Japanese Patent Laid-Open No. 61-108610)
JP-A-61-296008), a catalyst system comprising a reaction mixture of a reaction product of a trialkylaluminum and an alumoxane with an inorganic oxide and a metallocene compound (JP-A-61-276805), organic A catalyst system comprising a solid catalyst component in which a metallocene compound treated with a metal compound is supported on a fine particle carrier and alumoxane (JP-A-63-22804), a catalyst system comprising a reaction product of a metallocene compound and a metal oxide, and alumoxane. (JP-A-1-101315, JP-A-1-259004) and the like. When these catalyst systems are used, a copolymer having a narrow composition distribution can be obtained, but the catalytic activity is remarkably reduced as compared with the above-mentioned soluble catalyst, and the powder properties of the copolymer are still insufficient. .

Further, a catalyst system comprising a reaction product of a metallocene compound and an organomagnesium compound and alumoxane (JP-A-63-168409, JP-A-63-17).
It is hard to say that the performance is sufficiently satisfactory in terms of catalytic activity, molecular weight controllability, etc., even in Japanese Patent No. 5004).

[0006]

Under the present circumstances,
The present invention uses a solid catalyst component having a sufficiently high catalytic activity per solid catalyst and per transition metal so that the removal of the catalyst residue is unnecessary, and the ethylene-α-olefin copolymer having a narrow composition distribution and a good powder property is used. It is intended to provide a method for producing a polymer.

[0007]

The present invention provides (A) (1) the general formula R ¹ _m (C ₅ R ² _n ) ₂ ZrR ³ R
⁴ (wherein (C ₅ R ² _n ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, R ² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ²
May be the same as or different from each other, and R ² to which two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group are bonded respectively
And may form a ring having 4 to 6 carbon atoms, and R ¹ is 2
A group for connecting ^two (C ₅ R ² _n ) and having 1 to 1 carbon atoms.
4 is an alkylene group, R ³ and R ⁴ are each a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a hydrogen atom, m is 0 or 1, and n is 5 when m is 0. , M is 1, it is 4. ) And a reaction mixture (I) of the zirconium compound represented by the formula (2) and an organosilicon compound having a Si—O bond, and (3) a hydrocarbon which is a reaction product of the organomagnesium compound or the organomagnesium compound and the organometallic compound. The reaction product (II) obtained by reacting with a soluble complex,
(4) General formula R ⁵ _c AlX _3-c (wherein, R ⁵ represents a hydrocarbon group containing 1 to 20 carbon atoms, X represents a halogen atom, and c represents a number of 0 <c <3. Ethylene) and a carbon number of 3 or more by using an olefin polymerization catalyst comprising a solid catalyst component obtained by contacting with an organic aluminum halide compound represented by (4) and (B) an organoaluminum compound having an Al—O bond. Is a method for producing an ethylene copolymer in which one or more α-olefins are copolymerized.

The present invention will be specifically described below. Book
Zirconization used in the synthesis of the inventive solid catalyst component
The compound is the general formula R¹ _m(C_FiveR² _n)₂ZrR³R^Four(formula
Medium, (C_FiveR² _n) Is a cyclopentadienyl group or
A substituted cyclopentadienyl group, R²Is also a hydrogen atom
Or a hydrocarbon group having 1 to 20 carbon atoms, wherein R²Is
They may be the same or different from each other, and cyclopentadiene
Forming an nyl group or a substituted cyclopentadienyl group
R having two adjacent carbon atoms bound to each other²And
R may form a ring having 4 to 6 carbon atoms, and R¹Is two
(C_FiveR² _nA group having 1 to 4 carbon atoms.
An alkylene group, R³And R^FourIs the number of carbon
1 to 20 hydrocarbon groups, halogen atoms or hydrogen atoms
And m is 0 or 1, and n is 5 when m is 0.
And when m is 1, it is 4. ). R
¹Specific examples of methylene, ethylene, propylene, etc.
Can be mentioned. R², R³And R ^FourWith a concrete example of
Is hydrogen, methyl, ethyl, propyl, iso-propyl
Ropyl, butyl, iso-butyl, t-butyl, ami
Le, iso-amyl, hexyl, heptyl, octyl,
Alkyl groups such as 2-ethylhexyl and decyl, phenyl
Aryl, cresyl, xylyl, naphthyl, etc.
Cycloalkyl groups such as chlorhexyl and cyclopentyl,
Allyl group such as propenyl, aralkyl group such as benzyl, etc.
Is exemplified. Also R³, R^FourIs chlorine, bromine, iodine, etc.
May be a halogen atom. R², R³And R^FourAre the same
May also be different.

As specific examples of the zirconium compound, the following can be exemplified. Bis (cyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) methylchlorozirconium, bis (cyclopentadienyl) ) Dichlorozirconium, bis (indenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) ) Zirconium monobromide monohydride, bis (cyclopentadienyl) methyl zirconium hydride, bis (cyclopentadienyl) ethyl Ruconium hydride, bis (cyclopentadienyl) cyclohexyl zirconium hydride, bis (cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (Methylcyclopentadienyl) zirconium monochloride monohydride, bis (indenyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) ethylzirconium monochloride, bis (cyclopenta) Dienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis Cyclopentadienyl) benzyl zirconium monochloride, bis (indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl)
Zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) dibenzylzirconium, ethylenebis ( Indenyl) methylzirconium monobromide, ethylenebis (indenyl) ethylzirconium monochloride, ethylenebis (indenyl) benzylzirconium monochloride, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) Zirconium dibromide, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) Methylzirconium, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4 5, 6, 7
-Tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1)
-Indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride, ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, Ethylene bis (4,7-dimethyl-1-indenyl) zirconium dichloride. Among the above compounds, biscyclopentadienyldimethylzirconium and biscyclopentadienyldichlorozirconium are particularly preferably used.

Used in the synthesis of the solid catalyst component of the present invention
As the silicon compound having a Si—O bond, one of the following
It is represented by a general formula. Si (OR⁶)_pR⁷ _4-p R⁸(R⁹ ₃SiO)_qSiR^Ten ₃ Or (R¹¹ ₂SiO)_r Where R⁶Is a hydrocarbon group having 1 to 20 carbon atoms, R⁷,
R⁸, R⁹, R^TenAnd R ¹¹Is carbonized water having 1 to 20 carbon atoms
A basic group or a hydrogen atom, and m is a number of 0 <p ≦ 4
, Q is an integer of 1 to 1,000, and r is 2 to 1,0
00 is an integer.

Specific examples of the organic silicon compound include the following. Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-iso-
Propoxysilane, di-iso-propoxydi-iso
-Propylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxy Phenylsilane, hexamethyldisiloxane, hexaethyldisiloxane,
Examples include hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, and the like. Among these organosilicon compounds, preferred ones are those of the general formula Si (O
R ⁶ ) _p is an alkoxysilane compound represented by R ⁷ _{4 -p} , preferably 1 ≦ p ≦ 4, and a tetraalkoxysilane compound having p = 4 is particularly preferable. Among the above compounds, tetraethoxysilane and tetrabutoxysilane are particularly preferable.

Next, as the organomagnesium used in the present invention, any type of organomagnesium compound containing a magnesium-carbon bond can be used. Particularly, a Grignard compound represented by the general formula R ¹² MgX (wherein R ¹² represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom) and the general formula R ¹³ R ¹⁴ Mg (in the formula, R A dialkyl magnesium compound or a diaryl magnesium compound represented by ¹³ and R ¹⁴ represents a hydrocarbon group having 1 to 20 carbon atoms is preferably used. Where R ¹² , R
¹³ , R ¹⁴ may be the same or different, and are methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, amyl, iso-amyl, hexyl, octyl, 2-ethylhexyl, phenyl, benzyl. An alkyl group having 1 to 20 carbon atoms, an aryl group,
An aralkyl group or an alkenyl group is shown.

Specifically, as the Grignard compound,
Methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, sec-butyl magnesium chloride, sec-butyl magnesium bromide, tert-butyl magnesium chloride , Tert
-Butylmagnesium bromide, n-amylmagnesium chloride, iso-amylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide and the like are diethyl magnesium, dipropyl magnesium, di-i as compounds represented by R ¹³ R ¹⁴ Mg.
so-propyl magnesium, dibutyl magnesium,
Di-sec-butyl magnesium, di-tert-butyl magnesium, butyl-sec-butyl magnesium, diamyl magnesium, diphenyl magnesium, etc. are mentioned.

Solvents for synthesizing the above organomagnesium compound include diethyl ethyl, dipropyl ether, di-iso-propyl ether, dibutyl ether and di-ether.
iso-butyl ether, diamyl ether, di-is
o-amyl ether, dihexyl ether, dioctyl ether, diphenyl ether, dibenzyl ether,
Ethers such as phenetole, anisole, tetrahydrofuran and tetrahydropyran can be used.
Also, hexane, heptane, octane, cyclohexane,
Hydrocarbons such as methylcyclohexane, benzene, toluene and xylene, or a mixed solvent of ether and hydrocarbon may be used. The organomagnesium compound is preferably used in the form of an ether solution. As the ether compound in this case, an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used.

Also, a hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and organometallic compound can be used. Examples of organometallic compounds include Li, Be, B,
Examples thereof include organic compounds such as Al and Zn.

Organohalogenated aluminum used in the present invention
The nickel compound has the general formula R^Five _cAlX _3-c(In the formula, R^Five
Contains 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms
Represents an organic group, preferably a hydrocarbon group, and X is a halogen atom
Indicates a child, and c indicates a number 0 <c <3. )
It Cl is particularly preferable as X, and c is preferably 1
≦ c ≦ 2, particularly preferably c = 1. R^FiveIs preferred
Ku alkyl, cycloalkyl, aryl, aralkyl
And an alkenyl group. Organic halogenated aluminum
Ethyl aluminum dichloride,
Isobutyl aluminum dichloride, ethyl aluminum
Musesquichloride, isobutylaluminum sesquichlor
Lido, diethyl aluminum monochloride, isobutyl
Examples include aluminum monochloride. These
Chidemo ethyl aluminum dichloride, isobutyl al
Alkyl aluminum dichloride such as minium dichloride
Can be used particularly preferably. Organic aluminum halide
Multiple different organoaluminium halides as um compounds
It is also possible to use um compounds, in which case the halogen
To adjust the amount of organic aluminum halide compound
Triethylaluminum, triisobutylal
Trialkyl aluminum such as minium, or trial
Kenyl aluminum can also be used.

Synthesis of Solid Catalyst Component The solid catalyst component of the present invention is obtained by reacting a reaction mixture of a zirconium compound and an organosilicon compound with an organomagnesium compound and then contacting the organoaluminum halide compound. All synthesis reactions are carried out in an atmosphere of an inert gas such as nitrogen or argon.

First, as a method of reacting a zirconium compound with an organomagnesium compound, a method of adding an organomagnesium compound to a mixture of a zirconium compound and an organosilicon compound, or conversely, a zirconium compound and a zirconium compound in a solution of the organomagnesium compound are added. A mixture of organosilicon compounds may be added.

The zirconium compound and the organosilicon compound are preferably dissolved or diluted in a suitable solvent before use. Such solvents include hexane, heptane, octane, decane, and aliphatic hydrocarbons such as decalin, toluene, aromatic hydrocarbons such as xylene, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane, diethyl ether, dibutyl ether, and diether. Examples of the ether compound include isoamyl ether and tetrahydrofuran. These solvents may be used alone or as a mixture. Particularly, aromatic hydrocarbons are preferably used.

The reaction temperature is preferably -20 ° C to 100 ° C, but may be carried out by heating to about 120 ° C. The dropping time is not particularly limited, but is usually about 30 minutes to 6 hours. After completion of the reaction, a post-reaction may be further carried out at a temperature of 20 to 120 ° C.

The amount of the organic silicon compound used is an atomic ratio of silicon atoms to zirconium atoms in the zirconium compound, Si / Zr = 1 to 100, preferably 3 to 7.
0, particularly preferably 5 to 50.

The amount of the organomagnesium compound used is Zr + Si / Mg = 0.1-10, preferably 0.2-5.0, and particularly preferably, in terms of the sum of zirconium atoms and silicon atoms and the atomic ratio of magnesium atoms. Is 0.5-2.
The range is 0. Reaction product (I) obtained in this reaction
Is subjected to solid-liquid separation, and washed several times with an inert hydrocarbon solvent such as hexane and heptane.

Next, the contact between the reaction product (II) and the organic aluminum halide compound is usually -7 in a slurry state.
It is carried out at a temperature of 0 to 200 ° C., preferably −30 to 150 ° C., more preferably 30 to 100 ° C. for several minutes to several hours. The method for adding the reaction product (II) and the organic aluminum halide compound is arbitrary, and the reaction product (I
Any of a method of adding an organic aluminum halide compound to I), a method of adding a reaction product (II) to an organic aluminum halide compound, a method of simultaneously adding a reaction product (II) and an organic aluminum halide are used. be able to. The reaction ratio of the reaction product (II) and the organic aluminum halide compound can be selected within a wide range. Usually, the amount of the organic aluminum halide compound is 0.01 mmol to 1 g of the reaction product (II).
It is selected in the range of 1 mol, preferably 0.1 mmol to 0.5 mol, and more preferably 0.5 mmol to 0.1 mol.

Examples of the solvent used in this reaction include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, halogenated hydrocarbons such as carbon tetrachloride and dichloroethane, benzene, toluene, xylene and chlorobenzene. Examples thereof include aromatic hydrocarbons and alicyclic hydrocarbons such as cyclohexane and cyclopentane. These solvents are used alone or as a mixture. The solid product thus obtained is subjected to solid-liquid separation and washed several times with an inert hydrocarbon solvent such as hexane or heptane. As such or after drying, it is used as a catalyst for olefin polymerization. In carrying out the present invention, a porous carrier such as silica gel may be allowed to coexist during the reaction of the zirconium compound and the organomagnesium compound, and the catalyst component may be immobilized in the pores thereof. Further, prior to carrying out the olefin copolymerization, the solid catalyst component in the presence of the organoaluminum compound by a known method,
Small amounts of olefins (eg ethylene, propylene, etc.)
Can also be prepolymerized.

In the present invention, the organoaluminum compound used in combination with the above-mentioned solid catalyst component has at least an Al--O bond in the molecule. A typical one is shown below by a general formula. The general formulas [Al (R ³ ) -O] _k and R ³ ₂ Al [Al (R
³ ) —O] _k AlR ³ ₂ (wherein R ³ is a hydrocarbon group having 1 to 8 carbon atoms, k is an integer of 1 or more), and cyclic and chain aluminoxanes are exemplified. You can More preferably, k is an integer of 2-30. Specific examples include tetramethyldialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, and hexylaluminoxane. Particularly preferred is methylaluminoxane.

Aluminoxanes are produced by various methods.
It Preferably they are water, toluene or aliphatic
Trimethyi diluted with a suitable organic solvent such as hydrocarbon
Solution of trialkylaluminum such as aluminum
It is to be made in contact with liquid. For example, alkyl
Aluminum is treated with water in the form of a moist solvent
It Alternatively, trimethylaluminum
Hydrate alkylaluminum with copper sulfate or sulfuric acid No. 1
Desirably it can be contacted with a hydrated salt such as iron. Aluminum
Noxane is made in the presence of hydrated ferrous sulfate
preferable. This method is similar to trimethylaluminum
For example, dilute solution in toluene can be represented by the general formula FeSO _Four・ 7H₂O
By treating with ferrous sulfate.
The ratio is 6 to 7 moles of trimethylaluminum
Desirably about 1 mole of ferrous sulfate. The reaction is meta
Proved by the occurrence of Organic aluminum compound
The amount used is 1 per mol of zirconium atom in the solid catalyst.
Can be selected over a wide range such as ~ 50,000 mol
However, the range of 5 to 20,000 mol is particularly preferable.

Ethylene-α-olefin Copolymerization Method There are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that it is supplied in the presence of water in an inert gas such as nitrogen or argon. . The solid catalyst component and the organoaluminum compound component may be supplied individually or may be contacted in advance and supplied. The polymerization can be carried out over -30 to 200 ° C. The polymerization pressure is not particularly limited, but a pressure of about 3 to 100 atm is desirable from the viewpoint of being industrial and economical. The polymerization method may be either continuous or batch. Further, slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, octane, liquid phase polymerization without solvent or gas phase polymerization is also possible.

The olefin used in the present invention is an olefin having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms and having an unsaturated terminal such as ethylene, propylene, butene-1,4-methylpentene-1, and hexene. -1, octene-1, decene-1 and the like. It is also possible to carry out copolymerization of a plurality of these olefins and copolymerization of these olefins with diolefins having preferably 4 to 20 carbon atoms. As diolefins, 1,4-hexadiene, 1,7-octadiene, vinylcyclohexene, 1,3-divinylcyclohexene,
Examples thereof include cyclopentadiene, 1,5-cyclooctadiene, dicyclopentadiene, norbornadiene, 5-vinylnorbornene, ethylidenenorbornene, butadiene and isoprene.

The present invention is especially a copolymer of ethylene containing at least 90 mol% ethylene with other olefins (especially propylene, butene-1,4-methylpentene-1, hexene-1, octene-1). Can be effectively applied to the manufacture of. Also, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out. It is also possible to add a chain transfer agent such as hydrogen to adjust the molecular weight of the polymer.

[0030]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. Molecular weight is ASTM 1238-57T
The melt index (MI) at a load of 2.160 kg was measured. The α-olefin content was determined by characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (JASCO-302) manufactured by JASCO.
A differential scanning calorimeter (DS) is used as a measure of the composition distribution.
The melting point (Tm) of the copolymer was determined using C). Same α
The smaller the Tm value of the olefin content copolymer, the narrower the composition distribution.

Example 1 (A) Synthesis of Organomagnesium Compound A flask having an internal volume of 1 liter equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was replaced with argon, and then 32.0 g of milled magnesium for Grignard was charged. did. A dropping funnel was charged with 120 g of n-butyl chloride and 500 ml of di-n-butyl ether, and about 30 ml was added dropwise to magnesium in the flask to start the reaction. After starting the reaction
Continue dripping at 50 ° C for 4 hours, and after finishing dripping, 60 ° C
Then, the reaction was continued for another hour. Then, the reaction solution was cooled to room temperature, and the solid content was filtered off. When n-butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid and back-titrated with 1N aqueous sodium hydroxide solution to determine the concentration (phenolphthalein was used as an indicator), the concentration was 2 It was 0.1 mol / l.

(B) Synthesis of Reaction Product A flask having an inner volume of 300 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then 180 ml of toluene and 1.9 of biscyclopentadienylzirconium dichloride were added.
5 g (6.6 mmol) and tetraethoxysilane 4
2 g (202 mmol) was added to make a uniform solution. Next, di-n of the organomagnesium compound synthesized in (A)
-Butyl ether solution 99.3 ml was gradually added dropwise from a dropping funnel over 2 hours while maintaining the temperature in the flask at 45 ° C. After completion of dropping, the mixture was stirred at 60 ° C. for 1 hour and then solid-liquid separated at room temperature.
After repeating repeated washings, the product was dried under reduced pressure to obtain 30.2 g of a light brown solid product.

(C) Synthesis of solid catalyst component After a flask having an internal volume of 100 ml equipped with a stirrer and a dropping funnel was replaced with argon, 50 ml of heptane and 8.6 g of the reaction product obtained in the above (B) were charged. . While maintaining the temperature inside the flask at 60 ° C., 12.4 ml (43 mmol) of an ethylaluminum dichloride / hexane solution was added dropwise. After the dropping was completed, the mixture was stirred at 65 ° C. for another hour, and then solid-liquid separated at room temperature, and hexane 50 ml
The washing was repeated 3 times. Then, it was dried under reduced pressure to obtain 8.2 g of a solid product. The solid product contained 0.30% by weight of zirconium atoms and 19.3% by weight of magnesium atoms.

(D) Copolymerization of ethylene-butene-1 After evacuating a 0.4 l autoclave equipped with a stirrer, 17 g of butene-1 and 83 g of butane were added. After the temperature was raised to 70 ° C., ethylene was added until the partial pressure reached 6 kg / cm ² . Solid catalyst component 9.1 m synthesized in (C) above
g and methylalumoxane (Schering Co. 1.7 m
ol / l) 2.0 mmol was added to initiate polymerization.
Then, polymerization was carried out at 70 ° C. for 1 hour while continuously supplying ethylene and keeping the total pressure constant. After the completion of the polymerization, the produced polymer was dried under reduced pressure at 60 ° C. to obtain 18.7 g of a spherical polymer having an excellent powder property. In this case, the catalytic activity was 2050 g polymer / g solid catalyst · hr and was 6
It was 2.1 ton polymer / mol · Zr · hr. This polymer had MI of 5.2 g / 10 min and ethyl branch of 1
It was 8.3 / 1000C and Tm was 109 ° C.

Comparative Example 1 Biscyclopentadienyl zirconium dichloride dissolved in toluene instead of the solid catalyst component of Example 1.
Example 1 (D) except that 56 × 10 ⁻⁴ mmol was used.
Polymerization was carried out in the same manner as in. The yield of the polymer was 31 g, and the catalytic activity was 87 ton polymer / mol · Zr · hr.
Met. However, MI could not be measured at 30 g / 10 minutes or more. Although the catalytic activity was very high, a practically useful copolymer having a molecular weight could not be obtained.

Comparative Example 2 (A) Synthesis of solid catalyst component A flask having an internal volume of 100 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then 65 ml of toluene and 0.61 of biscyclopentadienylzirconium dichloride were added.
g (2.1 mmol) was added to make a uniform solution. Next, the organomagnesium compound 1. synthesized in Example 1 (A).
0 ml was gradually added dropwise from the dropping funnel over 2 hours while maintaining the temperature in the flask at 45 ° C. After stirring at 60 ° C for an additional 1 hour, solid-liquid separation was performed at room temperature, and hexane 5 was added.
Washing with 0 ml was repeated three times, followed by drying under reduced pressure to obtain 0.3 g of a light brown solid product. The solid product contains 16.4% by weight of zirconium atoms and 6.
The content was 3% by weight.

(B) Copolymerization of ethylene-butene-1 Solid product 3 obtained in (A) above as a solid catalyst component
Polymerization was performed in the same manner as in Example 1 (D) except that 3.2 mg was used. The polymer yield was 25.5 g, and the catalyst activity was 0.4 ton-polymer / mol · Zr · hr. The MI of this polymer was 13.7 g / 10 minutes, and the ethyl branch was 22.5 co / 1000C. The catalytic activity was lower than that of Example 1.

Comparative Example 3 (A) Synthesis of Solid Catalyst Component A flask having an inner volume of 200 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then 65 ml of toluene and 0.65 of biscyclopentadienylzirconium dichloride.
g (2.2 mmol) and tetraethoxysilane 1
4.0 g (67.4 mmol) was added to make a uniform solution. Next, 33.1 ml of a di-n-butyl ether solution of the organomagnesium compound synthesized in Example 1 (A) was added,
While maintaining the temperature in the flask at 45 ° C., the solution was gradually added dropwise from the dropping funnel over 2 hours. After completion of the dropping, the mixture was further stirred at 60 ° C. for 1 hour, solid-liquid separated at room temperature, repeatedly washed with 50 ml of hexane three times and dried under reduced pressure to obtain 9.8 g of a light brown solid product. The solid product contains 0.38% by weight of zirconium atom and 1 magnesium atom.
It was contained in an amount of 8.4% by weight.

(B) Copolymerization of ethylene-butene-1 Example 1 except that 30.0 mg of the solid product obtained in (A) above was used in place of the solid catalyst component of Example 1.
Polymerization was carried out in the same manner as in (D). Polymer yield is 12g
Thus, a spherical polymer having an excellent powder property was obtained. The catalyst activity in this case is 400 g polymer / g solid catalyst / hr,
It was 9.5 ton polymer / mol · Zr · hr, which was low. The MI of this polymer was 2.2 g / 10 minutes, the ethyl branch was 19.6 co / 1000 C, and the Tm was 109 ° C.

Comparative Example 4 (A) Synthesis of solid catalyst component A flask having an inner volume of 100 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then a styrene-divinylbenzene copolymer (average particle size: 50 μm, porosimeter As a result of the measurement, the pore volume (cc / g) (hereinafter abbreviated as dVp) in the pore radius of 100 to 5,000Å is dVp.
= 1.05 cc / g. ) Was dried under reduced pressure at 80 ° C for 30 minutes, 7.4 g, heptane 37 ml, tetrabutoxytitanium 0.67 g (2.0 mmol) and tetraethoxysilane 7.1 g (34 mmol) were added and 30 ° C was added.
And stirred for 45 minutes.

Next, 18 ml of the organomagnesium compound synthesized in (A) was added dropwise from the dropping funnel over 45 minutes while maintaining the temperature in the flask at 5 ° C. After completion of the dropping, the mixture was stirred at 5 ° C. for 45 minutes and further at 30 ° C. for 45 minutes, washed twice with 30 ml of hexane and dried under reduced pressure to obtain 12.6 g of a brown solid product.

After replacing the flask having an inner volume of 500 ml with argon, 12.6 g of the solid product synthesized by the reduction reaction of the above (B), 42 ml of toluene and 3.7 ml (13.2 mmol) of diisobutyl phthalate were added. In addition,
The reaction was carried out at 95 ° C for 1 hour. After the reaction, solid-liquid separation was performed, and washing with 40 ml of toluene was performed twice. After washing, add 40 ml of toluene and 0.5 ml of butyl ether to the flask.
(3 mmol) and titanium tetrachloride 7.6 ml (68 mmol) were added, and the reaction was carried out at 95 ° C. for 3 hours. After completion of the reaction, solid-liquid separation was performed at 95 ° C, and toluene 40 was added at the same temperature.
It was washed twice with ml. 2 more with 40 ml of hexane
After repeating washing twice, it was dried under reduced pressure to obtain 11.3 g of a brown solid catalyst component. The solid catalyst component contained 0.55% by weight of titanium atoms, 7.2% by weight of magnesium atoms, and 1.5% by weight of phthalic acid ester.

(B) Copolymerization of ethylene-butene-1 After evacuating a 0.4 l autoclave equipped with a stirrer, 25 g of butene-1 and 75 g of butane were added. After the temperature was raised to 70 ° C., hydrogen was added at a partial pressure of 2.3 kg / cm ² and ethylene was added at a partial pressure of 6 kg / cm ² . 3 mm of the solid catalyst component synthesized above and 2.0 mm of triethylaluminum (1.0 mol / l manufactured by Toso Akzo Co., Ltd.)
ol was added to initiate polymerization. After that, continuously supply ethylene and keep the total pressure constant at 70 ° C for 1 hour.
Polymerization was carried out for a time. After the polymerization was completed, the resulting polymer was 6
It was dried under reduced pressure at 0 ° C. The polymer yield was 28.8 g. In this case, the catalytic activity is 900 g polymer / g solid catalyst · hr, and 7.8 ton polymer / mol · Ti · hr.
Met. The MI of this polymer was 1.3 g / 10 minutes, the ethyl branch was 20.8 co / 1000 C, and the Tm was 124 ° C.

[0044]

EFFECTS OF THE INVENTION A solid catalyst component having sufficiently high catalytic activity per solid catalyst and per transition metal is used so that removal of catalyst residue is unnecessary, and ethylene-α having a narrow composition distribution and good powder properties is used. -Olefin copolymers can be produced.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention. This flowchart is a typical example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (2)

[Claims] 1. (A) (1) The general formula R ¹ _m (C
₅ R ² _n ) ₂ ZrR ³ R ⁴ (wherein (C ₅ R ² _n ) is a cyclopentadienyl group or a substituted cyclopentadienyl group, and R ² is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms. A hydrogen group, R ²
May be the same as or different from each other, and R ² to which two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group are bonded respectively
And may form a ring having 4 to 6 carbon atoms, and R ¹ is 2
A group for connecting ^two (C ₅ R ² _n ) and having 1 to 1 carbon atoms.
4 is an alkylene group, R ³ and R ⁴ are each a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom or a hydrogen atom, m is 0 or 1, and n is 5 when m is 0. , M is 1, it is 4. ) And a reaction mixture (I) of the zirconium compound represented by the formula (2) and an organosilicon compound having a Si—O bond, and (3) a hydrocarbon which is a reaction product of the organomagnesium compound or the organomagnesium compound and the organometallic compound. The reaction product (II) obtained by reacting with the soluble complex is (4)
General formula R ⁵ _c AlX _3-c (In the formula, R ⁵ is 1 to 2 carbon atoms.
It represents a hydrocarbon group containing 0, X represents a halogen atom, and c represents a number of 0 <c <3. ) A catalyst for olefin polymerization, which comprises a solid catalyst component obtained by contact with an organic aluminum halide compound represented by the formula (4) and (B) an organic aluminum compound having an Al-O bond. 2. A method for producing an ethylene-α-olefin copolymer, which comprises copolymerizing ethylene and one or more α-olefins having 3 or more carbon atoms with the catalyst for olefin polymerization according to claim 1.