JPH07133306A - Olefin polymerization catalyst and preparation of polyolefin - Google Patents

Abstract

PURPOSE:To produce a polyolefin with a high polymerization activity while avoiding polymer deposition on the inner wall surface of a polymerizer. CONSTITUTION:The catalyst comprises (a) an adduct formed between an organoaluminumoxy compound and a polar organic compound possessing within its molecule at least one atom selected from among phosphorus, nitrogen, sulfur and oxygen atoms but not possessing active hydrogen and (b) an olefin polymerization catalyst comprising at least one metallocene compound of a Group 3, 4, 5 or 6 transition metal of the Periodic Table. The process comprises (co) polymerizing an olefin in the presence of the above catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing a polyolefin using the catalyst.
More specifically, the present invention relates to an olefin polymerization catalyst that can be produced with high activity even when the amount of an organoaluminum oxy compound used is reduced, and can be produced without adhering a polymer to the wall of a polymerization vessel, and a method for producing a polyolefin using this catalyst.

[0002]

Polyethylene and ethylene-α-using metallocene compounds and methylaluminoxane as catalysts
A method for producing an olefin copolymer is known. For example, JP-A-58-19309 discloses that ethylene and a copolymer of ethylene and a C ₃ -C ₁₂ α-olefin are catalyzed by biscyclopentadienyl zirconium dichloride and linear or cyclic methylaluminoxane. A manufacturing method is disclosed. This method has a large activity per transition metal and is excellent in copolymerizability, but it is necessary to use a large amount of expensive methylalumoxane, which is problematic from an industrial viewpoint. Further, since these catalyst systems are homogeneous, the resulting polymer particles become fine powder and are difficult to handle, and fouling occurs, which makes stable industrial production difficult.

In order to solve these problems, attempts have been made to improve aluminoxane. For example, JP-A-6
In Japanese Patent Publication No. 1-211307, a unit of aluminum is 40.
A method for polymerizing olefins using aluminoxane in the form of a monomer or higher is described. Also, Japanese Patent Laid-Open No. 61-13060
4, JP-A-60-245604, JP-A-63-2609
Japanese Patent Publication No. 03 describes a method using aluminoxane containing halogen.

Japanese Unexamined Patent Publication (Kokai) No. 64-16803 describes a method using an aluminoxane partially crosslinked with water. Further, JP-A-1-240504 describes a method using a heat-treated aluminoxane. JP-A-1-242607 describes a method using an aluminoxane obtained by reacting an organic aluminum compound with water and an organic polyhydroxy compound.

Further, JP-A-3-103407 discloses a method of using an aluminoxane composed of organic aluminum having normal alkyl, organic aluminum having branched alkyl, and water. Japanese Patent Application Laid-Open No. 2-22308 describes a method of simultaneously using an aluminoxane derived from trinormal alkylaluminum and an aluminoxane derived from organoaluminum having a substituent other than the normal alkyl group.

US Pat. Nos. 5,091,352 and 5,
No. 171,799 describes a method of using an aluminoxane, which is hardly soluble in benzene, obtained by contacting an organoaluminum compound with water or a compound having active hydrogen. Japanese Unexamined Patent Publication (Kokai) No. 3-139503 describes a method using an aluminoxane in which a part of an alkyl group is replaced with a hydrogen atom.

However, in the catalyst systems described in these prior arts, the activity per aluminoxane is not sufficient and the effect of preventing fouling is not sufficient, and particularly in slurry polymerization, continuous operation for a long time is difficult.

[0008]

SUMMARY OF THE INVENTION The present invention provides an olefin polymerization catalyst which is highly active even when the amount of the organoaluminum oxy compound used is reduced and which can be produced without the adhesion of the polymer to the wall of the polymerization vessel. In addition, it is intended to produce a polyolefin using this catalyst.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors finally found a novel olefin polymerization catalyst and a method for producing a polyolefin, which meet the objectives. Arrived That is, the olefin polymerization catalyst according to the present invention comprises (a) an organoaluminumoxy compound and at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in the molecule.
It is characterized by comprising an addition reaction product of an organic polar compound which has a longevity and does not have active hydrogen, and (b) at least one kind of metallocene compound of a transition metal of Group 3, 4, 5 or 6 of the periodic table. Further, the method for producing a polyolefin according to the present invention is characterized by polymerizing or copolymerizing an olefin in the presence of the above-mentioned polymerization catalyst.

The olefin polymerization catalyst according to the present invention and the method for producing a polyolefin using this catalyst will be specifically described below. (A) an organoaluminum oxy compound used in the present invention and an organic polar compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in the molecule and having no active hydrogen Examples of the organoaluminum oxy compound used in the addition reaction product include aluminoxane.

The aluminoxane used in the catalyst is an organoaluminum compound represented by the general formula (8) or the general formula (9). General formula (8)

[Chemical 1] General formula (9)

[Chemical 2] R ²⁰ is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. m is an integer of 1 to 100, preferably 4 or more and particularly 8 or more. A method for producing a compound of this kind is known, for example, a method in which a salt having water of crystallization is added to a hydrocarbon solvent suspension of (copper sulfate hydrate, aluminum sulfate hydrate) by adding trialkylaluminum or carbonization. A method of reacting trialkylaluminum with solid, liquid or gaseous water in a hydrogen solvent can be exemplified.

Further, the general formula (10) or the general formula (1
You may use the aluminoxane shown by 1). General formula (10)

[Chemical 3] General formula (11)

[Chemical 4] R ²¹ is a methyl group, an ethyl group, a propyl group, a butyl group,
A hydrocarbon group such as an isobutyl group, preferably a methyl group or an isobutyl group. R ²² is a methyl group,
It is a hydrocarbon group such as an ethyl group, a propyl group, a butyl group or an isobutyl group, or a halogen or hydrogen atom such as chlorine or bromine, or a hydroxyl group, which is different from R ²¹ .
R ²² may be the same or different. m is usually 1
To an integer of 100, preferably 3 or more, m
+ N is 2 to 100, preferably 6 or more.

In the general formula (10) or (11),

[Chemical 5] The blocks may be connected in a block manner, or may be randomly connected in a regular or irregular manner. The method for producing such an aluminoxane is the same as that for the aluminoxane represented by the general formula described above. Instead of one kind of trialkylaluminum, two or more kinds of trialkylaluminum are used, or one or more kinds of trialkylaluminum and one kind are used. The above dialkylaluminum monohalide or dialkylaluminum monohydride may be used. Further, as the organoaluminum oxy compound according to the present invention, aluminoxane which is heat-treated or treated with water may be used. Further, as the organoaluminum oxy compound according to the present invention, two or more of the general formulas (8), (9), (10) and (11) may be mixed and used.

The organoaluminum oxy compound (a) used in the present invention and at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule.
The organic polar compound used in the addition reaction product with the organic polar compound having a constant and no active hydrogen means a compound having a functional group containing the atom and having no active hydrogen. Active hydrogen refers to hydrogen directly bonded to a phosphorus atom, a nitrogen atom, a sulfur atom or an oxygen atom, and compounds having active hydrogen include alcohols such as methanol and ethanol, diols such as ethylene glycol and hydroquinone, acetic acid and propione. Examples thereof include carboxylic acids such as acids, amines such as methylamine and dimethylamine, thiols such as ethanethiol, phosphines such as methylphosphine and dimethylphosphine, but such compounds are not preferred in the present invention.

The addition reaction according to the present invention means O, P, N,
An atom with a high electronegativity such as S and a lone electron pair,
This is a reaction in which the lone pair of electrons is used to coordinate to the empty conformation of Al. The reaction of a compound having active hydrogen, such as an alcohol or a diol, with an organoaluminum causes a substitution reaction with an alkyl group to generate a corresponding hydrocarbon. On the other hand, in the addition reaction, only the coordination to the empty conformation occurs, and the generation of hydrocarbon does not occur. The organic polar compound according to the present invention is preferably a compound which, in the reaction with the organoaluminum oxy compound, causes only coordination to an aluminum atom and does not generate hydrocarbons.

The organic polar compound will be described in detail below. The organic polar compound containing a nitrogen atom is a compound having no active hydrogen in the molecule and having at least one functional group selected from dialkylamino group, nitrile group, N-alkylamide group and pyridyl group. Or pyridines are preferred.

Specific examples of the compounds having the above functional groups will be shown below. Examples of the compound having an amino group include N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N, N'-dimethylpiperazine, N,
N, N ', N'-tetramethyl-1,4-phenylenediamine, N, N, N', N'-tetramethyl-1,3-
Phenylenediamine, bis [2- (dimethylamino) ethoxy] methane, N-methyl-N, N-bis- (3-dimethylaminopropyl) amine, 3,3 ′, 3 ″ -tris (dimethylamino) tripropylamine Etc. can be illustrated.

Examples of the compound having a nitrile group include succinic acid dinitrile, malonnitrile, biscyanomethylbenzene, tetracyanoethane, fumaronitrile, terephthalonitrile, phthalonitrile and tetramethylenedioxydipropiononitrile.

Examples of the compound having an N-alkylamide group include N, N-dimethylacetic acid amide, N, N-dimethylformic acid amide, N, N, N ', N'-tetramethylglutaric acid diamide, N, N, N ', N'-tetramethyl succinic acid diamide etc. can be illustrated. Examples of the compound having a pyridyl group include 4,4′-bipyridine.

The pyridine compound according to the present invention refers to a heterocyclic compound containing a nitrogen atom as an atom constituting a ring system, and in this case, a compound containing two or more nitrogen atoms is desirable. Specific examples include pyridazine, pyrimidine, pyrazine, cinnoline, quinazoline, quinoxaline, phthalazine, triazine and the like.

Among the above organic polar compounds containing a nitrogen atom, compounds having at least one amino group in the molecule and having no active hydrogen are more preferable. Furthermore, a compound having two or more amino groups in the molecule is more preferable. The organic polar compound containing an oxygen atom, which does not have active hydrogen in the molecule, and a carbonyl group,
It is necessary that the compound has at least one functional group selected from an alkoxy group, an aryloxy group and an isocyano group.

Specific examples of the compounds having the above functional groups will be shown below. As the compound having an alkoxy group, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, polyethylene glycol dimethyl ether, 1,3-dioxalane, 1,4
-Dioxane, trioxane, 1,7-octadiene dioxide, trimethyl orthoformate, trimethyl orthoacetate and the like can be exemplified.

The compound having an aryloxy group is
Examples thereof include hydroquinone dimethyl ether, resorcinol dimethyl ether, veratrol and the like. The compound having a carbonyl group is preferably selected from ketones, esters, lactones and acid anhydrides. Examples of ketones include quinone, cyclohexanedione, butanedione, acetylacetone, hexanedione and the like.

Examples of the esters include methyl acetate, ethyl acetate, benzyl acetate, cyclohexyl acetate, methyl benzoate, methyl formate, methyl hexanoate, dimethyl phthalate, dimethyl isophthalate, dimethyl terephthalate, diethyl terephthalate and diisobutyl terephthalate. , Dimethyl fumarate, dimethyl maleate, dimethyl adipate, dimethyl oxalate, dimethyl succinate, tetrahydrofuran-2, 4-dione, ethylene carbonate, propylene carbonate, dimethyl carbonate, dimethyl dicarbonate, ditert-dicarbonate, etc. it can.

Examples of lactones include γ-butyrolactone, ε-caprolactone, coumarin, furanone, γ-pentanolactone and phthalide. Examples of the acid anhydride include acetic anhydride, benzoic anhydride, maleic anhydride, phthalic anhydride, oxalic acid monomethyl ester anhydride and the like.

As the compound having an isocyanate group,
Examples thereof include ethyl isocyanate, phenyl isocyanate, cyctohexyl isocyanate, hexamethylene diisocyanate, phenylene diisocyanate, silicon tetraisocyanate and diphenylmethane diisocyanate.

Among the above organic polar compounds containing an oxygen atom, compounds having at least one functional group selected from a carbonyl group in the molecule and having no active hydrogen are more preferable. Furthermore, compounds having two or more functional groups selected from carbonyl groups in the molecule are preferable.

As the organic polar compound containing a sulfur atom,
Of the functional groups that do not have active hydrogen in the molecule and are selected from alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups, thiocarbonyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups It is preferable that the compound has at least one functional group.

Specific examples of the compounds having the above functional groups are shown below. 1,2-dimethylthioethane, 1,2-diethylthioethane, 1,1-bis (ethylthio) propane, 1,2-diphenylthioethane,
3,5,7-trithianonane, dithiane, 2,3-dihydro-1,4-benzodithiin, diethyl disulfide, ethylphenyldisulfane, cyclohexanedithione, butanedithione, S-methylhexanethioate, O-ethylhexanethioate, Examples include methyl dithioacetate, butyl methyl sulfoxide, diethyl sulfone and the like.

Further, it is preferable that there is a compound having at least one thiocarbonyl group in the molecule and having no active hydrogen. Furthermore, compounds having two or more thiocarbonyl groups in the molecule are preferable.

As the organic polar compound containing a phosphorus atom,
A compound having at least one phosphorus atom in the molecule and further containing at least one atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom is more preferable. Specifically, the general formula (4) or the general formula (5) [wherein, R ^{14 to} R ¹⁶ are alkyl groups having 1 to 20 carbon atoms, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, Arylthio group, dialkylamino group, acyl group and the like,
At least one of them is an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a dialkylamino group, an acyl group, and Z is ═O, ═S, an alkylidene group, an imino group, etc.] It is desirable to be selected.

More preferably, the compound is represented by the general formula (6) or the general formula (7) [in the formula, R ^{17 to} R ¹⁹ are an alkyl group having 1 to 20 carbon atoms or an aryl group]. .

In the above formula, R ^{14 to} R ¹⁶ and R ^{17 to} R
¹⁹ will be specifically described. As the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group,
t-butyl group, amyl group, isoamyl group, hexyl group,
Examples thereof include heptyl group, octyl group, nonyl group, decyl group, cetyl group, cyclopentyl group and cyclohexyl group.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group, hexyloxy group, octyloxy group and cyclohexyloxy group. it can.

As the alkylthio group, a methylthio group,
Examples thereof include ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, t-butylthio group, hexylthio group, octylthio group and cyclohexylthio group.

Examples of the aryl group include a phenyl group, a tolyl group and a naphthyl group. A phenoxy group etc. can be illustrated as an aryloxy group. A phenylthio group etc. can be illustrated as an arylthio group. Examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a dibutylamino group, a methylethylamino group and a methylphenylamino group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group and a benzoyl group.

Next, Z will be specifically described. Examples of the alkylidene group include a methylene group, an ethylidene group, a propylidene group, a cyclopentadienylidene group, a cyclohexylidene group, a benzylidene group and the like. Examples of the imino group include a methylimino group, an ethylimino group, a butylimino group, a benzylimino group, and a phenylimino group.

Specific examples of the organic polar compounds represented by the general formulas (4) and (5) are shown below. Trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide, tributylphosphine oxide, triallylphosphine oxide, tricyclohexylphosphine oxide, dimethylethylphosphine oxide, dimethylphenylphosphine oxide, methylethylphenylphosphine oxide, diethylvinylphosphine oxide, diphenyl-
p-tolylphosphine oxide, acetyldiphenylphosphine oxide, benzoyldiphenylphosphine oxide,

Trimethylphosphine sulfide, triethylphosphine sulfide, triphenylphosphine sulfide, tributylphosphine sulfide, triallylphosphine sulfide, tricyclohexylphosphine sulfide, dimethylethylphosphine sulfide,
Dimethylphenylphosphine sulfide, methylethylphenylphosphine sulfide, diethylvinylphosphine sulfide, diphenyl-p-tolylphosphine sulfide,

Methoxydimethylphosphine, ethoxydimethylphosphine, butoxydimethylphosphine, ethoxydiethylphosphine, ethoxydipropylphosphine, ethoxydibutylphosphine, methoxydiphenylphosphine, ethoxydiphenylphosphine, ethoxyethylbutylphosphine, ethoxymethylphenylphosphine, butoxyphenylvinyl. Phosphine, phenoxydiphenylphosphine, phenoxydibenzylphosphine,

Trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tricyclohexyl phosphate, triallyl phosphate, triphenyl phosphate, tri-p
-Tolyl phosphate,

Trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tricyclohexyl phosphite, triallyl phosphite, triphenyl phosphite, tri-p
-Tolyl phosphite, tribenzyl phosphite,

Tris (dimethylamino) phosphine, tris (diethylamino) phosphine, tris (dipropylamino) phosphine, tris (dibutylamino) phosphine, phosphorous tripiperidide, phosphorous tri (N-methylanilide) phosphine,

Methyldimethylphosphinate, methyldiethylphosphinate, ethyldiethylphosphinate, ethyldipropylphosphinate, ethyldibutylphosphinate, methyldicyclohexylphosphinate, ethyldiphenylphosphinate, O-methyldimethylphosphinothioate, O- Methyldiethylphosphinothioate, O-ethyldiethylphosphinothioate, O-methyldipropylphosphinothioate, O
-Phenyldiethylphosphinothioate, methyldiethylphosphinodithioate, ethyldiethylphosphinodithioate, methyldipropylphosphinodithioate, phenyldiethylphosphinodithioate,

Diethylmethylphosphonit, Diphenylmethylphosphonit, Dimethylethylphosphonit, Diethylethylphosphonit, Diphenylethylphosphonit, Diethylpropylphosphonit, Diethylbutylphosphonit,
Diethyl phenyl phosphonite, dimethyl phenyl phosphonite, diethyl benzyl phosphonite,

Diethylmethylphosphonate, diphenylmethylphosphonate, dimethylethylphosphonate, diethylethylphosphonate, diphenylethylphosphonate, diethylpropylphosphonate, diethylbutylphosphonate, diethylphenylphosphonate, dimethylphenylphosphonate, diethylbenzylphosphonate, diethylcyclohexylphosphonate, diethylvinylphosphonate , Ethylmethyl methylphosphonate,
Diethyl acetyl phosphonate, diethyl benzyl phosphonate,

O, O-dimethylmethylphosphonothioate, O, O-diethylmethylphosphonothioate, O,
O-dipropylmethylphosphonothioate, O, O-dibutylmethylphosphonothioate, O, O-diethylethylphosphonothioate, O, O-dibutylethylphosphonothioate, O, O-diethylphenylphosphonothioate, O , S-diethylmethylphosphonothioate, O-ethyl-S-methylethylphosphonothioate, O-ethyl-O-methylethylphosphonothioate, O-ethyl-S-phenylethylphosphonothioate, ethyl-N, N -Diethyl-P-methylphosphonamidiate, S-ethyl-N, N-diethyl-P-methylphosphonamidothioate, O-ethyl-N, N-diethyl-P-methylphosphonamidothioate, O-ethyltriethylphosphonamidothio Ato,

Examples thereof include N-ethyl-P, P, P-triphenylphosphine imide, N-phenyl-P, P, P-triphenylphosphine imide and benzoyldiphenylphosphine.

As the organic polar compound containing a phosphorus atom,
In the general formula (4) and the general formula (5), a compound in which at least one of R ^{14 to} R ¹⁶ is an alkoxy group or an aryloxy group is preferable, and R ^{14 to} R ¹⁶ are each an alkoxy group or an aryloxy group. More preferred are compounds that are either. Moreover, the compound represented by the general formula (6) or the general formula (7) is more preferable, and the compound represented by the general formula (7) is particularly preferable. R ^{17 to} R ¹⁹ in the general formula (7) are an alkyl group having 1 to 20 carbon atoms or an aryl group, preferably an alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably a methyl group or an ethyl group.

As the organic polar compound according to the present invention, a compound having a functional group containing different atoms selected from the above-mentioned preferable functional groups in the molecule may be used. For example, a combination of a dialkylamino group and an alkoxy group or a carbonyl group and an arylthio group may be used. Further, regarding the organic polar compound containing a phosphorus atom, the general formula (4),
Among R ^{14 to} R ¹⁶ and R ^{17 to} R ^{19 in} the general formula (5), the general formula (6) and the general formula (7), an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom which are not bonded to the phosphorus atom You may have the functional group containing an atom. Also in this case, it is desirable that the molecule does not have active hydrogen. Desirable functional groups include
It is preferably selected from the desirable functional groups referred to in the present invention. Specifically, a dialkylamino group, a carbonyl group, an alkoxy group, an aryloxy group, an isocyano group,
It is preferably selected from among thiocarbonyl groups.

Further, in the addition reaction, use of two or more kinds of organic polar compounds having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen. You can also Also in that case, it is desirable that the compound having a preferable functional group according to the present invention is selected.

The organoaluminum oxy compound according to the present invention and an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen. The characteristics of the addition reaction product will be described below.

Here, an organic polar compound containing a phosphorus atom will be described as an example. First, the addition reaction product is significantly different from the organoaluminum oxy compound used in the reaction in solubility in various inert solvents. Solubility can be evaluated by carrying out Soxhlet extraction using an inert hydrocarbon solvent such as hexane or toluene and examining the amount of extraction. The specific method of Soxhlet extraction is shown below. The flask equipped with the Soxhlet extractor is thoroughly replaced with nitrogen. The addition reaction product obtained by distilling off the solvent to dryness is weighed in a predetermined amount in terms of aluminum atom, transferred to a glass fiber cylindrical filter paper under nitrogen, and extracted with a predetermined inert solvent for 8 hours. The amount of extraction is measured by measuring the aluminum concentration in the extract. When the solubility is evaluated using this method, it can be seen that unlike the aluminoxane used in the reaction as shown in Examples, it is hardly soluble in various solvents.

In order to suppress fouling, it is advantageous that it is insoluble in the polymerization medium. It is also effective in suppressing problems during polymerization due to migration, adhesion, etc. of catalyst components to the reactor wall. On the other hand, when the insolubilization progresses remarkably, the activity decreases. In order to prevent fouling, transfer catalyst components to the reactor wall, suppress adhesion and improve activity, there are restrictions in catalyst production, and the evaluation method is effective in evaluating these restrictions. Find and use as an indicator.

The preferred range of the extraction amount is as follows. The extraction amount of hexane (an index of fouling prevention, migration of catalyst components, inhibition of adhesion) is preferably 20% or less, and 15%.
The following is more desirable. Moreover, it is desirable that the amount of extracted toluene (index of activity expression) is 15% or more. Further, heptane is 25% or less, more preferably 20% or less, and benzene is 10% or less.
It is desirable that the amount is more and 30% or less.

Secondly, the addition reaction product is also characteristic in terms of composition. The organic polar compound containing a phosphorus atom contained in the adduct can be quantified by a method using gas chromatography or an inductively coupled plasma emission spectrometry (ICP method). The specific measurement method by the ICP method is shown below. After evaporating the solvent to dryness, a predetermined amount of addition reaction product is weighed. The addition reaction product is sufficiently decomposed with an acidic aqueous solution such as a sulfuric acid aqueous solution, and then diluted to a fixed amount to be used as a measurement sample. Measure phosphorus and aluminum,
Quantify using a calibration curve prepared in advance.

From these measurements, as shown in the examples,
The organic polar compound containing a phosphorus atom that has been subjected to the reaction reacts almost quantitatively, and forms an adduct having a composition according to the amount of the compound added. Thirdly, when the infrared absorption spectrum of the addition reaction product is measured, it is found that the peak of the spectrum of the organic polar compound containing a phosphorus atom shifts. For example, when triethyl phosphate is used as the organic polar compound containing a phosphorus atom, 1240 cm derived from P = O stretching vibration.
The peak at ^-1 shifts to a low wave number at 1180 cm ^-1 . This indicates that P = O is added to the aluminum atom. The method for measuring the infrared absorption spectrum is shown below.
The addition reaction product obtained by distilling off the solvent to dryness was mixed with Nujol which had been sufficiently degassed by heating under nitrogen, and the mixture was sandwiched between KRS plates for measurement.

Considering these three points, it can be said as follows. When an organic polar compound containing a phosphorus atom and an organoaluminum oxy compound undergo an addition reaction, the polar compound undergoes an addition reaction between molecules of a linear or cyclic organoaluminum oxy compound to form a crosslinked structure, resulting in various Solubility in an inert solvent changes. As mentioned above,
The addition reaction product is characteristic in solubility in various inert solvents, composition, and infrared absorption spectrum, and can be said to be substantially different from conventionally known aluminoxanes.

The features described above are not only the features of the organic polar compound containing a phosphorus atom, but are the features common to the organic polar compound according to the present invention.

The amount of dissolution in benzene at 60 ° C. is 10
% Aluminoxane is, for example, JP-A-2-167
However, the addition reaction product of the present invention is also different from this. First, as shown in the examples of the present specification, the extraction amount in Soxhlet extraction using benzene as a solvent was more than 10%, and secondly, the composition was different as described above. 3, the ratio of the alkyl group to the aluminum atom in each organoaluminum compound is different. The aluminoxane disclosed in JP-A-2-167307 is insolubilized by the reaction with water or a compound having active hydrogen such as alcohol, diol, or carboxylic acid. In the reaction with the compound having active hydrogen, the reaction proceeds as in the following general formula.

[Chemical 6]

That is, the reaction produces hydrocarbons corresponding to the type of alkyl group of the aluminoxane. For example,
When aluminum sulfate monohydrate is used as in the method described in the examples of US Pat. No. 5,091,352, the reaction produces methane gas. That is, the reaction reduces the number of alkyl groups in the aluminoxane, and as a result, the ratio of aluminum atoms to alkyl groups is smaller than that before the reaction. When the ratio of the alkyl group to the aluminum atom of the raw material aluminoxane is 1.32, according to the method described in the example of US Pat. No. 5,091,352, the aluminum atom of the benzene-insoluble aluminoxane is shown in Comparative Example 2. Ratio of alkyl groups to 0.57. That is, about half of the methyl groups have reacted before and after the reaction. On the other hand, in the addition reaction product according to the present invention, even if the same raw material aluminoxane was used, substantially no generation of methane gas was observed as in the example, and the ratio of aluminum atom to alkyl group after the reaction was 1 .24, it is clear that these two organoaluminum compounds are different.

The quantification of the alkyl group in the organoaluminum compound can be carried out, for example, by TR Crompton, Comprehensive Organo.
It can be performed by the method described in metallic Analysis, page 6 (1987). Specifically, an organoaluminum compound is first reacted with an alcohol having a relatively high boiling point, for example, normal butanol, isobutanol, or 2-ethylhexanol, and then an aqueous sulfuric acid solution is added, and the generated gas amount is quantified with a gas buret. By doing. As described above, the addition reaction product is a novel organoaluminum compound because the solubility, composition, and ratio of aluminum atom to alkyl group are different from those of conventionally known aluminoxanes.

In the catalyst, an organoaluminum oxy compound and an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen The addition reaction can be carried out in the polymerization system or in advance before the polymerization, but it is usually preferable to carry out the reaction in an inert solvent in advance before use. Examples of the solvent used here include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane. Can be used.

Used in the reaction of an organoaluminum oxy compound with an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen. The organoaluminum oxy compound to be used may be used in a solution state, a solid state, or a state of being supported on a kind of carrier. Further, the addition reaction product of an organoaluminum oxy compound and an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen is used as a carrier. You may carry on top.

As the carrier for supporting the organoaluminum oxy compound, a metal oxide such as silica or alumina, a metal chloride such as magnesium chloride or an organic polymer such as polyethylene or polypropylene may be used.

Amount of an organic polar compound having at least one atom selected from the group consisting of phosphorus atom, nitrogen atom, sulfur atom and oxygen atom used in the reaction with the organoaluminum oxy compound and having no active hydrogen. Is 0.0001 to 0.5 mol, preferably 0. 0, per 1 equivalent of aluminum atom of the organoaluminum oxy compound.
001-0.3 mol, more preferably 0.005-
It is desirable to use 0.2 mol amount. Within this range, the organic polar compound reacts with almost all the organoaluminum oxy compound to give the corresponding addition product (Table 1).
reference).

The reaction between the organoaluminum oxy compound and the organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen is usually carried out. -50 to 20
0 ° C, preferably 0-150 ° C, more preferably 50-
Perform at 150 ° C. The reaction time is 0.05 to 200.
The time is preferably about 0.5 to 50 hours. A reaction product of an organoaluminum oxy compound and an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen is used as it is. Inert hydrocarbon solvents, for example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane, alicyclic hydrocarbons such as cyclopentane and cyclohexane It is preferable to wash with, for example. The washing temperature at that time is usually -50 to 20.
0 ° C, preferably 0-150 ° C, more preferably 50-
It is 150 ° C.

Periodic Tables Nos. 3, 4, 5 used in the present invention
And metallocene compounds (b) of Group 6 transition metals have the general formula (1)

[Chemical 7] Or the general formula (2)

[Chemical 8] Alternatively, the general formula (3)

[Chemical 9] [In the formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (having 1 carbon atom).
Is an alkyl, alkenyl, aryl, alkylaryl, arylalkyl, etc. having .about.20), an alkylsilyl group, an alkylgermyl group, or a 4- to 6-membered ring having a carbon-carbon bond, which may be the same or different. , R ¹¹ is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene, and each Q is a hydrocarbon group such as aryl, alkyl, alkenyl, alkylaryl or arylalkyl having 1 to 20 carbon atoms, alkoxy, Aryloxy, siloxy, hydrogen or halogen, which may be the same or different, and Y is -O-,
^{-S -, - NR 12 -,} - PR 12 -, a is either also -O
^{R 12, -SR 12, -NR 12} R 13, -PR 12 R 13 (R 12 and R ¹³ are alkyl having 1 to 20 carbon hydrogen or carbon,
Is a hydrocarbon group such as alkenyl, aryl, alkylaryl, arylalkyl, or an alkyl halide or an aryl halide), and Me is a third, fourth, fifth and sixth element of the periodic table.
It is a transition metal of the group and p is 0 or 1. ] It is preferable that at least one kind is selected from the transition metal compounds represented by

In the above equation, Me is the third and third of the periodic table.
Although it is a transition metal element of groups 4, 5 and 6 (groups are according to the 1990 rules of nomenclature of inorganic chemistry), preferably selected from transition metal elements of group 4 of the Periodic Table, ie titanium, zirconium, hafnium. Zirconium and hafnium are particularly preferable.

In the above formula, R ^{1 to} R ¹⁰ are hydrogen or a hydrocarbon group (such as an alkyl, alkenyl, aryl, alkylaryl, arylalkyl having 1 to 20 carbon atoms) or 4 to 6 having a carbon-carbon bond. It is a member ring and may be the same or different. Examples of the hydrocarbon group as described above include methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Groups, cetyl groups, phenyl groups, etc., alkylsilyl groups include trimethylsilyl groups, and alkylgermyl groups include trimethylgermyl groups.

Examples of the ligand having a substituent as described above include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and n-.
Alkyl-substituted cyclopentadienyl groups such as butylcyclopentadienyl group, t-butylcyclopentadienyl group, trimethylsilylcyclopentadienyl group, dimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and similar Examples thereof include an indenyl group with or without a substituent and a fluorenyl group.

In the above formula, R ¹¹ is an alkylene group having 1 to 20 carbon atoms, alkylgermylene or alkylsilylene. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, an isopropylidene group, a cyclopentylidene group, a cyclohexylidene group, a tetrahydropyran-4-ylidene group, a diphenylmethylene group, and the like. , A dimethylsilylene group, a diphenylsilylene group, and the like, and an alkylgermylene group includes a dimethylgermylene group, a diphenylgermylene group, and the like.

In the above formula, Q is a hydrocarbon group having 1 to 20 carbon atoms such as aryl, alkyl, alkenyl, alkylaryl and arylalkyl, or halogen, which may be the same or different. In the above formula, Y is -O -, - S -, - NR 12 -, - PR 12 - a either, also ^{-OR 12, -SR 12, -NR 12} R 13, -PR
¹² R ¹³ is an electron donor ligand. Where R ¹²
And R ¹³ is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms such as alkyl, alkenyl, aryl, alkylaryl, arylalkyl, or a halogenated alkyl or a halogenated aryl. Specifically, methyl group, ethyl group, propyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, phenyl group. Examples thereof include groups and benzyl groups. In ^{this, -NR 12 -, - PR 12} - type ligand is preferred.

Specific examples of the transition metal compound represented by the general formula (1), (2) or (3) when Me is zirconium are shown below. As the transition metal compound represented by the general formula (1), bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis ( n-Butylcyclopentadienyl) zirconium dimethyl, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (methylcyclopentadienyl) ) Zirconium dichloride, (cyclopentadienyl) (n-butylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (indenyl) zirconium dichloride, (cyclopentadienyl) (fluorenyl) ) Zirconium dichloride, cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium trimethyl, pentamethylcyclopentadienyl zirconium trichloride, pentamethylcyclopentadienyl zirconium trimethyl like.

As the transition metal compound represented by the general formula (2), dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (indenyl) ) Zirconium dichloride, ethylenebis (4,5,6,7, -tetrahydro-1-indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butylindenyl) Zirconium dichloride, isopropylidene (t-butylcyclopentadienyl) (t-butyl Ndeniru) zirconium dimethyl and the like.

As the transition metal compound represented by the general formula (3), ethylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, ethylene (methylamido) (tetramethylcyclopentadienyl) zirconium Dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dichloride, dimethylsilylene (t-butylamide) (tetramethylcyclopentadienyl) zirconium dibenzyl, dimethylsilylene (benzylamide) (tetramethylcyclopenta) (Dienyl)
Examples thereof include zirconium dibenzyl, dimethylsilylene (phenylamide) (tetramethylcyclopentadienyl) zirconium dichloride and the like.

In the zirconium compound as described above, a transition metal compound in which zirconium is changed to hafnium or titanium can be exemplified. Regarding the use of the transition metal compound according to the present invention, one kind or a combination of two or more kinds of the above-mentioned transition metal compounds can be used.

Addition of the organoaluminum oxy compound of the present invention to an organic polar compound having at least one atom selected from phosphorus atom, nitrogen atom, sulfur atom and oxygen atom in the molecule and having no active hydrogen. The reactant and the transition metal compound may be pre-contacted in the presence or absence of a monomer, or may be introduced into the polymerization system without prior contact. Here, an addition reaction product of an organoaluminum oxy compound and an organic polar compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in the molecule and having no active hydrogen, and If pre-contacted with the transition metal compound, the reactions are usually carried out in an inert solvent. Examples of the solvent used here include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane and decane,
Alicyclic hydrocarbons such as cyclopentane and cyclohexane can be used.

The contact ratio between the addition reaction product and the transition metal compound is 1/5 to 1/10000 mol, preferably 1/10 to 1/2000 mol, based on 1 equivalent of aluminum atom of the addition reaction product of the present invention. It is desirable to use the transition metal component of The contact temperature of the two components used in the present invention is usually -50 to 150 ° C, preferably 0 to 100 ° C.
Is.

In the method of the present invention, the olefins to be polymerized are ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 1-heptene, 1-octene, isooctene, 1-decene, 4-methyl-1-pentene, cyclopentene, cyclopentadiene, butadiene, 1,5-hexadiene, 1,4-hexadiene,
Examples thereof include olefins such as 1,4-pentadiene, cyclic olefins, and dienes. Homopolymerization using these olefins or copolymerization using a mixture of two or more olefins can be performed.

The polymerization catalyst according to the present invention can be used in conventionally known production methods such as a solution polymerization method, a high temperature melt polymerization method, a slurry polymerization method and a gas phase polymerization method. However, it is desirable to perform the slurry polymerization or the gas phase polymerization method from the viewpoint of manufacturing cost. In addition, it is possible to control the molecular weight distribution or composition distribution by multistage polymerization. Alternatively, it is also possible to prepolymerize the olefin.

Regarding the amount of the polymerization catalyst used in the present invention, when expressed in terms of the concentration of the transition metal compound in the polymerization reaction system, it is usually 10 ^-8 to 10 ^-2 mol / l, preferably 10 ^-7 to 10
It is preferably in the range of ^-3 mol / l.

The polymerization catalyst of the present invention can be used as it is at the time of polymerization, but it is preferably used together with an organoaluminum compound. The organoaluminum compound used in the polymerization is not particularly limited, but trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-aluminum
-Butyl aluminum, triisobutyl aluminum,
Trisec-butylaluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trioctylaluminum, and other trialkylaluminums, dimethylaluminum chloride, diethylaluminum chloride, diisobutylaluminum chloride, and other dialkylaluminum halides. , A dialkylaluminum alkoxide such as dimethylaluminum methoxide and diethylaluminum ethoxide, a dialkylaluminum aryloxide such as diethylaluminum phenoxide, and an aluminoxane. Among them, trialkylaluminum, particularly trimethylaluminum, triethylaluminum, triisobutylaluminum, and trioctylaluminum are preferably selected.

The amount used is the atomic ratio (Me / A) of the transition metal of the transition metal compound and the organoaluminum compound.
1), 1/10 to 1/100000, preferably 1 /
It is in the range of 100 to 1/10000. Further, the organoaluminum compound used during the polymerization, may be used in advance with the addition reaction product of the organoaluminum oxy compound and the organic polar compound immediately before the polymerization, or with the transition metal compound, or in prior contact with these contact products, It may also be used without prior contact.

[0085]

EXAMPLES Next, the present invention will be specifically described by way of examples. The analytical instruments used for measuring the physical properties are as follows. The melting point was measured using a Perkin Elmer (DSC-7) at a temperature rising rate of 10 ° C / min. MFR (melt flow rate) is measured according to JIS K-6760 under conditions of a temperature of 190 ° C. and a load of 2.16 kg.
FR (high load melt flow rate) has a temperature of 190
The measurement was carried out under the conditions of ° C and a load of 21.6 kg. The solvent and liquid organic polar compound used for the catalyst preparation were dried by a conventional method.

Reference Example 1 [Extraction of aluminoxane] Methylaluminoxane (MAO1) (manufactured by Tosoh Akzo, 1.3M (Al atom conversion) toluene solution, methyl group / aluminum atom = 1.32) was placed in a flask which had been sufficiently replaced with nitrogen. In addition, toluene was distilled off under reduced pressure to dryness. A flask equipped with a Soxhlet extractor was sufficiently replaced with nitrogen, and 0.02 mol of dried methylaluminoxane in terms of aluminum atom was weighed and transferred to a glass fiber cylindrical filter paper in a Soxhlet extractor under nitrogen. Add 200 ml of hexane to the flask,
Extraction was carried out for 8 hours. When the aluminum concentration in the extract was measured, 30.3% of methylaluminoxane in terms of aluminum atom was extracted. When the same operation was performed for heptane, benzene and toluene, 32.
It was 6%, 41.8%, and 48.5%.

Example 1 [Catalyst Preparation] Preparation of Reactant (a) To a 300 ml flask sufficiently replaced with nitrogen, 50 ml of methylaluminoxane (MAO1) and 50 ml of toluene were added, and then 290 mg of triethyl phosphate (1.6 mmo).
1) was added, and the mixture was heated and stirred at 80 ° C. for 4 hours. At this time, generation of methane gas was not observed. When the hexane, heptane, benzene, and toluene were extracted from this addition reaction product, the extracted content was 11.9% and 1 respectively.
The percentages were 3.1%, 14.6% and 18.2%. Further, the alkyl group / aluminum atom of this addition reaction product is 1.
It was 24. Further, from the results of ICP, the added triethyl phosphate reacted almost quantitatively, and it was an addition reaction product having a molar composition ratio (Al / P) of aluminum and phosphorus of 39.

[Polymerization] Fully nitrogen-substituted internal volume 1.5
3.2 ml of a hexane solution of triisobutylaluminum (0.5 mol / l) was added to 1 SUS autoclave.
l, 10 mg of the above-prepared addition reaction product washed with toluene, and 800 ml of isobutane and 1.5 ml of hydrogen.
After introducing mmol, polymerization was started by introducing together with ethylene a solution of 0.14 mg of bis (n-butylcyclopentadienyl) zirconium dichloride dissolved in 5 ml of toluene. Ethylene pressure 10 kg / cm ² ,
Polymerization was carried out at 70 ° C. for 30 minutes to obtain 27 g of polymer. At this time, no polymer adhered to the wall of the polymerization vessel. The activity per addition reaction product is 530 g-polymer / g-
The addition reaction product was hr.atm, and the activity per complex was 38000 g-polymer / g-complex.hr.atm. The MFR of this polymer at 190 ° C. and a load of 2.16 kg is 0.7 g / 10 min, and the MFR at 190 ° C. and a load of 21.6 kg and 190 ° C. and a load of 2.16 kg.
The ratio of MFR (HLMFR / MFR) was 16.5.

Examples 2 to 7 [Catalyst preparation] The procedure of Example 1 was repeated, except that the organic polar compounds containing phosphorus atoms shown in Table 1 were used at the indicated molar ratios. Generation of methane gas was not observed in each of the examples. [Polymerization] The same procedure as in Example 1 was carried out. In all of the examples, there was no adhesion of polymer to the wall of the polymerization vessel. The results are shown in Table 2.

Reference Example 2 [Extraction of aluminoxane] MAO2 (manufactured by Toso Akzo Co., Ltd., 2.78M (Al atom conversion) toluene solution as methylaluminoxane, methyl group / aluminum atom = 1.
64) was used for solvent extraction in the same manner as in Reference Example 1.
Extraction amounts in hexane, heptane, benzene, and toluene are 58.0%, 63.3%, 95.6%,
It was 100%.

Example 8 [Catalyst preparation] The same procedure as in Example 1 was carried out except that MAO2 shown in Reference Example 2 was used as methylaluminoxane and the reaction was carried out under the conditions shown in Table 1. Evolution of methane gas was not observed in this reaction either. [Polymerization] The same procedure as in Example 1 was carried out. At this time, no polymer adhered to the wall of the polymerization vessel. The results are shown in Table 2.

Comparative Example 1 A catalyst was prepared and polymerized in the same manner as in Example 1 except that MAO1 was used without using an organic polar compound containing a phosphorus atom. However, the polymer adhered to the wall of the polymerization vessel from the beginning of the polymerization, and the polymerization for a long time was impossible.

Comparative Example 2 [Catalyst preparation] 2.4 g of aluminum sulfate 14 hydrate was prepared in the same manner as in Example 2 of US Pat. No. 5,091,352 without using an organic polar compound containing a phosphorus atom. A catalyst was prepared in the same manner as in Example 1 except that it was used. At this time, generation of methane gas was observed. The alkyl group / aluminum atom of this solid aluminxane was 0.57. [Polymerization] The same procedure as in Example 1 was carried out to obtain 18 g of a polymer. The activity per addition reaction product is 360 g-polymer / g-
Aluminoxane.hr.atm, activity per complex is 26000 g-polymer / g-complex.hr.atm
Met. MFR of this polymer with a load of 2.16 kg
Is 0.7 g / 10 min, 190 ° C., load 21.
MFR at 6kg and M at 190 ° C, load 2.16kg
The FR ratio was 17.3.

Example 9 Example 9 was repeated except that 0.20 mg of bis (n-butylcyclopentadienyl) zirconium dichloride was used in the polymerization. At this time, no polymer adhered to the wall of the polymerization vessel. The results are shown in Table 2.

Example 10 Example 10 was repeated except that 0.70 mg of bis (n-butylcyclopentadienyl) zirconium dichloride was used in the polymerization. At this time, no polymer adhered to the wall of the polymerization vessel. The results are shown in Table 2.

Examples 11 to 14 As a complex, bis (n-butylcyclopentadienyl)
The procedure of Example 3 was repeated except that the complexes shown in Table 3 were used instead of zirconium dichloride. In all of the examples, there was no adhesion of polymer to the wall of the polymerization vessel.

Example 15 42 g of a polymer was obtained in the same manner as in Example 3 except that 30 g of 1-hexene was introduced together with ethylene during the polymerization. At this time, no polymer adhered to the wall of the polymerization vessel. Activity per addition reaction product is 840 g-polymer / g
-Addition reaction product-hr-atm, and activity per complex was 60,000 g-polymer / g-complex-hr-atm. The MFR of the polymer under a load of 2.16 kg was 2.1 g / 10 min, 190 ° C. and a load of 21.6.
MFR in kg and MF at 190 ° C, load 2.16 kg
The ratio of R was 17.2. The melting point was 112.8 ° C.

Examples 16 to 23 [Catalyst preparation] The procedure of Example 1 was repeated, except that the organic polar compound containing a nitrogen atom, an oxygen atom or a sulfur atom shown in Table 4 was used at the indicated molar ratio. . Generation of methane gas was not observed in each of the examples. [Polymerization] The same procedure as in Example 1 was carried out. In all of the examples, there was no adhesion of polymer to the wall of the polymerization vessel. The results are shown in Table 4.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

INDUSTRIAL APPLICABILITY According to the present invention, in the production of a polyolefin using a metallocene compound and an organoaluminum oxy compound as a catalyst, the trouble of polymer adhesion to the wall of the polymerization vessel can be eliminated, and the polyolefin can be produced with high polymerization activity. .

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Hori No. 2 Nakanoshima, Oita, Oita Prefecture Showa Denko Oita Research Institute (72) Inventor Shigenobu Miyake No. 2 Naka, Oita, Oita Prefecture Showa Denko Oita Laboratory Co., Ltd. (72) Inventor Shintaro Inazawa, Oita City, Oita Prefecture, No. 2 Nakasu, Showa Denko Co., Ltd. Oita Laboratory

Claims (5)

[Claims] 1. An (a) organoaluminum oxy compound and an organic polar compound having at least one atom selected from a phosphorus atom, a nitrogen atom, a sulfur atom and an oxygen atom in the molecule and having no active hydrogen. An addition reaction product,
(B) An olefin polymerization catalyst comprising at least one metallocene compound of a transition metal of Group 3, 4, 5 or 6 of the periodic table. 2. The organic polar compound has the general formula (4) R ¹⁴ R ¹⁵ R ¹⁶ P or the general formula (5) R ¹⁴ R ¹⁵ R ¹⁶ P = Z [wherein R ^{14 to} R ¹⁶ have 1 carbon atoms] An alkyl group having 20 to 20, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, a dialkylamino group,
And an acyl group, at least one of which is an alkoxy group, an alkylthio group, an aryloxy group, an arylthio group, a dialkylamino group, or an acyl group, and Z is
O, = S, an alkylidene group, an imino group, etc.] is an organic polar compound containing a phosphorus atom, and the olefin polymerization catalyst according to claim 1. 3. The organic polar compound has the general formula (6) (R ¹⁷ O) (R ¹⁸ O) (R ¹⁹ O) P [wherein R ^{17 to} R ¹⁹ are alkyl groups having 1 to 20 carbon atoms, It is an aryl group], and is an organic polar compound, The olefin polymerization catalyst of Claim 1 characterized by the above-mentioned. 4. The organic polar compound is represented by the general formula (7) (R ¹⁷ O) (R ¹⁸ O) (R ¹⁹ O) P═O [wherein R ^{17 to} R ¹⁹ are alkyl having 1 to 20 carbon atoms]. Group, which is an aryl group], is an organic polar compound represented by the formula 1. The olefin polymerization catalyst according to claim 1. 5. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 4.