JPH06228228A - Production of polyolefin - Google Patents

Abstract

PURPOSE:To obtain a polyolefin having low crystallinity, free from solvent odor and useful for a modifying material, etc., in high efficiency using a simplifiable drying process by polymerizing an olefin in the presence of a specific catalyst in an aliphatic hydrocarbon medium, etc. CONSTITUTION:The objective polyolefin is produced by (co)polymerizing an olefin in an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium in the presence of a catalyst composed of (A) a metallocene compound of a transition metal selected from the group IVB metal of the periodic table [e.g. bis(indenyl) zirconium dichloride] and (B) an organic aluminum oxy compound such as aluminoxane slurried with an aliphatic hydrocarbon or alicyclic hydrocarbon. The organic aluminum oxy compound preferably has a specific surface area of >=10m<2>/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyolefin, and more particularly to a method for producing a polyolefin capable of simplifying a drying process of a produced polymer.

[0002]

BACKGROUND OF THE INVENTION Conventionally, low crystalline ethylene copolymers, which are copolymers of ethylene and α-olefins, have been modified from thermoplastic resins such as polyethylene, polypropylene and ethylene / vinyl acetate copolymers. Widely used as quality material.

As a method for producing a polyolefin such as an ethylene-based copolymer, the presence of a titanium-based catalyst composed of a titanium compound and an organoaluminum compound or a vanadium-based catalyst composed of a vanadium compound and an organoaluminum compound has hitherto been known. Below, methods for copolymerizing α-olefins are known.

In recent years, as such an olefin polymerization catalyst, a new Ziegler type olefin polymerization catalyst composed of a transition metal compound such as zirconocene and an organoaluminum oxy compound has been proposed. It is known that an olefin copolymer having excellent composition distribution (narrow composition distribution) can be obtained while being polymerized or copolymerized with.

Such an organoaluminum oxy compound is usually produced by contacting an organoaluminum compound such as trialkylaluminum with a metal salt hydrate in a hydrocarbon solvent. At this time, as the hydrocarbon, an aromatic hydrocarbon excellent in solubility of the obtained organoaluminum oxy compound, particularly toluene is used. However, if the contact between the organoaluminum compound and the metal salt hydrate is carried out in an aliphatic hydrocarbon solvent such as hexane, the resulting organoaluminum oxy compound is difficult to dissolve in the aliphatic hydrocarbon, so that the organoaluminum oxy compound is not easily dissolved. Separation of the compound from the metal salt becomes difficult.

Therefore, conventionally, the organoaluminum oxy compound was produced in the state of being dissolved in an aromatic hydrocarbon such as toluene, that is, as a toluene solution of the organoaluminum oxy compound, and added to the polymerization system.

When it is attempted to produce a polyolefin in the presence of a hydrocarbon solvent by using a solution of such an organoaluminum oxy compound in toluene by a method such as a solution polymerization method or a suspension polymerization method, the polymer produced contains a solvent. Since it is obtained in the state of, it is necessary to heat or reduce the pressure to dry this produced polymer, but when toluene is used as the solvent, toluene has a high boiling point and has a bad odor, making it difficult to simplify the drying process, In addition, the obtained polymer has a problem that odor tends to remain.

It is also conceivable to use benzene having a low boiling point instead of toluene, but the use of benzene is not preferable in terms of work hygiene. Therefore, there has been a demand for a polyolefin production method capable of simplifying the drying step when producing a polyolefin by a solution polymerization method or the like in the presence of a hydrocarbon solvent.

[0009]

OBJECT OF THE INVENTION It is an object of the present invention to provide a method for producing a polyolefin which can simplify the drying step when producing a low crystalline polyolefin in the presence of a hydrocarbon solvent.

[0010]

SUMMARY OF THE INVENTION The method for producing a polyolefin according to the present invention is carried out in the presence of [A] a metallocene compound of a transition metal selected from Group IVB of the Periodic Table and [B] an olefin polymerization catalyst comprising an organoaluminumoxy compound. In addition, when the polyolefin is produced by polymerizing or copolymerizing an olefin, the organoaluminum oxy compound [B] is added to the polymerization system as a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon, and an aliphatic hydrocarbon medium is added. Alternatively, the polymerization is carried out in the presence of an alicyclic hydrocarbon medium.

In the present invention, the above-mentioned organoaluminum oxy compound [B] preferably has a specific surface area of 10 m ² / g or more. The olefin polymerization catalyst may be formed from the organoaluminum compound [C] together with the metallocene compound [A] and the organoaluminum oxy compound [B].

[0012]

DETAILED DESCRIPTION OF THE INVENTION The method for producing a polyolefin according to the present invention will be specifically described below.

First, the catalyst used in the present invention will be described. FIG. 1 shows the steps for preparing the olefin polymerization catalyst used in the present invention. The olefin polymerization catalyst used in the present invention is formed from [A] a metallocene compound of a transition metal selected from Group IVB of the periodic table and [B] an organoaluminumoxy compound.

The metallocene compound [A] of a transition metal selected from Group IVB of the periodic table is specifically represented by the following formula [I]. ML _x ... [I] [In the formula, M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, and L is a ligand coordinated to the transition metal, At least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom Alternatively, it is a hydrogen atom, and x is the valence of the transition metal. Examples of the ligand having a cyclopentadienyl skeleton include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl group. , A pentamethylcyclopentadienyl group,
Ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group Groups such as alkyl-substituted cyclopentadienyl group or indenyl group, 4,5,
Examples thereof include a 6,7-tetrahydroindenyl group and a fluorenyl group. These groups are halogen atoms,
It may be substituted with a trialkylsilyl group or the like.

Of these ligands which coordinate to the transition metal, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the above general formula contains two or more groups having a cyclopentadienyl skeleton, two of them are
Groups having two cyclopentadienyl skeletons are substituted with alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene groups, diphenylsilylene groups, and methylphenylsilylene groups. It may be bound via a silylene group or the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. Containing a ligand having such a cyclopentadienyl skeleton [A-3]
When the transition metal has a valence of 4, the metallocene compound is more specifically represented by the following formula [II].

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ... [II] (In the formula, M is the above transition metal, and R ² is a group (ligand) having a cyclopentadienyl skeleton. , R ³ , R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃ R groups, halogen atoms Or a hydrogen atom, k is an integer of 1 or more, and k + l + m + n = 4.) In the present invention, in the above formula R ² _k R ³ _l R ⁴ _m R ⁵ _n M, R ² ,
A metallocene compound in which at least two of R ³ , R ⁴ and R ⁵ , that is, R ² and R ³ are groups (ligands) having a cyclopentadienyl skeleton is preferably used. Groups having these cyclopentadienyl skeletons include alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or dimethylsilylene, diphenylsilylene,
It may be bonded via a substituted silylene group such as a methylphenylsilylene group. R ⁴ and R ⁵ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO
₃ R, a halogen atom or a hydrogen atom.

Specific examples of the transition metal compound in which M is zirconium are shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis ( Indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (4,5,6, 7-Tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride , Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (trimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride, dimethyl Silylenebis (2-methylindenyl) zirconium dichloride, dimethylsilylenebis (2-methyl 4-Isopropylindenyl) zirconium dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylenebis (4,5,6 ,
7-tetrahydroindenyl) zirconium dichloride,
Dimethyl silylene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenyl silylene bis (indenyl) zirconium dichloride, diphenyl silylene bis (2-methyl, 4-isopropylindenyl) zirconium dichloride, diphenyl silylene bis (2,4,
7-trimethylindenyl) zirconium dichloride, methylphenylsilylene bis (indenyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride Chloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) benzyl zirconium monochloride, Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis Cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxy chloride , Bis (cyclopentadienyl) zirconium bis (methanesulfonate),
Bis (cyclopentadienyl) zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadiene) (Enyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclo) Pentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, Bis (butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) zirconium dichloride , Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above examples, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

In the zirconium compound as described above, a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium can also be used.

In the present invention, as the metallocene compound [A-3], a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used.

These compounds may be used alone,
You may use it in combination of 2 or more type. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. In the present invention, the metallocene compound [A] is preferably used by diluting it with a hydrocarbon, particularly an aliphatic hydrocarbon or an alicyclic hydrocarbon (b) described later.

Further, the above metallocene compound [A]
Can also be used with the carrier compound in contact with the particulate carrier compound. Examples of carrier compounds include Si
O ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO,
Inorganic carrier compounds such as TiO ₂ , ZnO, Zn ₂ O, SnO ₂ , BaO and ThO, resins such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, styrene-divinylbenzene copolymer Can be used. These carrier compounds can be used in combination of two or more kinds.

Next, the organoaluminum oxy compound [B] used in the present invention will be described. In the present invention, the organoaluminum oxy compound [B] is used as a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon (b) as described later.
Will be described.

The organoaluminum oxy compound [B] used in the present invention is a conventionally known aluminoxane [B-
1] or a benzene-insoluble organoaluminum oxy compound [B-2].

Such conventionally known aluminoxane [B-1] is specifically represented by the following general formulas (1) and (2).

[0029]

[Chemical 1]

(In the general formula (1) or (2), R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group or a butyl group, preferably a methyl group or an ethyl group, particularly preferably a methyl group. Yes, m is 2 or more, preferably 5
It is an integer of 40. ) Here, the aluminoxane is an alkyloxyaluminum unit represented by the formula (OAl (R ¹ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ² )) [wherein R ¹ and R ² are The same hydrocarbon group as R can be exemplified, and R ¹ and R ² represent different groups].

The conventionally known aluminoxane [B-1] is
For example, it is produced by the following method and is usually recovered as a solution of aromatic hydrocarbon. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the suspended aromatic hydrocarbon and reacted to recover the aromatic hydrocarbon solution as a solution. (2) A method in which water (water, ice, or steam) is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover it as a solution of the above medium.

Of these methods, the method (1) is preferably adopted. The organoaluminum compound used in producing the solution of aluminoxane specifically includes trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec- Butyl aluminum, tri
tert-Butylaluminium, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, trialkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminium chloride, diethylaluminium chloride, diethylaluminum bromide, diisobutylaluminum chloride. Dialkyl aluminum hydrides such as dialkyl aluminum hydride, diethyl aluminum hydride, diisobutyl aluminum hydride, etc., dialkyl aluminum alkoxides such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, etc.
Examples thereof include dialkylaluminum aryloxides such as diethylaluminum phenoxide.

Of these, trialkylaluminum is particularly preferred. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula [III] can also be used.

(I-C ₄ H ₉ ) _x Al _y (C ₅ H ₁₀ ) _z ... [III] (where x, y, and z are positive numbers, and z ≧ 2x). Such organoaluminum compounds may be used alone or in combination.

The benzene-insoluble organoaluminum oxy compound [B-2] used in the present invention is, for example, a method of bringing a solution of aluminoxane into contact with water or an active hydrogen-containing compound, or the above-mentioned organoaluminum. It can be obtained by a method of bringing a compound into contact with water.

Benzene-insoluble organic used in the present invention
In the case of aluminum oxy compounds, the compound is analyzed by infrared spectroscopy.
Analysis by method (IR), 1220 cm^-1In the vicinity
Absorbance (D₁₂₂₀) And 1260 cm^-1In the vicinity
Absorbance (D₁₂₆₀) And (D ₁₂₆₀/ D₁₂₂₀) Is 0.0
9 or less, preferably 0.08 or less, particularly preferably 0.0
It is preferably in the range of 4 to 0.07.

The above-mentioned benzene-insoluble organoaluminum oxy compound [B-2] is presumed to have an alkyloxy aluminum unit (i) represented by the following formula [IV].

[0038]

[Chemical 2]

In the formula, R ⁷ is a hydrocarbon group having 1 to 12 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n- group.
Examples thereof include a butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, cyclohexyl group and cyclooctyl group. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

The benzene-insoluble organoaluminum oxy compound [B-2] has the following formula [V] in addition to the alkyloxy aluminum unit (i) represented by the above formula [IV].
It may contain an oxyaluminum unit (ii) represented by

[0041]

[Chemical 3]

In the formula, R ⁸ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, halogen or hydrogen.
Further, R ⁸ and R ⁷ in the above formula [IV] represent different groups.

When the benzene-insoluble organoaluminum oxy compound [B-2] contains the above oxyaluminum unit (ii), the above alkyloxyaluminum unit
An organoaluminum oxy compound having (i) in an amount of 30 mol% or more, preferably 50 mol% or more, particularly preferably 70 mol% or more is desirable.

The organoaluminum oxy compound [B] as described above is usually commercially available or handled as a toluene solution. The organoaluminum oxy compound [B] used in the present invention may contain a small amount of an organic compound component of a metal other than aluminum.

The organoaluminum oxy compound [B] can also be used by supporting it on the above-mentioned carrier compound. In the present invention, the above organoaluminum oxy compound [B] is supplied to the polymerization system as a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon (b).

The aliphatic hydrocarbon or alicyclic hydrocarbon (b) used in the present invention preferably has a boiling point of 100 ° C or lower, more preferably 90 ° C or lower, and particularly preferably 75 ° C or lower.

Specific examples of such an aliphatic hydrocarbon or alicyclic hydrocarbon (b) include 2,2-dimethylpropane, 2-methylbutane, 2,2-dimethylbutane and 2,3-dimethylbutane. , 2,2,3-trimethylbutane, n-pentane, 2-methylpentane, 3-methylpentane, 2,2-dimethylpentane, 3,3-dimethylpentane, 2,3-dimethylpentane, 2,
4-dimethylpentane, n-hexane, 2-methylhexane,
3-methylhexane, n-heptane, cyclohexane, methylcyclopentane, dimethylcyclopentane and the like can be mentioned. These may be mixed and used.

The slurry of the organoaluminum oxy compound [B] is appropriately prepared by dispersing the organoaluminum oxy compound [B] in the aliphatic hydrocarbon or alicyclic hydrocarbon (b). It is prepared as follows. (1) Toluene was distilled off from a toluene solution of the organoaluminum oxy compound [B], and the resulting powdery organoaluminum oxy compound [B] was mechanically pulverized to obtain an aliphatic hydrocarbon or an alicyclic hydrocarbon ( b) suspension, (2)
Toluene was distilled off from the toluene solution of the organoaluminum oxy compound [B], and aliphatic hydrocarbon or alicyclic hydrocarbon (b) was added to the obtained powdery organoaluminum oxy compound [B], and then organoaluminum Method of mechanically pulverizing oxy compound [B], (3) contacting a toluene solution of organoaluminum oxy compound [B] with an aliphatic hydrocarbon or alicyclic hydrocarbon (b), Method of exchanging the medium after depositing B].

The toluene solution of the organoaluminum oxy compound [B] used in this case usually has a concentration of 0.1 to 10 g atom / liter, preferably 0.5 to 7 g atom / liter in terms of aluminum atom. , And more preferably 0.5 to 5 grams atom / liter.

In the above contact, the aliphatic hydrocarbon or the alicyclic hydrocarbon (b) is 0.3 volume ratio to the toluene solution of the organoaluminum oxy compound [B].
It is used in an amount of -10, preferably 0.5-5.

In the above description, the case where the toluene solution of the organoaluminum oxy compound [B] is used has been described, but the organoaluminum oxy compound [B] is used.
It is also possible to use a benzene solution of the organoaluminum oxy compound [B] instead of the toluene solution of.

In the present invention, the specific surface area of the solid organoaluminum oxy compound [B] in the slurry thus prepared is preferably 10 m ² / g or more, more preferably 100 m ² / g or more. Is more preferable.

In the present invention, the specific surface area is GUANTA
Using the CHROME MONOSORB-MS-12, a general B
It can be measured by the ET method. When measuring the specific surface area, an organoaluminum oxy compound [B]
It is desirable to dry under a reduced pressure, sample under a nitrogen atmosphere, and perform the measurement operation.

When the organoaluminum oxy compound [B] is supplied as a slurry of the aliphatic hydrocarbon or the alicyclic hydrocarbon (b) to the polymerization vessel as described above, the olefin can be polymerized or copolymerized with high polymerization activity. it can.

The olefin polymerization catalyst used in the present invention is formed from the metallocene compound [A] and the organoaluminum compound [B] as described above, and together with them, the organoaluminum compound [C] is optionally added. It may be contained. As such an organoaluminum compound [C], for example, an organoaluminum compound represented by the following formula [VI] can be exemplified.

R ⁹ _n AlX _3-n ... [VI] In the formula, R ⁹ 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 such a hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. 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.

As such an organoaluminum compound, the following compounds are specifically used. Trialkyl aluminum such as trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri-2-ethylhexyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl. Dialkyl aluminum halides such as aluminum chloride and dimethyl aluminum bromide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, methyl Aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, alkyl aluminum dihalides such as ethyl aluminum dibromide, diethyl aluminum hydride, alkyl aluminum hydride such as diisobutyl aluminum hydride.

As the organoaluminum compound [C], a compound represented by the following formula [VII] can also be used. During ^{_{R 9 n AlY 3-n ...}} [VII] formula, R ⁹ is the same as the formula [VI], Y is -OR ¹⁰
Group, -OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR
¹³ ₂ group, —SiR ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group. R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, A trimethylsilyl group and the like, and R ¹⁴ and R ¹⁵ are a methyl group, an ethyl group and the like. n is 1-2.

As such an organoaluminum compound, the following compounds are specifically used. (i) compounds represented by R ⁹ _n Al (OR ¹⁰ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ⁹ _n Al (OSi R ¹¹ ₃ ) A compound represented by _3-n , for example, Et ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Me ₃ ) (iso-Bu) ₂ Al (OSi Et ₃ ), (iii) R ⁹ _n A
a compound represented by l (OAlR ¹² ₂ ) _3-n , for example,
Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) _2, etc., (iv) R ⁹ _n A
a compound represented by l (NR ¹³ ₂ ) _3-n , such as Me ₂
AlNEt ₂ Et ₂ AlNHMe Me ₂ AlNHET Et ₂ AlN (Si Me ₃ ) ₂ (iso-Bu) ₂ AlN (SiMe ₃ ) ₂ etc., (V) R ⁹ _n Al
A compound represented by (Si R ¹⁴ ₃ ) _3-n , for example, (is
o-Bu) ₂ AlSi Me _3, etc.,

[0061]

[Chemical 4]

In the present invention, among the above-mentioned organoaluminum compounds [C], trialkylaluminum is preferable, and triisobutylaluminum is particularly preferable. Two or more kinds of these organoaluminum compounds [C] can be mixed and used.

The olefin polymerization catalyst used in the present invention is formed from the above catalyst components [A], [B] and, if necessary, [C]. At this time, the metallocene compound [A] is usually used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0.05 mmol, calculated as transition metal atoms per liter of polymerization volume. In the organoaluminum oxy compound [B], the amount of the aluminum atom in the organoaluminum oxy compound [B] is usually about 1 to 10000 mol, preferably 10 to 1 mol of the transition metal atom of the metallocene compound [A]. 5
It is used in an amount such that it is 000 mol. Furthermore, when the organoaluminum compound [C] is used, the organoaluminum compound [C] is usually about 0 to 200 mol, preferably about 10 mol, relative to 1 mol of aluminum atom in the organoaluminum oxy compound [B]. It is used in an amount such that it is from 0 to 100 mol.

In the present invention, olefin is polymerized or copolymerized in the presence of such an olefin polymerization catalyst to produce a polyolefin. Examples of such olefins include α-olefins having 2 to 20 carbon atoms and, if necessary, non-conjugated dienes.

Α- having 2 to 20 carbon atoms used in the present invention
As the olefin, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-
Pentene, 1-octene, 1-decene, 1-dodecene and the like can be mentioned.

As the non-conjugated diene, 5-ethylidene
Cyclic non-conjugated dienes such as -2-norbornene, 5-propylidene-5-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4-hexadiene, 4-methyl-1,4
-Hexadiene, 5-methyl-1,4-hexadiene, 5-methyl
Examples include chain-like non-conjugated dienes such as -1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,7-octadiene, 7-methyl-1,6-octadiene.

In the present invention, an aliphatic hydrocarbon or an alicyclic hydrocarbon is used as a medium when carrying out the polymerization.
This aliphatic hydrocarbon or alicyclic hydrocarbon has a boiling point of 10
The temperature is preferably 0 ° C. or lower, and the aliphatic hydrocarbon or alicyclic hydrocarbon specifically used in preparing the slurry of the organoaluminum oxy compound [B] described above.
It is particularly preferable that it is the same as in (b). You may use these aliphatic hydrocarbons or alicyclic hydrocarbons in combination of 2 or more types. Of these, hexane, methylpentane, methylcyclopentane and mixtures thereof are preferably used.

Such an aliphatic hydrocarbon or alicyclic hydrocarbon (b) does not have an offensive odor and is easily volatilized, the drying process of the produced polymer can be simplified, and the final obtained polymer is No odor remains.

The polymerization is usually carried out at a temperature of -20 ° C to 200 ° C.
° C, preferably 0 ° C to 150 ° C, particularly preferably 20
℃ ~ 120 ℃, the pressure is usually atmospheric pressure ~ 100Kg / cm
² , preferably from atmospheric pressure to 50 kg / cm ² , particularly preferably from atmospheric pressure to 30 kg / cm ² .

The molecular weight can be adjusted by changing the polymerization conditions such as the polymerization temperature, or can be adjusted by controlling the amount of hydrogen (molecular weight modifier) used.

The above-mentioned polymerization can be carried out by a solution polymerization method, a suspension polymerization method or the like. Of these, the solution polymerization method is preferred in the invention. Also, the polymerization is batch type,
It can be carried out by either a semi-continuous method or a continuous method, but it is preferably carried out continuously. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The polymer produced immediately after the polymerization can be recovered by a conventionally known separation / recovery method. In the case of solution polymerization, the solvent is evaporated directly to dryness, or after phase separation,
A method of evaporating the solvent of the concentrated phase and drying to dryness is preferable.

According to the present invention, since the aliphatic hydrocarbon or the alicyclic hydrocarbon is used as the polymerization medium, the drying step can be simplified, and a polyolefin having no odor in the polymerization medium can be easily obtained. You can

The polyolefin obtained in the present invention is an α-olefin homopolymer or an α-olefin copolymer as described above, and a copolymer of α-olefin and, if necessary, a non-conjugated diene.

The polyolefin obtained in the present invention is preferably a copolymer of ethylene, an α-olefin and, if necessary, a non-conjugated diene, and the constitutional unit derived from ethylene is 30 to 95 mol. %, More preferably from 40 to 93 mol%, from 5 to 70 mol%, preferably from 7 to 60 mol%, of the constituent units derived from an α-olefin having 3 or more carbon atoms, from the non-conjugated diene. Particularly preferred are low crystalline polyolefins which contain derived structural units in an amount of 0 to 10 mol%.

The polyolefin obtained in the present invention is 13
The intrinsic viscosity [η] measured in decalin at 5 ° C. is usually 0.
It is 5 to 20 dl / g, preferably 0.7 to 10 dl / g, and more preferably 1.0 to 5.0 dl / g.

The polyolefin obtained by using the olefin polymerization catalyst as described above in the present invention is excellent in composition distribution of each component.

[0078]

According to the present invention, when a polyolefin is produced in the presence of a hydrocarbon medium, the drying step can be simplified, and a polyolefin free of odor of a polymerization solvent can be easily produced.

[0079]

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

In the following examples, n-hexane 6
A mixed medium consisting of 0% by volume, 22% by volume of methylcyclopentane, and 18% by volume of 3-methylpentane is called hexane.

[0081]

Example 1 Preparation of Methylalumoxane Hexane Slurry (1) In a nitrogen atmosphere, a glass reactor equipped with a stirring blade has a toluene solution of methylalumoxane of 1.5 gram atom / liter in terms of aluminum atom. 1 liter was charged, and 1 liter of hexane substituted with nitrogen was added dropwise at room temperature over 1 hour with stirring. The produced solid methylalumoxane was filtered, washed with hexane, dried under reduced pressure, and except a part thereof taken out for analysis, suspended in hexane to obtain a hexane slurry (1) of methylalumoxane. Prepared.

The specific surface area of the obtained methylalumoxane was 180 m ² / g. 2 liter autoclave (polymerizer) equipped with a pressure batch copolymerization stirring blade of ethylene and propylene
Was used to copolymerize ethylene and propylene.

0.9 liters of hexane dehydrated and refined from the upper part of the polymerization vessel, 0.1 liters of propylene, and a hexane slurry (1) of methylalumoxane obtained above (1.1 mg atom / aluminum atom / ml)
And 0.9 ml of a hexane solution of triisobutylaluminum (1 mmol / ml). System 70
After the temperature was raised to ℃, ethylene was charged so that the total pressure would be 7 kg / cm ² . After charging 0.29 ml of a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (0.0034 mmol / ml) using a pressure equalizing tube, the temperature was 80 ° C. and the total pressure was 8 kg / cm ^2. While maintaining 1
Polymerization was carried out for a time. After depressurization, the polymer solution was taken out and dried.

The yield was 56.7 g. The obtained copolymer had an ethylene content of 86 mol% and an intrinsic viscosity [η] measured in 135 ° C. decalin of 1.8 dl / g.

[0085]

Example 2 Preparation of Methylalumoxane Hexane Slurry (2) Under a nitrogen atmosphere, in a glass reactor equipped with a stirring blade, a toluene solution of methylalumoxane of 1.5 gram atom / liter in terms of aluminum atom. After charging 1 liter and distilling off toluene, a hexane slurry (2) of methylalumoxane was prepared by adding hexane which had been replaced with nitrogen except for taking it out for analysis.

The specific surface area of the obtained methylalumoxane particles was 25 m ² / g. Pressure-Batch Copolymerization of Ethylene and Propylene Copolymerization of ethylene and propylene was performed in the same manner as in Example 1 except that the hexane slurry (2) of methylalumoxane was used.

The polymer yield was 18.2 g. The resulting copolymer had an ethylene content of 84 mol%, 135
Intrinsic viscosity [η] measured in decalin at 1.7 ° C is 1.7 dl / g
Met.

[0088]

Example 3 Pressurized Continuous Copolymerization of Ethylene and Propylene Using a 15-liter stainless steel polymerization vessel equipped with a stirring blade, ethylene and propylene were continuously copolymerized.

3.5 liters of hexane dehydrated and purified from the upper part of the polymerization vessel per hour, and a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (0.
0.25 liters per hour (03 mmol / liter), 0.5 liters per hour of a hexane solution of triisobutylaluminum (8 mmol / liter), hexane slurry (1) of methylalumoxane (1.33 in terms of aluminum atoms). 0.7 per milligram atom / liter)
5 liters were continuously supplied.

Further, ethylene was fed from the upper part of the polymerization vessel at 360 hr.
Lithium and propylene were continuously supplied at 340 liters per hour. The polymerization pressure was 7.9 kg / cm ² , and the residence time was about 1 hour.

Then, a small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction,
The copolymer was separated from the solvent by steam stripping treatment, and then dried at 80 ° C. under reduced pressure (100 mmHg) for 2 hours.

The polymer obtained had no solvent odor. With the above operation, the ethylene / propylene copolymer is 42 per hour.
Obtained at a rate of 0 g. The resulting copolymer had an ethylene content of 80 mol% and an intrinsic viscosity [η] of 2.3 dl / g measured in decalin at 135 ° C.

[0093]

Comparative Example 1 In the copolymerization of Example 3, the same operation was performed except that a toluene solution of methylalumoxane was used instead of the hexane slurry (1) of methylalumoxane. The copolymer obtained is at 80 ° C under reduced pressure (100 mm
Hg), there is a toluene odor even after drying for 24 hours,
It was found that the drying was insufficient.

[0094]

Example 4 In Example 3, bis (1,3-dimethylcyclopentadienyl) zirconium bistrifluoromethanesulfonyl was used in place of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, and ethylene was added. The same operation was carried out except that 320 liters / hour, 390 liters / hour of propylene were continuously fed so that the hydrogen concentration in the gas phase part of the polymerization vessel was 0.07 mol%.

By the above operation, an ethylene / propylene copolymer was obtained at a rate of 430 g / hr. The obtained copolymer had an ethylene content of 78 mol% and an intrinsic viscosity [η] measured in decalin at 135 ° C. of 1.1 dl / g.

[0096]

Example 5 Pressure Batch Copolymerization of Ethylene, Propylene and Diene 2 liter autoclave equipped with stirring blade (polymerizer)
With ethylene, propylene and 7-methyl-1,6-
Copolymerization of octadiene was performed.

0.86 liter of hexane dehydrated and purified from the upper part of the polymerization vessel, 185 ml of propylene, 7-methyl-
40 ml of 1,6-octadiene, 0.18 ml of the hexane slurry (1) of methylalumoxane obtained in Example 1 (1.1 mg atom / ml in terms of aluminum atom),
0.8 ml of a hexane solution of triisobutylaluminum (1 mmol / ml) was charged. After heating the system to 70 ° C., ethylene was charged so that the total pressure became 7 kg / cm ² .
Using a pressure equalizing tube, a solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride in hexane (0.0
(034 mmol / ml) was charged at 0.44 ml and the temperature was adjusted to 6
Polymerization was carried out for 1 hour while maintaining a total pressure of 8 kg / cm ² at 0 ° C. After depressurization, the polymer solution was taken out and dried.

The yield was 72.8 g. The obtained copolymer had an ethylene content of 78 mol%, an intrinsic viscosity [η] measured in decalin at 135 ° C. of 2.6 dl / g, and an iodine value of 13.

[0099]

Example 6 Copolymerization of ethylene and 1-butene 2 liter autoclave equipped with stirring blade (polymerizer)
Was used to copolymerize ethylene with 1-butene.

0.7 liter of hexane dehydrated and purified from the upper part of the polymerization vessel, 300 ml of 1-butene, hexane slurry of methylalumoxane (1) obtained in Example 1 (1.1 mg atom in terms of aluminum atom) / Ml) and 0.9 ml of a hexane solution of triisobutylaluminum (1 mmol / ml). 70 ℃
After raising the temperature to 1, ethylene was charged so that the total pressure became 7 kg / cm ² . After charging 0.29 ml of a hexane solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride (0.0034 mmol / ml) using a pressure equalizing tube, the temperature was 90 ° C. and the total pressure was 8 kg / cm ^2. Was maintained for 1 hour to carry out polymerization. After depressurization, the polymer solution was taken out and dried.

The yield was 54.1 g. The obtained copolymer had an ethylene content of 91 mol% and an intrinsic viscosity [η] measured in decalin at 135 ° C. of 3.5 dl / g.

[0102]

Example 7 Pressure Batch Copolymerization of Ethylene and Propylene Using a 2 liter autoclave equipped with a stirring blade,
Copolymerization of ethylene and propylene was performed.

0.8 liters of hexane dehydrated and refined from the upper part of the polymerization vessel, and a hexane slurry (1) of the methylalumoxane obtained above (1 in terms of aluminum atom).
0.9 ml of 1 mg atom / ml) was charged. System 80
Total pressure then the temperature was raised to ℃ is charged with propylene so that 14.5 kg / cm ^2, further total pressure was charged with ethylene to a 15 Kg / cm ^2. Using a pressure equalizing tube, 3.4 ml of a hexane solution of bis (methylcyclopentadienyl) zirconium dichloride (0.0029 mmol / ml) was prepared.
After charging, polymerization was carried out for 1 hour while maintaining the temperature at 80 ° C. and the total pressure at 15 kg / cm ² . After depressurization, the polymer solution was taken out and dried.

The yield was 29.1 g. The obtained copolymer had an ethylene content of 55 mol% and an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.18 dl / g.

[0105]

Example 8 Using a 2-liter autoclave equipped with a pressure batch copolymerization stirring blade of propylene and 1-butene ,
Copolymerization of propylene and 1-butene was performed.

0.67 liters of hexane dehydrated and purified from the upper part of the polymerization vessel, 220 g of 1-butene, a hexane slurry of methylalumoxane (1) obtained above (1.1 mg atom / ml in terms of aluminum atom) ) To 0.
36 ml, hexane solution of triisobutylaluminum (1 mg atom / ml in terms of aluminum atom)
1 ml was charged. After heating the system to 70 ° C, the total pressure is 14
Propylene was charged so as to be Kg / cm ² . Dimethylsilylenebis (2-methylindenyl) using a pressure equalizing tube
Zirconium dichloride in hexane (0.0008
(2 mmol / ml), temperature 70 ℃, total pressure 1
Polymerization was carried out for 1 hour while maintaining 4 kg / cm ² . After depressurization, the polymer solution was taken out, hexane was removed, and then dried.

The yield was 81.1 g. The obtained copolymer had a propylene content of 76 mol% and an intrinsic viscosity [η] measured in decalin at 135 ° C. of 1.3 dl / g.

[Brief description of drawings]

FIG. 1 shows a process for preparing an olefin polymerization catalyst used in the present invention.

Claims (4)

[Claims] 1. An olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising [A] a metallocene compound of a transition metal selected from Group IVB of the periodic table and [B] an organoaluminumoxy compound. In producing a polyolefin, the organoaluminum oxy compound [B] is added to the polymerization system as a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon, and in the presence of an aliphatic hydrocarbon medium or an alicyclic hydrocarbon medium. A method for producing a polyolefin, characterized in that polymerization is carried out. 2. The organoaluminum oxy compound [B]
The method for producing a polyolefin according to claim 1, wherein the specific surface area is 10 m ² / g or more. 3. An olefin in the presence of a catalyst for olefin polymerization comprising [A] a metallocene compound of a transition metal selected from Group IVB of the periodic table, [B] an organoaluminum oxy compound, and [C] an organoaluminum compound. In producing a polyolefin by polymerizing or copolymerizing the above, the organoaluminum oxy compound [B] is added to the polymerization system as a slurry of an aliphatic hydrocarbon or an alicyclic hydrocarbon, and an aliphatic hydrocarbon medium or an alicyclic hydrocarbon is added. A method for producing a polyolefin, which comprises polymerizing in the presence of a group hydrocarbon medium. 4. The organoaluminum oxy compound [B]
The method for producing a polyolefin according to claim 3, wherein the specific surface area of the polyolefin is 10 m ² / g or more.