JP3237250B2 - Olefin polymerization catalyst and method for producing ethylene-α-olefin copolymer using the catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for olefin polymerization. The present invention also relates to a method for producing an ethylene-α-olefin copolymer using the catalyst. More specifically, in various polymerization processes (slurry polymerization, gas-phase polymerization, etc.), a solid catalyst component having a sufficiently high catalytic activity per solid catalyst and per transition metal is used so that the removal of the catalyst residue is not necessary. The present invention relates to a method for producing an ethylene-α-olefin copolymer having a small particle size and good powder properties.

[0002]

2. Description of the Related Art In recent years, copolymers of ethylene and α-olefin 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 “LLDPE”). It is sometimes referred to as “LDPE”), and is widely used as a soft resin or elastomer. Among them, linear low-density polyethylene and soft resin are mainly produced by a gas phase method using a Ziegler catalyst represented by titanium trichloride or Ti / Mg composite,
It is manufactured by a slurry method, a solution method, a high-pressure ionic polymerization method, or the like. These composition distributions are generally broad, and have problems such as poor transparency due to the presence of highly crystalline components, and stickiness 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 comprising a zirconium compound and an aluminoxane has recently been proposed. For example, a catalyst system composed of a biscyclopentadienyl zirconium compound and an aluminoxane (Japanese Patent Publication No. Hei 4-12283), a catalyst system composed of a metallocene compound containing two or more different IVb, Vb, and VIb group metals and alumoxane (particularly, Kaisho 60
JP-A-35-006, JP-A-60-35008), a catalyst system comprising a metallocene compound having a cyclopentadiene having a substituent as a ligand and alumoxane (JP-A-60-35007). When these catalyst systems are used, the catalyst activity is remarkably high, and a copolymer having a narrow composition distribution can be obtained.However, these catalyst systems are soluble in the polymerization system, and the bulk specific gravity of the copolymer, powder properties, etc.
It is still insufficient from an industrial point of view.

[0004] Further, many attempts have been made to improve the above problems by using a catalyst in which a metallocene compound and / or an aluminoxane is supported on a porous compound such as silica or alumina. For example, a catalyst system comprising a metallocene compound and an inorganic substance containing water reacted with aluminum trialkyl (JP-A-61-31404), a reaction product of a metallocene compound and an alumoxane supported on an inorganic oxide Catalyst system (JP-A-61-108610)
JP-A-61-296008), a catalyst system comprising a metallocene compound and a reaction mixture obtained by reacting an inorganic oxide with a reaction product of a trialkylaluminum and alumoxane (JP-A-61-276805), and an organic compound. Catalyst system comprising alumoxane and a solid catalyst component in which a metallocene compound treated with a metal compound is supported on a fine particle carrier (JP-A-63-22804), 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 significantly reduced as compared with the above-mentioned soluble catalyst, and the powder properties of the copolymer are still insufficient. .

A catalyst system comprising an alumoxane and a reaction product of a metallocene compound and an organomagnesium compound (JP-A-63-168409, JP-A-63-17)
Japanese Patent No. 5004) still does not say that the performance is sufficiently satisfactory with respect to the catalytic activity, the molecular weight controllability and the like.

[0006]

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

[0007]

The present invention provides (A) (1) a compound represented by the following general formula: R ¹ _m (C ₅ R ² _n ) ₂ ZrR ³ R
⁴ (in the formula, (C ₅ R ² _n) is a cyclopentadienyl group or substituted cyclopentadienyl group, R ² is a hydrocarbon group of a hydrogen atom or a carbon number of 1 to 20, R ²
May be the same as or different from each other, and two adjacent carbon atoms forming a cyclopentadienyl group or a substituted cyclopentadienyl group may be bonded to each other by R ²
May form a ring having 4 to 6 carbon atoms together with R ¹
A group linking ^two (C ₅ R ² _n ), wherein
And 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 4 when m is 1. ) And (2) a reaction mixture of an organosilicon compound having a Si-O bond with (3) an organomagnesium compound or a hydrocarbon which is a reaction product of an organomagnesium compound and an organometallic compound. The reaction product (II) obtained by reacting the soluble complex with
(4) 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. Using a solid catalyst component obtained by contacting with an organic aluminum halide compound represented by the formula (1) and (B) an olefin polymerization catalyst comprising an organic aluminum compound having an Al-O bond and ethylene and C3 or more. Is a method for producing an ethylene copolymer by copolymerizing one or more α-olefins.

Hereinafter, the present invention will be described specifically. Book
Zirconium used in the synthesis of the solid catalyst component of the invention
The compound has the general formula R¹ _m(C_FiveR^Two _n)_TwoZrR^ThreeR^Four(formula
Medium, (C_FiveR^Two _n) Is a cyclopentadienyl group or
A substituted cyclopentadienyl group,^TwoIs also a hydrogen atom
Or a hydrocarbon group having 1 to 20 carbon atoms,^TwoIs phase
Cyclopentadiene may be the same or different from each other.
Forming a phenyl or substituted cyclopentadienyl group
Two adjacent carbon atoms are bonded to each other^TwoAnd
And may form a ring having 4 to 6 carbon atoms.¹Is two
(C_FiveR^Two _n), Which has 1 to 4 carbon atoms.
An alkylene group;^ThreeAnd R^FourIs the carbon number of each
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. R^Two, R^ThreeAnd R ^FourExamples of
Hydrogen, methyl, ethyl, propyl, iso-
Propyl, butyl, iso-butyl, t-butyl,
, Iso-amyl, hexyl, heptyl, octyl,
Alkyl groups such as 2-ethylhexyl and decyl;
Aryl, cresyl, xylyl, naphthyl, etc.
Cycloalkyl groups such as clohexyl and cyclopentyl,
Allyl groups such as propenyl, aralkyl groups such as benzyl, etc.
Is exemplified. Also R^Three, R^FourIs chlorine, bromine, iodine, etc.
May be a halogen atom. R^Two, R^ThreeAnd R^FourAre the same
May also be different.

Specific examples of the zirconium compound include the following. Bis (cyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, 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) ethyl zirconium monochloride, bis (cyclopentane 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, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) dibenzyl zirconium, ethylene bis ( (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) Methyl zirconium, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) methyl zirconium monochloride, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylene bis (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.

[0010] Used in the synthesis of the solid catalyst component of the present invention
Examples of the silicon compound having a Si—O bond include:
It is represented by a general formula. Si (OR⁶)_pR⁷ _4-p R⁸(R⁹ _ThreeSiO)_qSiR^Ten _Three Or (R¹¹ _TwoSiO)_r Where R⁶Is a hydrocarbon group having 1 to 20 carbon atoms, R⁷,
R⁸, R⁹, R^TenAnd R ¹¹Is a hydrocarbon having 1 to 20 carbon atoms
And m is a number satisfying 0 <p ≦ 4.
And q is an integer of 1 to 1,000, and r is 2 to 1,0
It is an integer of 00.

Specific examples of the organosilicon 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 thereof include hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, and phenylhydropolysiloxane. Preferred among these organosilicon compounds are those of the general formula Si (O
R ⁶⁾ is an alkoxysilane compound represented by _p R ⁷ _{4 -p,} preferably 1 ≦ p ≦ 4, particularly tetraalkoxysilane compounds of p = 4 is preferable. Among the above compounds, tetraethoxysilane and tetrabutoxysilane are particularly preferred.

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 a general formula R ¹³ R ¹⁴ Mg (wherein R ¹³ and R ¹⁴ represent a hydrocarbon group having 1 to 20 carbon atoms.) A dialkylmagnesium compound or a diarylmagnesium compound represented by the formula: Where R ¹² , R
¹³ and R ¹⁴ may be the same or different and include 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 such as an aryl group,
It represents an aralkyl group or an alkenyl group.

Specifically, as the Grignard compound,
Methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, propyl magnesium chloride, propyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, sec-butyl magnesium chloride, sec-butyl magnesium bromide, tert-butyl magnesium chloride , Tert
- butylmagnesium bromide, n- amyl magnesium chloride, iso- amyl magnesium chloride, phenyl magnesium chloride, phenyl magnesium bromide and the like, diethyl magnesium as a compound represented by R ¹³ R ¹⁴ Mg, dipropyl magnesium, di -i
so-propyl magnesium, dibutyl magnesium,
Examples thereof include di-sec-butylmagnesium, di-tert-butylmagnesium, butyl-sec-butylmagnesium, diamylmagnesium, and diphenylmagnesium.

As a solvent for synthesizing the above-mentioned organomagnesium compound, diethyl ethyl, dipropyl ether, di-iso-propyl ether, dibutyl ether, di-
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,
A hydrocarbon such as methylcyclohexane, benzene, toluene, 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.

A hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and organometallic compound can also be used. Examples of organometallic compounds include Li, Be, B,
Organic compounds, such as Al or Zn, are mentioned.

The organic aluminum halide used in the present invention
The compound of the general formula R^Five _cAlX _3-c(Where R^Five
Contains 1-20, preferably 1-6, carbon atoms
X represents an organic group, preferably a hydrocarbon group, and X represents a halogen atom.
And c indicates a number of 0 <c <3. )
You. X is particularly preferably Cl, and c is preferably 1
.Ltoreq.c.ltoreq.2, particularly preferably c = 1. R^FiveIs preferred
Or alkyl, cycloalkyl, aryl, aralkyl
And alkenyl groups. Organic halogenated aluminum
As aluminum compounds, ethyl aluminum dichloride,
Isobutyl aluminum dichloride, ethyl aluminum
Musesquichloride, isobutyl aluminum sesquichlor
Lido, diethyl aluminum monochloride, isobutyl
Aluminum monochloride and the like can be mentioned. These
Chichimo ethyl aluminum dichloride, isobutyl alcohol
Alkyl aluminum dichloride such as minium dichloride
Can be particularly preferably used. Organic halogenated aluminum
Different organic halogenated aluminum
Compounds can also be used, in this case
Aluminum halide compound to adjust the amount of
With triethyl aluminum, triisobutyl aluminum
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 further contacting it with an organic aluminum halide compound. All the synthesis reactions are carried out under 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 method of adding a zirconium compound and a A mixture of organosilicon compounds may be added.

The zirconium compound and the organosilicon compound are preferably used after being dissolved or diluted in a suitable solvent. Examples of such a solvent include aliphatic hydrocarbons such as hexane, heptane, octane, decane, and decalin; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; diethyl ether; dibutyl ether; Ether compounds such as isoamyl ether and tetrahydrofuran are exemplified. These solvents are used alone or as a mixture. In particular, aromatic hydrocarbons are preferably used.

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

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

The amount of the organomagnesium compound used is Zr + Si / Mg = 0.1 to 10, preferably 0.2 to 5.0, particularly preferably 0.2 to 5.0 in terms of the atomic ratio of the sum of zirconium atoms and silicon atoms and magnesium atoms. Is 0.5-2.
It is in the range of 0. Reaction product (I) obtained by 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 carried out in a slurry state by -7.
The reaction 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 of adding the reaction product (II) and the organic aluminum halide compound is optional, and the reaction product (I)
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, and the like are used. be able to. The reaction ratio between the reaction product (II) and the organic aluminum halide compound can be selected in a wide range. Usually, the amount of the organic aluminum halide compound is from 0.01 mmol to 1 g per 1 g of the reaction product (II).
1 mol, preferably 0.1 mmol to 0.5 mol, 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, chlorobenzene and the like. Examples include aromatic hydrocarbons, 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. Used as it is or after drying as a catalyst for olefin polymerization. In carrying out the present invention, a porous carrier such as silica gel may coexist during the reaction between the zirconium compound and the organomagnesium compound, and the catalyst component may be immobilized in the pores. Prior to performing the olefin copolymerization, a solid catalyst component is added by a known method in the presence of an organoaluminum compound.
Small amounts of olefins (eg ethylene, propylene, etc.)
Can be prepolymerized.

In the present invention, the organoaluminum compound used in combination with the above-described solid catalyst component has at least an Al—O bond in the molecule. Typical examples are shown below by a general formula. General formula [Al (R ³⁾ -O] _k and R ³ ₂ Al [Al (R
³⁾ -O] _k AlR ³ ₂ (where R ³ is to illustrate the cyclic and linear aluminoxanes having a structure represented by the hydrocarbon group having 1 to 8 carbon atoms, k is an integer of 1 or more.) Can be. More preferably, k is an integer of 2 to 30. Specific examples include tetramethyldialuminoxane, tetraethyldialuminoxane, tetrabutyldialuminoxane, tetrahexyldialuminoxane, methylaluminoxane, ethylaluminoxane, butylaluminoxane, hexylaluminoxane and the like. Particularly preferred is methylaluminoxane.

Aluminoxane is produced by various methods.
You. Preferably they use water, toluene or aliphatic
Trimethylene diluted with a suitable organic solvent such as a hydrocarbon
Of trialkylaluminum such as aluminum
It is made by contact with liquid. For example, alkyl
Aluminum is treated with water in the form of a wet solvent
You. In another method, trimethylaluminum
Hydrated copper aluminum sulfate or sulfuric acid
Desirably, it can be contacted with a hydrated salt such as iron. Aluminum
Noxane is formed in the presence of hydrated ferrous sulfate
preferable. This method is analogous to trimethyl aluminum
If the dilute solution in toluene is represented by the general formula FeSO _Four・ 7H_TwoO
And treatment with ferrous sulfate represented by
The ratio is 6 to 7 moles of trimethylaluminum
Desirably, it is about 1 mole ferrous sulfate. Reaction is meta
Is proved by the occurrence of Organic aluminum compounds
Is used in an amount of 1 per mole of zirconium atoms in the solid catalyst.
Can be selected over a wide range, such as ~ 50,000 moles
However, the range of 5 to 20,000 mol is particularly preferable.

Ethylene-α-olefin copolymerization method The method of supplying each catalyst component to the polymerization tank is not particularly limited except that it is supplied in an inert gas such as nitrogen or argon without moisture. . The solid catalyst component and the organoaluminum compound component may be supplied individually or may be supplied in contact with each other in advance. 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 industrial and economical use. The polymerization method may be either a continuous type or a batch type. Slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, and octane, liquid phase polymerization without solvent, or gas phase polymerization are also possible.

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

The present invention relates to a copolymer of ethylene containing at least 90 mol% of ethylene and another olefin (particularly propylene, butene-1,4-methylpentene-1, hexene-1, octene-1). Can be effectively applied to the manufacture of Further, heteroblock copolymerization in which polymerization is carried out in two or more stages can also be easily carried out. In order to control the molecular weight of the polymer, a chain transfer agent such as hydrogen can be added.

[0030]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. The molecular weight is ASTM1238-57T
The melt index (MI) at a load of 2.160 kg was used as a scale. The α-olefin content was determined by the characteristic absorption of ethylene and α-olefin using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCO-302.
As a scale representing the composition distribution, a differential scanning calorimeter (DS)
C) was used to determine the melting point (Tm) of the copolymer. Same α
The smaller the value of Tm, the narrower the composition distribution of the copolymer having an olefin content.

Example 1 (A) Synthesis of an organomagnesium compound A 1-liter flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was purged with argon, and then 32.0 g of milled magnesium for Grignard was charged. did. 120 g of n-butyl chloride and 500 ml of di-n-butyl ether were charged into a dropping funnel, and about 30 ml was dropped into magnesium in the flask to start a reaction. After the reaction starts,
The dropwise addition was continued at 50 ° C. for 4 hours,
The reaction was continued for another hour. Thereafter, the reaction solution was cooled to room temperature, and the solid content was separated by filtration. N-Butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid, and the concentration was determined by back titration with a 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator). 0.1 mol / l.

(B) Synthesis of reaction product After a 300 ml flask equipped with a stirrer and a dropping funnel was purged with argon, 180 ml of toluene and 1.9 biscyclopentadienyl zirconium dichloride were added.
5 g (6.6 mmol) and tetraethoxysilane 4
2 g (202 mmol) were added to obtain a homogeneous solution. Next, di-n of the organomagnesium compound synthesized in (A)
99.3 ml of -butyl ether solution was gradually dropped from the dropping funnel over 2 hours while maintaining the temperature in the flask at 45 ° C. After completion of the dropwise addition, the mixture was further stirred at 60 ° C. for 1 hour, and then subjected to solid-liquid separation at room temperature.
After repeating the washing twice, 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 a 100 ml internal volume 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 in the flask at 60 ° C., 12.4 ml (43 mmol) of an ethyl aluminum dichloride / hexane solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at 65 ° C. for 1 hour, and then subjected to solid-liquid separation at room temperature.
Was repeated three times. Thereafter, the resultant 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 A 0.4-liter autoclave equipped with a stirrer was evacuated, and then 17 g of butene-1 and 83 g of butane were added. After the temperature was raised to 70 ° C., ethylene was added to a partial pressure of 6 kg / cm ² . 9.1 m of the solid catalyst component synthesized in (C) above
g and methylalumoxane (1.7m manufactured by Schering)
(ol / l) 2.0 mmol was added to initiate polymerization.
Thereafter, polymerization was carried out at 70 ° C. for 1 hour while continuously supplying ethylene and keeping the total pressure constant. After completion of the polymerization, the resulting polymer was dried under reduced pressure at 60 ° C. to obtain 18.7 g of a spherical polymer having excellent powder properties. The catalytic activity in this case is 2050 g polymer / g solid catalyst · hr,
It was 2.1 ton polymer / mol · Zr · hr. The MI of this polymer was 5.2 g / 10 min, and the ethyl branch was 1
8.3 / 1000C, 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 described above. 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 min or more. Although the catalyst 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 After replacing a 100 ml flask equipped with a stirrer and a dropping funnel with argon, 65 ml of toluene and 0.61 of biscyclopentadienyl zirconium dichloride were added.
g (2.1 mmol) was added to obtain a homogeneous solution. Next, the organomagnesium compound synthesized in Example 1 (A) 1.
While maintaining the temperature in the flask at 45 ° C., 0 ml was gradually dropped from the dropping funnel over 2 hours. After further stirring at 60 ° C. for 1 hour, the mixture was separated into solid and liquid at room temperature.
Washing was repeated three times with 0 ml, 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 6.30% by weight of magnesium atoms.
3% by weight was contained.

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

Comparative Example 3 (A) Synthesis of Solid Catalyst Component A 200-ml flask equipped with a stirrer and a dropping funnel was purged with argon, and then 65 ml of toluene and 0.65 of biscyclopentadienyl zirconium dichloride were added.
g (2.2 mmol) and tetraethoxysilane 1
4.0 g (67.4 mmol) was added to obtain a homogeneous solution. Next, 33.1 ml of a di-n-butyl ether solution of the organomagnesium compound synthesized in Example 1 (A)
While the temperature in the flask was maintained at 45 ° C., the solution was gradually dropped from the dropping funnel over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 60 ° C. for 1 hour, separated into solid and liquid at room temperature, washed three times with 50 ml of hexane, 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 atoms and 1% of magnesium atoms.
8.4% by weight.

(B) Copolymerization of ethylene-butene-1 Example 1 was repeated except that 30.0 mg of the solid product obtained in (A) was used in place of the solid catalyst component of Example 1.
Polymerization was carried out in the same manner as in (D). 12 g of polymer yield
And a polymer excellent in spherical and powder properties was obtained. The catalytic 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 min, the ethyl branch was 19.6 / 1000C, and the Tm was 109 ° C.

Comparative Example 4 (A) Synthesis of Solid Catalyst Component A 100 ml flask equipped with a stirrer and a dropping funnel was purged with argon, and then a styrene-divinylbenzene copolymer (having an average particle size of 50 μm and a porosimeter As a result of the measurement, the pore volume (cc / g) (hereinafter abbreviated as dVp) between the pore radii of 100 and 5,000 ° is dVp.
= 1.05 cc / g. ) Was dried at 80 ° C for 30 minutes under reduced pressure, and 7.4 g, 37 ml of heptane, 0.67 g (2.0 mmol) of tetrabutoxytitanium and 7.1 g (34 mmol) of tetraethoxysilane were added thereto, and 30 ° C was added.
For 45 minutes.

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

Next, after the flask having an inner volume of 500 ml was replaced 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 performed at 95 ° C. for 1 hour. After the reaction, solid-liquid separation was performed, and washing was performed twice with 40 ml of toluene. After washing, 40 ml of toluene and 0.5 ml of butyl ether are added to the flask.
(3 mmol) and 7.6 ml (68 mmol) of titanium tetrachloride were added and reacted at 95 ° C. for 3 hours. After completion of the reaction, solid-liquid separation was performed at 95 ° C, and toluene 40
Washing was performed twice with ml. Then add 40 ml of hexane for 2
After repeating washing twice, drying under reduced pressure gave 11.3 g of a brown solid catalyst component. The solid catalyst component contained 0.55% by weight of titanium atom, 7.2% by weight of magnesium atom, and 1.5% by weight of phthalate.

(B) Copolymerization of ethylene-butene-1 A 0.4-liter autoclave with a stirrer was evacuated, and then 25 g of butene-1 and 75 g of butane were added. After the temperature was raised to 70 ° C., hydrogen was added until the partial pressure became 2.3 kg / cm ² , and ethylene was added until the partial pressure became 6 kg / cm ² . 32.0 mg of the solid catalyst component synthesized above and 2.0 mm of triethylaluminum (1.0 mol / l, manufactured by Tohso Akzo)
ol was added to initiate polymerization. After that, while continuously supplying ethylene, the total pressure was kept constant at 70 ° C. for 1 hour.
Polymerization was carried out for hours. After the completion of the polymerization, the produced polymer is 6
It dried under reduced pressure at 0 degreeC. The yield of the polymer was 28.8 g. The catalytic activity in this case 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 min, the ethyl branch was 20.8 co / 1000C, and the Tm was 124 ° C.

[0044]

As the removal of the catalyst residue becomes unnecessary, a solid catalyst component having sufficiently high catalytic activity per solid catalyst and per transition metal is used, and ethylene-α having a narrow composition distribution and good powder properties is used. An olefin copolymer can be produced;

[Brief description of the drawings]

FIG. 1 is a flowchart for helping an understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08F 4/658 C08F 10/00

Claims (2)

(57) [Claims] (A) (1) A compound represented by 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 cyclopentadiene. R ² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ² may be the same or different, and may be a cyclopentadienyl group or a substituted cyclopentadiene group. Two adjacent carbon atoms forming an enyl group may form a ring having 4 to 6 carbon atoms with R ² bonded to each other, and R ¹ is a group bonding ^two (C ₅ R ² _n ) Is an alkylene group having 1 to 4 carbon atoms, 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
And when m is 1, it is 4. The reaction product (II) obtained by reacting the reaction mixture (I) of the zirconium compound represented by the formula (2) and (2) the organosilicon compound having a Si—O bond with the (3) organomagnesium compound is represented by the following formula : 4) General formula R ⁵ _c AlX _3-c (wherein, R ⁵ is a carbon atom 1
X represents a halogen atom, and c represents a number of 0 <c <3. (B) an organoaluminum compound having an Al-O bond. 2. A method for producing an ethylene-α-olefin copolymer, comprising copolymerizing ethylene with one or more α-olefins having 3 or more carbon atoms using the olefin polymerization catalyst according to claim 1.