JPH06220120A - Titanium catalyst component for ethylene polymerization and method for (co) polymerization of ethylene using this catalyst component - Google Patents

Abstract

(57) [Summary] (Modified) [Purpose] A titanium catalyst component for ethylene polymerization, which has a narrow particle size distribution and excellent particle properties, and is capable of producing an ethylene (co) polymer with high polymerization activity, and Provided is a method for polymerizing an olefin using a titanium catalyst component for olefin polymerization. A titanium catalyst component for ethylene polymerization according to the present invention comprises: [A] (a-1) a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a magnesium solution formed from a hydrocarbon solvent; 2) A solid magnesium / aluminum composite containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol obtained by contacting with an organoaluminum compound, and [B] a tetravalent titanium compound. Of the titanium contained in the catalyst, the valence of which is substantially tetravalent, and the alkoxy group and / or alcohol / Ti (molar ratio)
Is 0.26 to 6.0.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a titanium catalyst component for ethylene polymerization capable of producing ethylene polymer particles having a narrow particle size distribution with high polymerization activity and a method for polymerizing ethylene using the titanium catalyst component for ethylene polymerization.

[0002]

BACKGROUND OF THE INVENTION To produce an ethylene polymer,
Generally, a method of homopolymerizing ethylene or copolymerizing ethylene and an α-olefin in the presence of a Ziegler type catalyst is known. In such a method, a high temperature dissolution polymerization method in which a polymerization is carried out in a hydrocarbon solvent at a temperature equal to or higher than the melting point of the obtained polymer has been widely practiced. However, in this method, when a polymer having a large molecular weight is to be obtained, the viscosity of the polymerization solution increases with an increase in the molecular weight, and the polymer concentration in the solution must be reduced, and There is a problem that productivity decreases.

On the other hand, when this polymerization is carried out by a slurry polymerization method, the polymer easily swells in the polymerization solvent,
There was a problem that it was difficult to increase the slurry concentration.

The present applicants have also studied in view of such prior art, and first of all, ethylene having excellent slurry operability, capable of operating at a high slurry concentration, and having excellent composition (copolymerization) distribution. A titanium catalyst component for ethylene polymerization capable of producing a polymer with high polymerization activity is disclosed in, for example, JP-A-60
-195108, etc.

In the ethylene polymerization catalyst component disclosed in Japanese Patent Application Laid-Open No. 60-195108, 70% by weight or more of titanium is in a trivalent reduced state. Although an ethylene copolymer which can be polymerized and has a narrow composition distribution can be obtained, the advent of a titanium catalyst component for ethylene polymerization which is further excellent in polymerization activity is desired.

Further, Japanese Patent Publication No. 63-45404 discloses that
Disclosed is a method for producing a solid titanium catalyst component by reacting a magnesium-aluminum complex obtained by contacting an organoaluminum compound with a halogen-containing magnesium alcohol solution, an electron donor having no active hydrogen, and titanium tetrachloride. Has been done.

The solid titanium catalyst component has an excellent particle size distribution, and the polyolefin obtained by using the olefin polymerization catalyst containing the solid titanium catalyst component has an excellent particle size distribution, but is further polymerized with ethylene. The appearance of a solid titanium catalyst component having excellent activity has been desired.

Further, JP-A-57-159806 discloses a reaction product of a reaction product (a ₁ ) of a halogen-containing magnesium and an alcohol with an organoaluminum compound.
A solid titanium catalyst component obtained by contacting a halogen-containing titanium compound with an alkoxy group and / or alcohol / Ti (molar ratio) of 0.25 or less, and a reaction product (a ₁ ) of halogen-containing magnesium and alcohol. The reaction product with the organoaluminum compound is brought into contact with a halogen-containing titanium compound and then with an organoaluminum halide (halogenating agent), and the alkoxy group and / or alcohol / Ti (molar ratio) is 0.9. An organoaluminum halide (halogenating agent) is brought into contact with the following solid titanium catalyst component or a reaction product of a halogen-containing magnesium and alcohol (a ₁ ) with an organoaluminum compound, and then a halogen-containing titanium compound Contact the organic aluminum halide (halogenating agent Obtained by contacting the alkoxy group and / or alcohol / Ti (molar ratio) 0.9
The following solid titanium catalyst components are disclosed.

In such a solid titanium catalyst component, T
i ⁺³ / Ti ⁺⁴ (molar ratio) is in the range of 2.0 to 10, most of tetravalent titanium is reduced to trivalent, and ethylene can be polymerized with high polymerization activity. However, there is a demand for the appearance of a solid titanium catalyst component for ethylene polymerization capable of producing an ethylene polymer having a narrow particle size distribution with high polymerization activity.

Further, Japanese Patent Laid-Open No. 4-91106 discloses a solid magnesium-aluminum composite obtained by contacting a solution formed from a halogen-containing magnesium, an alcohol and a hydrocarbon solvent with organic aluminum, and a liquid state. A solid titanium catalyst component obtained by contacting a tetravalent titanium compound with a vanadium compound, a zirconium compound or a hafnium compound is disclosed.

The comparative example of JP-A-4-91106 shows an experimental example in which 2-ethylhexoxytitanium trichloride is used as a tetravalent titanium compound and no vanadium compound is used. In the solid titanium catalyst component thus obtained, titanium is reduced to trivalent, and there is a demand for a solid titanium catalyst component having low ethylene polymerization activity and high polymerization activity.

[0012]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a titanium catalyst component for ethylene polymerization capable of producing an ethylene polymer having a narrow particle size distribution with high polymerization activity. Another object of the present invention is to provide a method for polymerizing ethylene using the titanium catalyst component for ethylene polymerization.

[0013]

SUMMARY OF THE INVENTION A titanium catalyst component for ethylene polymerization according to the present invention comprises [A] (a-1) a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a magnesium solution formed from a hydrocarbon solvent, a-2) Solid magnesium-aluminum composite containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol obtained by contacting with an organoaluminum compound, and [B] tetravalent titanium It is brought into contact with a compound and contains magnesium, halogen, aluminum, an alkoxy group having 6 or more carbon atoms and / or alcohol and titanium as essential components.

The method for polymerizing ethylene according to the present invention comprises the above-mentioned [I] titanium catalyst component for ethylene polymerization and [I]
[I] In the presence of an ethylene polymerization catalyst comprising an organoaluminum compound catalyst component, ethylene is polymerized or ethylene and an α-olefin having 3 to 20 carbon atoms are copolymerized.

[0015]

DETAILED DESCRIPTION OF THE INVENTION The titanium catalyst component for ethylene polymerization, the ethylene polymerization catalyst containing the titanium catalyst component for ethylene polymerization, and the ethylene (co) polymerization method using the ethylene polymerization catalyst according to the present invention are described below. To explain.

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

FIG. 1 is an explanatory view showing an example of a process for producing a titanium catalyst component for ethylene polymerization according to the present invention. The titanium catalyst component for ethylene polymerization according to the present invention is [A] (a-1) a magnesium solution formed from a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent, and (a-2) an organic solution. By contacting a solid magnesium-aluminum composite containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol obtained by contacting with an aluminum compound, and [B] tetravalent titanium compound can get.

First, the solid magnesium-aluminum composite [A] containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol will be described. Is (a-1) a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms,
And a magnesium solution formed from a hydrocarbon solvent and (a-2) an organoaluminum compound are brought into contact with each other.

In this solid magnesium-aluminum composite [A], the Al / Mg (atomic ratio) is usually 0.1.
05 to 1, preferably 0.08 to 0.7, more preferably 0.12 to 0.6, and the alkoxy group having 6 or more carbon atoms and / or alcohol is usually 0.5 to 1 per 1 part by weight of magnesium. 15 parts by weight, preferably 2 to 13 parts by weight, more preferably 5 to 10 parts by weight, X
It is desirable that ¹ (halogen) / Mg (atomic ratio) is usually 1 to 3, and preferably 1.5 to 2.5.

The solid magnesium-aluminum composite [A] has a particle size of preferably 1 to 200 μm, more preferably 2 to 100 μm, and a particle size distribution of 1.0 to 2.0, preferably a geometric standard deviation. It is preferably 1.0 to 1.8 and granular.

In the present invention, the magnesium solution (a-1)
Specific examples of the halogen-containing magnesium compound used in the preparation of are as follows.

Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride, methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, alkoxy magnesium halides such as octoxy magnesium chloride, and phenoxy. Allyloxy magnesium halides such as magnesium chloride and methylphenoxy magnesium chloride, alkoxy magnesium such as diethoxy magnesium, diisopropoxy magnesium, dibutoxy magnesium and dioctoxy magnesium, allyloxy magnesium such as diphenoxy magnesium and dimethylphenoxy magnesium, laurin Magnesium such as magnesium acidate and magnesium stearate Such as carboxylic acid salt.

Further, it may be a complex compound of these compounds and another metal, a double compound or a mixture with another metal compound. Among these, magnesium halide and alkoxy magnesium halide are preferable, magnesium chloride and alkoxy magnesium chloride are more preferable, and magnesium chloride is particularly preferable.

These may be used alone or in combination. The liquid magnesium compound solution (a-1) used in the present invention is formed from a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent.

Specific examples of the alcohol having 6 or more carbon atoms used in the present invention include 2-methylpentanol, 2-ethylpentanol, 2-ethylbutanol, n-heptanol, n-octanol and 2-ethylhexanol. , Decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol and other aliphatic alcohols, cyclohexanol, methylcyclohexanol and other alicyclic alcohols, benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl Alcohol, α,
Examples thereof include aromatic alcohols such as α-dimethylbenzyl alcohol, n-butyl cellosolve, aliphatic alcohols containing an alkoxy group such as 1-butoxy-2-propanol, and the like.

Of these, alcohols having 7 or more carbon atoms are preferable, and 2-ethylhexanol is particularly preferable. These may be used alone or in combination.

When the halogen-containing magnesium compound is brought into contact with the alcohol having 6 or more carbon atoms and the hydrocarbon solvent, the halogen-containing magnesium compound is dissolved in the hydrocarbon solvent to obtain a magnesium solution.

Specific examples of the hydrocarbon solvent include propane, butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane and kerosene. Alicyclic hydrocarbons such as aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane,
Aromatic hydrocarbons such as benzene, toluene, xylene,
Halogenated hydrocarbons such as methylene dichloride, ethyl chloride, ethylene dichloride, chlorobenzene, etc. are used.

Of these, aliphatic hydrocarbons, particularly aliphatic hydrocarbons having 3 to 10 carbon atoms, are preferably used. These may be used alone or in combination.

The contact between the halogen-containing magnesium compound as described above, the alcohol having 6 or more carbon atoms and the hydrocarbon solvent varies depending on the kind of the compound and the alcohol used, but is usually room temperature or higher, preferably 65.
C. or higher, more preferably about 80 to 300.degree. C., particularly preferably about 100 to about 200.degree. C., about 15 minutes to 5 hours, more preferably about 30 minutes to 3 hours.

At this time, the alcohol is usually about 1 mol or more, preferably about 1.5 to about 20 mol, and more preferably 1 mol, per 1 mol of the halogen-containing magnesium compound, although it varies depending on the type of magnesium compound and solvent used. Is used in an amount of about 2.0 to about 12 moles.

A solid magnesium-aluminum composite [A] is obtained by bringing the magnesium solution (a-1) into contact with the organoaluminum compound (a-2).
As the (a-2) organoaluminum compound used in the present invention, specifically, for example, an aluminum compound represented by the following formula (iv) is preferably used.

R ^a _n AlX _3-n (iv) In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to 3.

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Such an organoaluminum compound (a-2)
More specifically, the following compounds may be mentioned. Trialkylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, trialkylaluminum such as tri-2-ethylhexylaluminum, alkenylaluminum such as isoprenylaluminum, dimethylaluminium chloride, diethylaluminum chloride, diisopropylaluminum chloride, Dialkyl aluminum halides such as diisobutyl aluminum chloride, dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, methyl Rumi um dichloride, ethylaluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

Further, a compound represented by the following formula (v) can also be used. ^{_{R a n AlY 3-n ...}} (v) wherein R ^a is the same as R ^a in the above formula (iv), n is 1 to
2 and Y is -OR ^b group, -OSi R ^c ₃ group, -OAl
R ^d ₂ group, -NR ^e ₂ group, -SiR ^f ₃ group or -N (R ^g ).
AlR ^h ₂ group.

R^b, R^c, R^dAnd R^hIs a methyl group,
Ethyl group, isopropyl group, isobutyl group, cyclohexyl
Syl group, phenyl group, etc., R^eIs a hydrogen atom,
Group, ethyl group, isopropyl group, phenyl group, trime
Such as a tylsilyl group, R ^fAnd R^gIs a methyl group,
For example, an ethyl group.

More specifically, the following compounds may be mentioned. (1) R ^a _n Al (OR ^b ) _3-n For example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

(2) R ^a _n Al (OSiR ^c ₃ ) _3-n For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSi
Me ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), and the like.

(3) R ^a _n Al (OAl R ^d ₂ ) _3-n For example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso
-Bu) ₂ etc., (4) R ^a _n Al (NR ^e ₂ ) _3-n For example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ Al.
NHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN (M
e ₃ Si) ₂ etc.

(5) R ^a _n Al (SiR ^f ₃ ) _3-n For example, (iso-Bu) ₂ AlSiMe _{3 and the} like. _{^{(6) R a n Al [}} N (R g) AlR h 2] 3-n for _{example, Et 2 AlN (Me) AlEt} 2, (iso-Bu) 2 Al
N (Et) Al (iso-Bu) _{2 and the} like.

Further, as the organoaluminum compound (a-2), a compound represented by the general formula M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na or K, and R ^j has 1 to 1 carbon atoms)
5 is a hydrocarbon group. It is also possible to use a complex alkylated product of a Group I metal represented by) and aluminum, and specific examples thereof include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of the above, trialkylaluminum,
Dialkyl aluminum halide, dialkyl aluminum hydride and dialkyl aluminum alkoxide are preferably used. Of these, trialkylaluminum, especially triethylaluminum, is preferable because a catalyst having a good shape can be easily obtained.

The above compounds can be used alone or in combination of two or more kinds. When forming the solid magnesium-aluminum composite [A], the organoaluminum compound (a-2) is an alcohol (ROH) having 6 or more carbon atoms and an organoaluminum used in the preparation of the magnesium solution (a-1). It is desirable that the aluminum atom contained in the compound (a-2) is used in an amount of about 0.5 to 7, preferably 1 to 5 in ROH / Al (molar ratio).

The contact between the magnesium solution (a-1) and the organoaluminum compound (a-2) as described above is specifically as follows.
The magnesium concentration in the solution is preferably 0.005 to 2
While stirring the magnesium solution (a-1), which is mol / liter, more preferably 0.05 to 1 mol / liter,
The organoaluminum compound (a-2) can be slowly added dropwise to the solution (a-1) over, for example, 0.2 to 2 hours. In this case, solid particles having good particle properties can be obtained. A magnesium / aluminum composite [A] is obtained.

The contact temperature between the magnesium solution (a-1) and the organoaluminum compound (a-2) is usually -50 to 150.
C, preferably -30 to 100C. Such a solid magnesium-aluminum composite [A] does not have a reducing organic group and does not exhibit reducing properties.

The titanium catalyst component [I] for ethylene polymerization according to the present invention is obtained by bringing the solid magnesium-aluminum composite [A] into contact with the tetravalent titanium compound [B].

The tetravalent titanium compound [B] is preferably a compound represented by the following formula (ii). Ti (OR ² ) _g X _4-g (ii) In formula (ii), R is a hydrocarbon group, X is a halogen atom, and 0 ≦ g ≦ 3.

Specific examples of the tetravalent titanium compound [B] include titanium tetrahalides such as TiCl ₄ , TiBr ₄ , TiI ₄ , Ti (OCH ₃ ) Cl ₃ , Ti (OC _2).
H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃
, Ti (O-iso-C ₄ H ₉ ) Br ₃ and other trihalogenated alkoxy titanium, Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ C
dihalogenated dialkoxytitanium such as l ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl
, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On-C ₄ H ₉ ) ₃ Cl, Ti
Examples thereof include monohalogenated trialkoxy titanium such as (OC ₂ H ₅ ) ₃ Br.

Of these, titanium tetrahalide, particularly titanium tetrachloride, is preferred.

These may be used alone or in combination. These tetravalent titanium compounds [B] are the solid magnesium-aluminum composite [A],
Ti / (Mg + Al) (atomic ratio), 0.005-1
It is used in an amount of 8, preferably 0.01 to 15.

The contact between the solid magnesium-aluminum composite [A] and the tetravalent titanium compound [B] is preferably carried out in a hydrocarbon solvent. As this hydrocarbon solvent, those similar to the above-mentioned hydrocarbons are used.

In the present invention, the contact is usually 0 to 150.
℃, preferably 50 ~ 130 ℃, more preferably 50 ~
It is carried out at a temperature of 120 ° C. The titanium catalyst component for ethylene polymerization according to the present invention is obtained as described above and contains magnesium, halogen, aluminum, titanium and an alkoxy group having 6 or more carbon atoms and / or alcohol as essential components. The titanium content in the titanium catalyst component for ethylene polymerization is 90% or more, preferably 95% or more.
% Or more, more preferably all titanium is in a tetravalent state.

The titanium catalyst component for ethylene polymerization has the following physical properties. Ti / Mg (atomic ratio) is usually 0.01 to 1.5, preferably 0.05 to
1.0, Al / Mg (atomic ratio) is usually 0.1
2.0, preferably 0.13 to 1.5, particularly preferably 0.15 to 1.2, and the alkoxy group having 6 or more carbon atoms and / or the alcohol is usually 0.1 to 1 part by weight of magnesium. 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 6 parts by weight.

The alkoxy group and / or alcohol / Ti (molar ratio) is 0.26 to 6.0, preferably 0.26 to 5.0, and more preferably 0.
26 to 4.0.

The titanium catalyst component for ethylene polymerization preferably has a particle size of 1 to 200 μm, preferably 2 to 100 μm, and a particle size distribution of 1.0 to geometric standard deviation.
It is desired to be 2.0, preferably 1.0 to 1.8.

The prepolymerized titanium catalyst component for ethylene polymerization according to the present invention is [I] [A] (a-1) halogen-containing magnesium compound,
Magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or obtained by bringing (a-2) an organoaluminum compound into contact with a magnesium solution formed from an alcohol having 6 or more carbon atoms and a hydrocarbon solvent Obtained by contacting a solid magnesium-aluminum complex containing alcohol with a [B] tetravalent titanium compound, the valence of titanium contained in the catalyst is substantially tetravalent, and an alkoxy group and / Or alcohol / Ti (molar ratio)
In an ethylene polymerization catalyst comprising a titanium catalyst component for ethylene polymerization having a content of 0.26 to 6.0 and a catalyst component [II] organoaluminum compound, wherein an olefin, preferably ethylene alone or a small amount of 3 carbon atoms with ethylene. .About.20 .alpha.-olefins are prepolymerized.

The ethylene polymerization catalyst according to the present invention comprises the above-mentioned [I] ethylene polymerization titanium catalyst component and the above-mentioned [II] organoaluminum compound catalyst component.

Furthermore, the ethylene polymerization catalyst according to the present invention comprises the above-mentioned [I] 'prepolymerized titanium catalyst component for ethylene polymerization and the above-mentioned [II] organoaluminum compound catalyst component. ing.

The method for polymerizing ethylene according to the present invention comprises polymerizing ethylene in the presence of an ethylene polymerization catalyst formed from the above titanium catalyst component [I] for ethylene polymerization and the organoaluminum compound [II]. Or copolymerize ethylene with an α-olefin having 3 to 20 carbon atoms.

3 carbon atoms copolymerized with ethylene in the present invention
Examples of the α-olefin of -20 include propylene, 2-methylpropylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene,
1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and the like. It is also possible to copolymerize an α-olefin and a polyene. Examples of such polyenes include butadiene, isoprene, 1,4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene.

In the copolymerization of ethylene with other α-olefins, it is preferable to produce a copolymer containing a constitutional unit derived from ethylene in an amount of 90 mol% or more.

As the organoaluminum compound [II] used in the polymerization, the organoaluminum compound (a) used in preparing the titanium catalyst component [I] for ethylene polymerization is used.
-Similar to 2).

In the polymerization, the titanium catalyst component [I] for ethylene polymerization is usually about 0.00001 to about 1 mmol, preferably about 0.0001 to about 0.1 mmol in terms of Ti atom per 1 liter of the polymerization reaction volume. Used in an amount of.

The organoaluminum compound [II] is used in an amount of 1-1000 mol, preferably 2-500 mol, per 1 g atom of titanium in the titanium catalyst component [I] for ethylene polymerization.

The titanium catalyst component for ethylene polymerization as described above may be used by supporting it on the following carrier compound. Such carrier compounds include Al ₂ O ₃ and S
iO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Zn
Resins such as ₂ O, SnO ₂ , BaO, ThO and styrene-divinylbenzene copolymers can be mentioned.

Further, ethylene may be prepolymerized in the above ethylene polymerization catalyst. If hydrogen is used during the polymerization, the molecular weight of the resulting polymer can be adjusted.

In the present invention, the polymerization of ethylene can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. Further, it can be carried out by any of batch method, anti-continuous method and continuous method.

When the polymerization takes the form of slurry polymerization, an inert solvent may be used as the reaction solvent, or liquid ethylene at the polymerization temperature may be used.

Examples of such an inert solvent include propane, butane, n-pentane, isopentane, n-hexane,
Isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, methylcyclopentane, cyclohexane, alicyclic hydrocarbons such as methylcyclohexane,
Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene are used. These may be used alone or in combination.

The polymerization temperature is usually 20 to 150 ° C., preferably 50 to 120 ° C., more preferably 70 to 110 ° C., and the polymerization pressure is usually 1 to 1000 kg / cm ² , preferably ² to 40 kg / cm ² . is there.

The above-mentioned copolymerization can be carried out in multiple stages of two or more. The ethylene polymer thus obtained is a homopolymer of ethylene, or ethylene.α-
Either an olefin random copolymer or a block copolymer may be used, but an ethylene homopolymer or a random copolymer of ethylene and α-olefin is preferable.

Particularly in the present invention, the density is 0.90 to 0.9.
70 g / cm ³ , preferably 0.91 to 0.970 g / cm ³
The ethylene homopolymer or ethylene / α-olefin copolymer is preferably produced. The density here is a value measured by ASTM D1505.

According to the present invention as described above, ethylene or ethylene and an α-olefin having 3 to 20 carbon atoms can be (co) polymerized with high polymerization activity.

The ethylene (co) polymer obtained in the present invention is obtained in the form of particles, but the particle size is usually 10 to 1500 μm.
m, preferably 10 to 1000 μm. The geometric standard deviation of the particles is 1.0 to 2.0, preferably 1.0 to
It is 1.8.

As described above, the ethylene (co) polymer obtained in the present invention has a narrow particle size distribution and a small content of fine powder of 100 μm or less. Specifically, in the ethylene (co) polymer powder obtained by the present invention, particles having a particle size of 850 μm or more are 1.0% by weight or less of the whole particles, preferably 0.8% by weight or less.
% Or less, particularly preferably 0.5% or less, 1
7.0 wt% or less of particles having a particle size of 00 μm or less, preferably 5.0 wt% or less, particularly preferably 3.0 wt%
It is desirable that the amount of particles having a particle size of 100 to 500 μm is 85% by weight or more, and preferably 90% by weight or more.

In the present invention, the ethylene (co) polymer obtained as described above may optionally contain a heat resistance stabilizer, a weather resistance stabilizer, an antistatic agent, an antiblocking agent, a lubricant,
Nucleating agents, pigments, dyes, inorganic or organic fillers and the like can also be added.

[0078]

The titanium catalyst component for ethylene polymerization according to the present invention comprises a halogen-containing titanium compound supported on a solid magnesium-aluminum composite. In this catalyst, titanium is in a tetravalent state and has a high polymerization activity. It is possible to polymerize ethylene or copolymerize ethylene with an α-olefin having 3 to 20 carbon atoms.

In particular, this titanium catalyst component for ethylene polymerization can produce ethylene (co) polymer particles having a narrow particle size distribution, and particularly the fine powdery ethylene (co) polymer particles are less produced.

The ethylene (co) polymerization method according to the present invention is carried out using such a titanium catalyst component for ethylene polymerization, and an ethylene (co) polymer having a high polymerization activity and a narrow particle size distribution is obtained. . When the polymerization is carried out by the slurry method, the slurry operability is also excellent.

[0081]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

In the following examples and comparative examples,
The catalyst composition and particle size distribution were measured as follows. 1) Mg, Al and Ti The amounts of Mg, Al and Ti in the catalyst component were analyzed by the ICP analysis method (ICPF1000TR manufactured by Shimadzu Corporation). 2) Cl The amount of Cl in the catalyst component was analyzed by the silver nitrate titration method. 3) OR group A sufficiently dried catalyst was added to a water / acetone solution containing 10% by weight of water for hydrolysis, and the obtained ROH was quantified by gas chromatography. 4) Particle size distribution and geometric standard deviation Vibrator (Iida Seisakusho, low tap type) and sieve (Iida Lasting Sieve (JIS-Z-8801) inner diameter 20
0 mm).

[0083]

Example 1 [Preparation of catalyst components] Commercially available anhydrous magnesium chloride 4.8
g, 2-ethylhexanol 19.5 g and decane 20
0 ml was heated at 140 ° C. for 3 hours to obtain a homogeneous solution containing magnesium chloride. A mixed solution of 60 mmol of triethylaluminum and 52 ml of decane was added dropwise to this solution at 20 ° C. under stirring for 30 minutes, and then 2
It heated up at 80 degreeC over time, and heated for 2 hours. After completion of the heating reaction, the solid portion was separated by filtration and washed once with 200 ml of decane to obtain a solid magnesium-aluminum complex.

The solid magnesium-aluminum complex thus obtained was resuspended in 200 ml of decane, 400 mmol of titanium tetrachloride was added, and the mixture was heated at 80 ° C. for 2 hours.
After reacting for a time, thoroughly wash with hexane,
A hexane suspension of the solid catalyst was obtained. The composition of the solid catalyst is shown in Table 2.

A part of the hexane suspension of the above solid catalyst (corresponding to 5 g of the solid catalyst) was sampled and added to a 300 ml reactor equipped with a Teflon stirrer. Furthermore, 0.5 g of liquid paraffin was also added and mixed with stirring. Nitrogen was passed through the reactor at a rate of 80 Nl / Hr, and the reactor was attached to a bath layer of 40 ° C. to evaporate hexane. By this drying, about 10%
A powdery Ti catalyst component containing the liquid paraffin of was obtained. [Polymerization] In a 2-liter autoclave under a nitrogen atmosphere,
After adding 1 liter of purified hexane, 1.0 mmol of triethylaluminum and the powdery T obtained above.
The i catalyst component was suspended in hexane to obtain Ti atom conversion of 0.
After adding 01 mmol equivalent, the temperature was raised to 80 ° C., hydrogen 4.0 kg / cm ² to supply G, then the total pressure 8.0 kg / cm ²
Ethylene was continuously fed for 2 hours so as to attain G. The temperature during the polymerization was adjusted to 80 ° C.

After completion of the polymerization, the ethylene polymer was separated from the hexane solvent and then dried. The results are shown in Table 2.
The yield of the obtained polymer powder was 227 g, the MFR was 2.7 g / 10 minutes, and the apparent bulk specific gravity was 0.33 g / cc.

The particle size distribution of the resulting polymer powder is shown in Table 1.
Shown in.

[0088]

[Table 1]

[0089]

Example 2 A catalyst component was prepared in the same manner as in Example 1 except that 19.5 g of 2-ethylhexanol was replaced with 16.3 g and 60 mmol of triethylaluminum was replaced with 46 mmol. , Was polymerized.

The results are shown in Table 3.

[0091]

Example 3 A catalyst component was prepared and polymerized in the same manner as in Example 2 except that the temperature condition after adding 400 mmol of titanium tetrachloride was changed from 80 ° C to 100 ° C. went.

The results are shown in Table 3.

[0093]

Example 4 A catalyst component was prepared in the same manner as in Example 1, except that 19.5 g of 2-ethylhexanol was replaced by 16.3 g and 60 mmol of triethylaluminum was replaced by 43 mmol. , Was polymerized.

The results are shown in Table 3.

[0095]

Example 5 A catalyst component was prepared in the same manner as in Example 1 except that 19.5 g of 2-ethylhexanol used in Example 1 was replaced with 15.3 g and 60 mmol of triethylaluminum was replaced with 41 mmol. Then, polymerization was performed.

The results are shown in Table 3.

[0097]

Comparative Example 1 Commercially available anhydrous magnesium chloride 4.8 g, 2-
19.5 g of ethylhexanol and 200 ml of decane were heated at 140 ° C for 3 hours to obtain a uniform solution containing magnesium chloride. A mixed solution of 52 mmol of triethylaluminum and 45 ml of decane was added dropwise to this solution at 20 ° C. over 30 minutes, and then the temperature was raised to 80 ° C. over 2 and a half hours and heated at 80 ° C. for 1 hour. After completion of the heating reaction, the reaction slurry is allowed to stand still, the supernatant liquid is removed, and decane 200 is added to the residual slurry containing the solid part produced in the above reaction.
ml and diethylaluminum chloride 50 mmol were added, and the reaction was carried out again at 80 ° C. for 1 hour. Then, the solid portion was separated by filtration and washed once with 100 ml of decane to prepare a solid component having a reducing organic group.

The solid component thus obtained was added to decane 20
After resuspending in 0 ml, 25 mmol of titanium tetrachloride was added, the reaction was carried out at 80 ° C. for 2 hours, and the produced solid was separated by filtration. The separated solid product was washed 5 times with hexane to obtain a titanium catalyst component.

Using the titanium catalyst component thus obtained, ethylene was polymerized under the same conditions as in Example 1. The results are shown in Table 3.

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

Comparative Example 2 30 mmol of commercially available anhydrous magnesium chloride was suspended in 150 ml of n-decane, and 120 mmol of n-butanol was added dropwise with stirring over 1 hour.
Heated at ° C for 1 hour. Then, 240 mmol of diethyl aluminum monochloride was added dropwise at room temperature, and the mixture was heated at 90 ° C. for 3 hours. After the completion of the heating reaction, the obtained solid part was washed and then made into an n-decane suspension, 3 mmol of titanium tetrachloride was added dropwise, and the mixture was reacted at 25 ° C for 10 minutes.

The catalyst composition (% by weight) thus obtained is shown in Table 4. [Polymerization] A stainless steel autoclave having an internal volume of 2 liters was sufficiently replaced with nitrogen, 1 liter of n-hexane was added, and the temperature was raised to 50 ° C. Next, 1.0 mmol of triisobutylaluminum, 0.5 mmol of ethylene dichloride, and 0.02 mmol of the catalyst obtained above in terms of Ti atoms were added, and after sealing, hydrogen was added at a gauge pressure of 4.5 kg. / cm ² and until further 8kg ethylene / cm ²
Pressed until it became. It was kept at 80 ° C. for 2 hours while continuously feeding ethylene so that the total pressure was kept at 8 kg / cm ² G.

The polyethylene obtained was 316 g, which corresponds to a polymerization activity of 16800 g PE / g catalyst.

[0105]

[Table 4]

[0106]

Example 6 [Preliminary Polymerization] 200 ml of purified hexane, 6 mmol of triethylaluminum and the powdery Ti catalyst component obtained in Example 1 were suspended in hexane in a 400 ml cylindrical flask equipped with a stirrer and converted into Ti atoms. After adding 2 mmol, ethylene was fed at 20 ° C. at a rate of 1.74 Nl / Hr for 3 hours to preliminarily polymerize ethylene. The amount of polyethylene produced was 5 g per 1 g of catalyst. [Polymerization] In a 2-liter autoclave under a nitrogen atmosphere,
After adding 1 liter of purified hexane, 1.0 mmol of triethylaluminum and the powdery Ti catalyst component prepolymerized as described above were added in an amount of 0.01 mmol in terms of Ti atom, and the temperature was raised to 80 ° C. Warm, 4.0 kg hydrogen
/ Cm ² G, and then ethylene was continuously fed for 2 hours so that the total pressure was 8.0 kg / cm ² G. The temperature during the polymerization was adjusted to 80 ° C.

After completion of the polymerization, the ethylene polymer was separated from the hexane solvent and then dried. The results are shown in Table 5.

[0108]

[Table 5]

[0109]

Comparative Example 3 In a four-necked flask having an internal volume of 400 ml, 30 mmol of anhydrous magnesium chloride was suspended in 150 ml of n-decane, 180 mmol of ethanol was added dropwise over 1 hour with stirring, and the mixture was reacted at room temperature for 1 hour. . It became a white powder in which the raw material magnesium chloride was swollen. Then, 84 mmol of diethyl aluminum monochloride was added dropwise at room temperature, and the mixture was reacted at 30 ° C. for 1 hour. Next, after adding 300 mmol of titanium tetrachloride, the mixture was heated and stirred at 80 ° C. for 3 hours. After completion of the reaction, solid-liquid separation was performed, and the obtained solid part was n-
It was washed with 2 liters of decane. [Polymerization] A stainless steel autoclave having an internal volume of 2 liters was sufficiently replaced with nitrogen, and then 1 liter of N-hexane was added and heated to 50 ° C. Triisobutylaluminum 1.
After adding 0 mmol, 0.5 mmol of ethylene dichloride and 0.02 mmol of the catalyst component obtained as described above in terms of Ti atom and sealing, hydrogen was added until the gauge pressure became 4.5 kg / cm ² . Further ethylene 8kg / cm ²
Pressed until it became. It was kept at 80 ° C. for 2 hours while continuously feeding ethylene so that the total pressure was kept at 8 kg / cm ² G.

The results are shown in Table 6.

[0111]

[Table 6]

[Brief description of drawings]

FIG. 1 shows a process for producing a titanium catalyst component for ethylene polymerization according to the present invention.

Claims (8)

[Claims] 1. A magnesium solution formed from [A] (a-1) a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent is contacted with (a-2) an organoaluminum compound. The solid magnesium / aluminum complex containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol is brought into contact with a tetravalent titanium compound [B] to obtain a catalyst in the catalyst. The valence of titanium contained is substantially tetravalent, and an alkoxy group and / or alcohol / Ti (molar ratio)
Is 0.26 to 6.0, a titanium catalyst component for ethylene polymerization. 2. The solid magnesium-aluminum composite [A] and the tetravalent titanium compound [B] are brought into contact with each other in a hydrocarbon solvent to obtain the compound.
The titanium catalyst component for ethylene polymerization described in 1. 3. The solid magnesium-aluminum composite [A] and the tetravalent titanium compound [B] are obtained by contacting them in a hydrocarbon solvent at a temperature of 50 to 120 ° C. The titanium catalyst component for ethylene polymerization according to claim 1. 4. A magnesium solution formed from [I] [A] (a-1) a halogen-containing magnesium compound, an alcohol having 6 or more carbon atoms, and a hydrocarbon solvent, and (a-2) an organoaluminum compound. A solid magnesium / aluminum composite containing magnesium, halogen, aluminum and an alkoxy group having 6 or more carbon atoms and / or alcohol obtained by contacting with [B] tetravalent titanium compound, The valence of titanium contained in the catalyst is substantially tetravalent, and an alkoxy group and / or alcohol / Ti (molar ratio)
Prepolymerized, characterized in that an olefin is prepolymerized on an ethylene polymerization catalyst comprising a titanium catalyst component for ethylene polymerization having a ratio of 0.26 to 6.0 and a catalyst component [II] organoaluminum compound. Titanium catalyst component for ethylene polymerization. 5. An ethylene polymerization catalyst comprising the titanium catalyst component for ethylene polymerization [I] according to claim 1 and the catalyst component for organoaluminum compound [II]. 6. An ethylene polymerization catalyst comprising a titanium catalyst component for ethylene polymerization in which the olefin according to claim 4 is prepolymerized, and an organoaluminum compound catalyst component [II]. 7. Polymerizing ethylene or ethylene and carbon in the presence of an ethylene polymerization catalyst comprising the titanium catalyst component for ethylene polymerization [I] and the catalyst component for organoaluminum compound [II] according to claim 1. Number 3 to α
-A method for polymerizing ethylene, which comprises copolymerizing with an olefin. 8. Ethylene is polymerized in the presence of an ethylene polymerization catalyst comprising a titanium catalyst component for ethylene polymerization prepolymerized with the olefin of claim 4 and a catalyst component [II] organoaluminum compound, or A method for polymerizing ethylene, which comprises copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms.