JP4108018B2 - Method for producing ethylene wax - Google Patents

Description

  The present invention relates to a method for producing an ethylene wax, and more particularly to a method for producing an ethylene wax that produces an ethylene wax having a narrow molecular weight distribution with high productivity.

  Olefinic low molecular weight polymers such as polyethylene wax are used in applications such as pigment dispersants, resin processing aids, printing ink additives, paint additives, rubber processing aids, fiber treatment agents, and the like. Olefin-based low molecular weight polymers are also used as toner release agents. In recent years, a low-temperature fixing toner has been demanded from the viewpoint of energy saving, and a wax having a good releasability at a low temperature, that is, a wax having a low melting point even with the same composition and the same molecular weight is desired.

  By the way, as a method for producing such an olefin-based low molecular weight polymer, a titanium-based catalyst has been conventionally used industrially. However, this catalyst system has the advantage that the yield of low molecular weight polymer per unit amount of catalyst is large and highly active, but it is necessary to maintain a large hydrogen partial pressure in the gas phase in the polymerization system, As a result, there was a drawback that there were many by-products of alkane. Furthermore, the molecular weight distribution of the obtained low molecular weight polymer is wide, especially in the case of a low molecular weight polymer having a molecular weight of 1000 or less, the stickiness is large. It was difficult.

  As a method for improving these drawbacks, a method for producing a low molecular weight polymer using a vanadium catalyst has been proposed (see Patent Document 1). This publication describes that a low molecular weight polymer having a narrow molecular weight distribution can be produced under a low hydrogen partial pressure as compared with a titanium-based catalyst, but the molecular weight distribution is not always sufficient.

  In the presence of a metallocene catalyst comprising (A) a transition metal compound selected from the group consisting of groups IVb, Vb and VIb of the periodic table, and (B) an aluminoxane, A method for producing an ethylene-based wax in which ethylene is polymerized or ethylene is polymerized with an α-olefin has been proposed (see Patent Document 2). According to this method, it is possible to produce an ethylene wax having a narrow molecular weight distribution, but there is a demand for a method for producing an ethylene wax having excellent productivity.

  Furthermore, although it is disclosed that an ethylene-based wax is produced using a metallocene-based catalyst composed of a metallocene and an aluminoxane (see, for example, Patent Documents 3 and 4), the productivity of these methods is not always sufficient. Increasing the polymerization temperature facilitates removal of the polymerization heat and can improve productivity, but there is a problem that the yield of the low molecular weight polymer per unit weight of the catalyst decreases.

As a result of intensive studies in view of the problems in the prior art as described above, the present inventors either homopolymerize ethylene in the presence of a specific metallocene catalyst, or ethylene and an olefin having 3 or more carbon atoms. It has been found that an ethylene-based wax having a high productivity and a narrow molecular weight distribution can be obtained by copolymerizing. Moreover, when the (co) polymerization is carried out at a temperature of 100 ° C. or higher, it has been found that an ethylene wax having a higher productivity, a narrow molecular weight distribution, and a low melting point can be obtained, thereby completing the present invention.
JP 59-210905 A JP 60-78462 A JP-A-1-203410 JP-A-6-49129

  An object of the present invention is to provide an ethylene wax having a narrow molecular weight distribution and to provide a method for efficiently producing such an ethylene wax.

The method for producing an ethylene-based wax according to the present invention includes:
(A) Transition metal compound represented by the following formula: R ¹ R ² R ³ R ⁴ M (I ′)
(In the formula, M is zirconium , and R ¹ and R ² are alkyl-substituted cyclopentadienyl groups (provided that the cyclopentadienyl skeleton of R ¹ and R ² is not bonded except for the zirconium atom). , R ³ and R ⁴ may be the same or different from each other, and may be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R or a hydrogen atom. And)
(B) a compound that reacts with the transition metal compound (A) to form an ion pair;
(C) Ethylene or ethylene and an olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst comprising an organoaluminum compound, the amount of hydrogen supplied to the polymerization reaction system is a molar ratio of hydrogen to ethylene The ethylene (co) polymer having an intrinsic viscosity [η] of 0.01 to 0.40 dl / g is formed by homopolymerization or copolymerization in the range of 0.01 to 2.

  In the present invention, the polymerization temperature in the polymerization or copolymerization is preferably 100 ° C. or higher. The average residence time in the polymerization or copolymerization is preferably 1 hour or less.

  In the present invention, it is particularly preferable that the polymerization temperature in the polymerization or copolymerization is 100 ° C. or more and the average residence time is 1 hour or less.

  The present invention can produce ethylene wax having a narrow molecular weight distribution with high production efficiency.

  When the polymerization temperature is 100 ° C. or higher, an ethylene wax having a narrow molecular weight distribution and a low melting point can be produced with high production efficiency. Furthermore, the heat removal apparatus can be reduced in size, the equipment cost can be reduced, and the residence time can be shortened.

Hereinafter, the manufacturing method of the ethylene-type wax based on this invention is demonstrated concretely.
In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. Sometimes used in the meaning of including a coalescence.

The method for producing an ethylene-based wax according to the present invention includes (A) a transition metal compound represented by the following formula (I), and (B) a compound that reacts with the transition metal compound (A) to form an ion pair. (C) Ethylene is homopolymerized in the presence of an olefin polymerization catalyst comprising an organoaluminum compound, or ethylene and an olefin having 3 or more carbon atoms are copolymerized to form an ethylene (co) polymer. I am letting.

  First, each component which forms the olefin polymerization catalyst used in the present invention will be described. Examples of the transition metal compound (A) that forms the olefin polymerization catalyst include compounds represented by the following formula (I).

ML _X (I)
In the formula, M is a transition metal of Group 4 of the periodic table, specifically, zirconium or titanium.

L is a ligand (group) coordinated to a transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, other than a ligand having a cyclopentadienyl skeleton. L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, or —SO ₃ R (where R is a carbon which may have a substituent such as halogen). Or a hydrogen atom.

  x is the valence of the transition metal and represents the number of L. Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl And an alkyl-substituted cyclopentadienyl group such as a hexylcyclopentadienyl group; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; a fluorenyl group, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

  Among the ligands coordinated to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula (I) includes two or more groups having a cyclopentadienyl skeleton, the group having two cyclopentadienyl skeletons is an alkylene group such as ethylene or propylene; It may be bonded via a substituted alkylene group such as diphenylmethylene; an alkylidene group such as isopropylidene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group or a methylphenylsilylene group. Further, the groups having two or more cyclopentadienyl skeletons are preferably the same.

  Examples of the ligand other than the ligand having a cyclopentadienyl skeleton include the following. Specific examples of the hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and pentyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; phenyl And aryl groups such as a tolyl group and aralkyl groups such as a benzyl group and a neophyll group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of halogen include fluorine, chlorine, bromine and iodine. Examples of the ligand represented by —SO ₃ R include a p-toluenesulfonate group, a methanesulfonate group, a trifluoromethanesulfonate group, and the like.

For example, when the valence of the transition metal is 4, the compound represented by the general formula (I) is more specifically represented by the following general formula (I ′).

R ¹ R ² R ³ R ⁴ M (I ')
(In the formula, M is zirconium or titanium, R ¹ is a group having a cyclopentadienyl skeleton, and R ² , R ³ and R ⁴ may be the same or different from each other. Groups having an enyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, halogen atoms, trialkylsilyl groups, —SO ₃
R or a hydrogen atom. )
In the present invention, a transition metal compound in which one of R ² , R ³ and R ^{4 in} the general formula (I ′) is a group having a cyclopentadienyl skeleton, for example, R ¹ and R ² are cyclopentadienyl skeletons. A transition metal compound which is a group having the following is preferably used. In this case, these groups having a cyclopentadienyl skeleton may be bonded via an alkylene group, a substituted alkylene group, an alkylidene group, a silylene group, a substituted silylene group, or the like. R ³ and R ⁴ are an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R, or a hydrogen atom.

Below, a specific compound is illustrated about the transition metal compound whose M is a zirconium. Bis (indenyl) zirconium dichloride,
Bis (indenyl) zirconium dibromide,
Bis (indenyl) zirconium bis (p-toluenesulfonate),
Bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Bis (fluorenyl) zirconium dichloride,
Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylene bis (trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (indenyl) zirconium dichloride,
Dimethylsilylene bis (indenyl) zirconium bis (trifluoromethanesulfonate),
Dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride,
Dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride,
Methylphenylsilylenebis (indenyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dichloride,
Bis (cyclopentadienyl) zirconium dibromide,
Bis (cyclopentadienyl) methylzirconium monochloride,
Bis (cyclopentadienyl) ethylzirconium monochloride,
Bis (cyclopentadienyl) cyclohexyl zirconium monochloride,
Bis (cyclopentadienyl) phenylzirconium monochloride,
Bis (cyclopentadienyl) benzylzirconium 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-toluenesulfonate),
Bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (methylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium ethoxy chloride,
Bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate),
Bis (ethylcyclopentadienyl) zirconium dichloride,
Bis (methylethylcyclopentadienyl) 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 and the like.

  In the above examples, the disubstituted product of the cyclopentadienyl ring includes 1,2- and 1,3-substituted products, and the trisubstituted product includes 1,2,3- and 1,2,4-substituted products. Including. Alkyl groups such as propyl and butyl include isomers such as n-, i-, sec- and tert-.

  Moreover, the transition metal compound which replaced the zirconium with titanium in the above zirconium compounds can also be used.

Furthermore, transition metal compounds represented by the following general formulas (II), (III) and (IV) can be exemplified.

  In the formula, M is a transition metal atom of Group 4 of the periodic table, specifically titanium or zirconium, and preferably zirconium.

R ¹ and R ^{2, which} may be the same or different from each other, are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or silicon-containing Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group,
Specifically, examples of the halogen atom include fluorine, chlorine, bromine, iodine,
Examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, octyl, nonyl, dodecyl, eicosyl, norbornyl, adamantyl; vinyl, propenyl, cyclohexenyl, etc. Alkenyl groups; arylalkyl groups such as benzyl, phenylethyl, phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, α- or β-naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl , Aryl groups such as pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl, etc.
Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include groups in which halogen is substituted for the hydrocarbon group having 1 to 20 carbon atoms,
Silicon-containing groups include methylsilyl, phenylsilyl, dimethylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tolylsilyl, trinaphthylsilyl, etc. A silicon-containing group of
Examples of the oxygen-containing group include hydroxy groups, alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy, aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and arylalkoxy groups such as phenylmethoxy and phenylethoxy.
The sulfur-containing group includes a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, trimethylbenzene sulfonate. Phosphonate, triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate and other sulfonate groups, methyl sulfinate, phenyl sulfinate, benzene sulfinate, p-toluene sulfinate , Sulfinate groups such as trimethylbenzene sulfinate and pentafluorobenzene sulfinate,
Nitrogen-containing groups include amino groups, alkylamino groups such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, and dicyclohexylamino, and aryls such as phenylamino, diphenylamino, ditolylamino, dinaphthylamino, and methylphenylamino. An amino group or an alkylarylamino group,
Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino.

Among these, R ¹ is preferably a hydrocarbon group, and particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. R ² is preferably a hydrogen atom or a hydrocarbon group, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, or propyl.

R ³ , R ⁴ and R ⁵ may be the same as or different from each other, and are alkyl groups having 1 to 20 carbon atoms, specifically methyl, ethyl, n-propyl, i-propyl, n- Butyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl, octyl, nonyl,
Examples include dodecyl, eicosyl, norbornyl, adamantyl and the like. These alkyl groups may be substituted with a halogen atom or a silicon-containing group.

Of these, R ³ is preferably a secondary or tertiary alkyl group. R ¹⁵ may contain a double bond or a triple bond. X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing Group or sulfur-containing group, specifically, the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, and Sulfur-containing groups can be exemplified.

Among these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, 2 valent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - NR 7 -, - P (R 7) -,
—P (O) (R ⁷ ) —, —BR ⁷ — or —AlR ⁷ — [wherein R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon atom number of 1 to 1. 20 halogenated hydrocarbon groups], specifically, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1, Divalent hydrocarbon groups having 1 to 20 carbon atoms, such as alkylene groups such as 2-cyclohexylene and 1,4-cyclohexylene, and arylalkylene groups such as diphenylmethylene and diphenyl-1,2-ethylene; A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group having 1 to 20 carbon atoms, such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) Silylene, Di ( Chlohexyl) silylene, methylphenylsilylene, diphenylsilylene, di (p-tolyl) silylene, di (p-chlorophenyl) silylene and other alkylsilylene, alkylarylsilylene, arylsilylene groups, tetramethyl-1,2-disilyl, tetraphenyl Divalent silicon-containing groups such as alkyldisilyl such as 1,2-disilyl, alkylaryldisilyl, and aryldisilyl groups; divalent germanium-containing groups obtained by replacing silicon in the above divalent silicon-containing groups with germanium A divalent tin-containing group in which the silicon of the divalent silicon-containing group is substituted with tin.

R ⁷ is the same halogen atom as described above, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Among these, Y is preferably a divalent silicon-containing group, a divalent germanium-containing group, more preferably a divalent silicon-containing group, and is alkylsilylene, alkylarylsilylene, or arylsilylene. Is more preferable.

Specific examples of the transition metal compound represented by the general formula (II) are shown below.
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-sec-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-pentylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-n-hexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-cyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenylethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-chloromethylindenyl)} zirconium dichloride,
rac-Dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsilylmethylindenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,7-dimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (i-propyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (n-butyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (cyclohexyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,7-dimethyl-4-ethylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis {1- (2,7-dimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-ethylindenyl)} zirconium dibromide,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-sec-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-pentylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-n-hexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-cyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-methylcyclohexylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsilylmethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-trimethylsiloxymethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenylethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-phenyldichloromethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2,3,7-trimethyl-4-chloromethylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (i-propyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (n-butyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (cyclohexyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-t-butylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2,3,7-trimethyl-4-ethylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis {1- (2,3,7-trimethyl-4-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (methanesulfonate)
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} zirconium-bis (p-phenylsulfinato),
rac-dimethylsilylene-bis {1- (2-methyl-3-methyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4,6-di-i-propylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-phenyl-4-i-propyl-7-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-i-propyl-7-methylindenyl)} titanium dichloride and the like.

Of these, those having a branched alkyl group such as i-propyl, sec-butyl and tert-butyl group at the 4-position are particularly preferred.

  In the present invention, a racemate of the transition metal compound represented by the general formula (II) is usually used as a catalyst component, but R-type or S-type can also be used.

  The transition metal compound represented by the general formula (II) as described above can be synthesized from an indene derivative by a known method, for example, a method described in JP-A-4-268307.

  Next, the transition metal compound represented by the general formula (III) will be described.

  In the formula, M is a transition metal atom of Group 4 of the periodic table, specifically titanium or zirconium, and preferably zirconium.

R ¹¹ may be the same as or different from each other, and is a hydrocarbon group having 1 to 6 carbon atoms, specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Examples thereof include alkyl groups such as butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl and cyclohexyl, and alkenyl groups such as vinyl and propenyl.

  Of these, a primary alkyl group in which the carbon bonded to the indenyl group is preferable, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group and an ethyl group are particularly preferable.

R ¹² may be the same as or different from each other, and is a hydrogen atom or an aryl group having 6 to 16 carbon atoms. Examples of the aryl group having 6 to 16 carbon atoms include phenyl, α-naphthyl, β- Examples include naphthyl, anthracenyl, phenanthryl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl, biphenylyl and the like. Of these, phenyl, naphthyl, anthracenyl, and phenanthryl are preferable.

  This aryl group may be substituted with a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an organic silyl group. Examples of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms include the same atom or group as in the general formula (II), and examples of the organic silyl group include trimethylsilyl, triethylsilyl, triphenylsilyl and the like. It is done.

X ¹ and X ² may be the same as or different from each other, and are the same as defined in the general formula (II). Y is the same as defined in the general formula (II).

Specific examples of the transition metal compound represented by the general formula (III) are shown below.
rac-dimethylsilylene-bis {1- (2-methylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (1-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (2-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-fluorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pentafluorophenyl) indenyl)
} Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, p-dichlorophenyl) phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o-tolyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (o, o'-dimethylphenyl) -1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-ethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (pi-propylphenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-benzylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-biphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (p-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4- (m-trimethylsilylenephenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-phenyl-4-phenylindenyl)} zirconium dichloride,
rac-diethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di- (i-propyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di- (n-butyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dicyclohexylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-tolyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-di (p-chlorophenyl) silylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-methylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-ethylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, rac-dimethyl gel Mylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylstannylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dibromide,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dimethyl,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium methyl chloride,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride SO ₂ Me,
rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium chloride OSO ₂ Me,
rac-dimethylsilylene-bis {1- (2-ethylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-methyl-1-naphthyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-methylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,5-dimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,4,6-trimethylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (o-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (m-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (p-chlorophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,3-dichlorophenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2,6-dichlorophenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3,5-dichlorophenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (2-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (3-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-bromophenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-biphenylyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-ethyl-4- (4-trimethylsilylphenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-anthracenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-propyl-4- (9-phenanthryl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (8-methyl-9-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-anthracenyl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-propyl-4- (9-phenanthryl) indenyl)}
Zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-s-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-pentyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (β-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (2-methyl-1-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (5-acenaphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-i-butyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-neopentyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (2-n-hexyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)
} Zirconium dichloride,
rac-Methylphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)
} Zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-anthracenyl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (9-phenanthryl) indenyl)} zirconium dichloride,
rac-diphenylsilylene-bis {1- (2-ethyl-4- (4-biferinyl) indenyl)} zirconium dichloride,
rac-dimethylgermyl-bis {1- (2-ethyl-4-phenylindenyl)} zirconium dichloride,
rac-dimethylgermyl-bis {1- (2-ethyl-4- (α-naphthyl) indenyl)} zirconium dichloride,
rac-dimethylgermyl-bis {1- (2-n-propyl-4-phenylindenyl)} zirconium dichloride and the like.

  Moreover, the compound which replaced the zirconium in the above compounds with titanium can also be mentioned.

In the present invention, a racemate of the transition metal compound represented by the general formula (III) is usually used as an olefin polymerization catalyst component, but R-type or S-type can also be used.

  Such a transition metal compound represented by the general formula (III) is produced according to Journal of Organometallic Chem. 288 (1985), pp. 63-67, European Patent Application Publication No. 0,320,762 and Examples. be able to.

  Next, the transition metal compound represented by the general formula (IV) will be described. The transition metal compound represented by the general formula (IV) is a compound described in EP-549900 and Canada-2084017.

  In the formula, M is a transition metal atom of Group 4 of the periodic table, specifically titanium or zirconium, and preferably zirconium.

R ²¹ may be the same or different from each other;
Hydrogen atom,
A halogen atom, preferably a chlorine or bromine atom,
An alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms,
A halogenated alkyl group having 1 to 10 carbon atoms,
An aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms,
_{-NR 2, -SR, -OSiR 3,} -SiR 3 or -PR ₂ groups [wherein, R represents a halogen atom, preferably a chlorine atom, from 1 to 10 carbon atoms, preferably 1 to 3 alkyl groups, Or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms].

R ^{22 to} R ²⁸ may be the same as or different from each other, and are the same atom or group as R ²¹ described above. Among the groups represented by R ^{22 to} R ²⁸ , at least two adjacent groups are An aromatic ring or an aliphatic ring may be formed together with the atoms to which they are bonded.

= BR ²⁹ , = AlR ²⁹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , =
NR ²⁹ , = CO, = PR ²⁹ or = P (O) R ²⁹ . However, R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, particularly a methyl group, and 1 carbon atom. -10 fluoroalkyl group, preferably CF ₃ group, aryl group having 6-10 carbon atoms, preferably 6-8 carbon atoms, fluoroaryl group having 6-10 carbon atoms, preferably pentafluorophenyl group, carbon An alkoxy group having 1 to 10, preferably 1 to 4 atoms, particularly a methoxy group, 2 to 10 carbon atoms, preferably 2 to 4 alkenyl groups, 7 to 40 carbon atoms, preferably 7 to 10 carbon atoms. An arylalkyl group having 8 to 40 carbon atoms, preferably 8 to 12 arylalkenyl groups having 7 to 40 or 7 to 12 carbon atoms.

R ²⁹ and R ³⁰ may each form a ring together with the atoms to which they are bonded. M ² is silicon, germanium or tin, preferably silicon or germanium.

  Here, the above-mentioned alkyl group is a linear or branched alkyl group, and the halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly a fluorine atom or a chlorine atom.

Among the compounds represented by the general formula (IV), M is zirconium,
R ²¹ is the same as each other, and is an alkyl group having 1 to 4 carbon atoms,
R ^{22 to} R ²⁸ may be the same as or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
X ³ and X ⁴ may be the same or different from each other, and are an alkyl group having 1 to 3 carbon atoms or a halogen atom,
Z is

(In the formula, M ² is silicon, and R ²⁹ and R ³⁰ may be the same or different from each other, and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. )
The substituents R ²² and R ²⁸ are hydrogen atoms, and R ^{23 to} R ²⁷ are more preferably compounds having an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

Further, among the compounds represented by the general formula (IV),
M is zirconium,
R ²¹ is the same alkyl group having 1 to 4 carbon atoms,
R ²² and R ²⁸ are hydrogen atoms;
R ^{23 to} R ²⁷ may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom,
X ³ and X ⁴ are both chlorine atoms,
Z is

(In the formula, M ² is silicon, and R ²⁹ and R ³⁰ may be the same or different from each other, and are an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms. is there)
Is preferred.

In particular, among the compounds represented by the general formula (IV),
M is zirconium,
R ²¹ is a methyl group;
R ^{22 to} R ²⁸ are hydrogen atoms;
X ³ and X ⁴ are chlorine atoms,
Z is

A compound in which M ² is silicon and R ²⁹ and R ³⁰ may be the same as or different from each other and is a methyl group or a phenyl group is preferable.

Specific examples of the transition metal compound represented by the general formula (IV) are shown below.
rac-dimethylsilylenebis {1- (4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylsilylenebis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylrylenebis {1- (2-methyl-4,5-acenaphthoindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride,
rac-methylphenyl-bis {1- (2-methyl-4,5-acetonaphthyindenyl)} zirconium dichloride,
rac-methylphenylsilylene-bis {1- (2-methyl-4,5-acenaphthoindenyl)} zirconium dichloride,
rac-dimethylsilylene-bis {1- (4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylsilylenebis {1- (2,6-dimethyl-4,5-benzoindenyl)} zirconium dichloride,
rac-dimethylrylenebis {1- (2,3,6-trimethyl-4,5-acenaphthoindenyl)} zirconium dichloride and the like.

  Moreover, the compound which replaced the zirconium in the above compounds with titanium can also be mentioned. In the present invention, the above transition metal compounds may be used in combination of two or more.

  (B) Forming an olefin polymerization catalyst (B) As a compound that reacts with the transition metal compound (A) to form an ion pair, JP-A-1-501950, JP-A-1-502036, Lewis acids, ionic compounds and borane compounds described in JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US-547718, Mention may be made of carborane compounds.

  Examples of the Lewis acid include Mg-containing Lewis acid, Al-containing Lewis acid, and B-containing Lewis acid. Among these, B-containing Lewis acid is preferable. Specific examples of the Lewis acid containing a boron atom include compounds represented by the following general formula.

BR ^p R ^q R ^r
(In the formula, R ^p , R ^q and R ^r may be the same or different from each other and may have a substituent such as a fluorine atom, a methyl group, a trifluoromethyl group, or a fluorine atom. Is shown.)
Specific examples of the compound represented by the above general formula include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, and tris (4-fluoromethylphenyl). Examples include boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron, and tris (3,5-dimethylphenyl) boron. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound used in the present invention is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the transition metal compound (A) by reacting with the transition metal compound (A) and stabilize the transition metal cation species by forming an ion pair. Examples of such anions include organoboron compound anions, organoarsenic compound anions, organoaluminum compound anions, and the like, which are relatively bulky and stabilize the transition metal cation species.
Examples of the cation include a metal cation, an organometallic cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, there are triphenylcarbenium cation, tributylammonium cation, N, N-dimethylammonium cation, ferrocenium cation and the like.

  Among these, an ionic compound containing a boron compound as an anion is preferable, and specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri ( n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p- Dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o- Yl) boron, tri (n-butyl) ammonium tetra (4-fluorophenyl) boron and the like. Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetra (phenyl) boron, N , N-diethylanilinium tetra (phenyl) boron, N, N-2,4,6-pentamethylanilinium tetra (phenyl) boron and the like. Examples of the dialkylammonium salt include di (n-propyl) ammonium. Tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like, and triarylphosphonium salts such as triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphonium tetra (phenyl) ) Boron, tri (dimethylphenyl) phosphonium Such as tiger (phenyl) boron and the like.

In the present invention, as an ionic compound containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl)
Borate can also be mentioned.

Moreover, the following compounds can also be illustrated. (In the ionic compounds listed below, the counter ion is tri (n-butyl) ammonium, but is not limited thereto.)
Anionic salts such as bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis [tri (n-butyl) ) Ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n-butyl) ammonium-1-carbadecaborate, Tri (n-butyl) ammonium-1-carbaundecaborate, tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n -Butyl) ammonium bromo-1-carbadodecaborate, etc .; Can be mentioned. These compounds are used as Lewis acids and ionic compounds.

Borane and carborane complex compounds and salts of carborane anions such as decaborane (14), 7,8-dicarbaundecaborane (13), 2,7-dicarboundecarborane (13), undecahydride-7,8-dimethyl -7,8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbound decaborane, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6 -Carbadecaborate (12), Tri (n-butyl) ammonium 7-Carbaundecaborate (13), Tri (n-butyl) ammonium 7,8-Dicarboundeborate (12), Tri (n-butyl) Ammonium 2,9-dicarbaundecaborate (12), tri (n-butyl) ammonium dodecahydride-8-methyl 7,9-dicarbaundecaborate, tri (n-butyl) ammonium undeca Iidolide 8-ethyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8 -Allyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6 -Dibromo-7-carbaoundecaborate etc .;
Carboranes and salts of carboranes, such as 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecarborane (14), dodecahydride-1-phenyl-1,3-di Carbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, etc.
Furthermore, the following compounds can also be illustrated. (In the ionic compounds listed below, the counter ion is tri (n-butyl) ammonium, but is not limited thereto.)
Metal carborane salts and metal borane anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7 , 8-Dicarbaundecaborate) ferrate (ferrate) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbundecaborate) cobaltate (III), tri (n-butyl) ) Ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) cuvate (cuprate) ) (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaoundecaborate) Metal salt) (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundeborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride) -7,8-Dimethyl-7,8-dicarboundecaborate) chromate (chromate) (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8-dicarboundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (dodecahydride dicarbadodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium]
Bis (dodecahydridododecaborate) nickelate (III), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) chromate (III), bis [tri (n-butyl) ammonium ] Bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [ And tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate (IV).

  The compound (B) that forms an ion pair by reacting with the transition metal compound (A) as described above can be used in combination of two or more. The (C) organoaluminum compound forming the olefin polymerization catalyst can be represented, for example, by the following general formula (i).

^{_{R a n AlX 3-n ...}} (i)
(In the formula, ^Ra 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).
In the above formula (i), R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, n -Propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.
Trialkylaluminiums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum,
Alkenyl aluminum such as isoprenyl aluminum,
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide,
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide,
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide,
Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

  Further, as the organoaluminum compound (C), a compound represented by the following formula (ii) can also be used.

^{_{R a n AlY 3-n ...}} (ii)
(Wherein, R ^a is the same as above, Y is —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group or —N (R ^g )) An AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like ^; Is hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g are methyl group, ethyl group, etc.)
Specific examples of such an organoaluminum compound include the following compounds.
_{^{(1) R a n Al (}} OR b) compounds represented by _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide.
_{^{(2) R a n Al (}} OSiR c 3) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OSi (CH 3) 3),
(Iso-C ₄ H ₉ ) ₂ Al (OSi (CH ₃ ) ₃ ),
Such as _{(iso-C 4 H 9)} 2 Al (OSi (C 2 H 5) 3).
_{^{(3) R a n Al (}} OAlR d 2) a compound represented by _3-n, e.g., _{(C 2 H 5) 2 Al} (OAl (C 2 H 5) 2),
Such as _{(iso-C 4 H 9)} 2 Al (OAl (iso-C 4 H 9) 2).
_{^{(4) R a n Al (}} NR e 2) a compound represented by _3-n, e.g., _{(CH 3) 2 Al (N} (C 2 H 5) 2),
(C ₂ H ₅ ) ₂ Al (NH (CH ₃ )),
(CH ₃ ) ₂ Al (NH (C ₂ H ₅ )),
(C ₂ H ₅ ) ₂ Al [N (Si (CH ₃ ) ₃ ) ₂ ],
(Iso-C ₄ H ₉ ) ₂ Al [N (Si (CH ₃ ) ₃ ) ₂ ] and the like.
_{^{(5) R a n Al (}} SiR f 3) a compound represented by _3-n, e.g., _{(iso-C 4 H 9)} 2 Al (Si (CH 3) 3) and the like.

In the present invention, R ^a ₃ Al Among _{^{them, R a n Al (OR b}} ) 3-n, R a n Al (OAl
A preferred example is an organoaluminum compound represented by R ^d ₂ ) _3-n . These organoaluminum compounds can be used in combination of two or more.

  The catalyst for olefin polymerization used in the present invention includes the transition metal compound (A) as described above, the compound (B) that reacts with the transition metal compound (A) to form an ion pair, and the organoaluminum compound (C). And formed from. Such an olefin polymerization catalyst can produce an ethylene (co) polymer having a high polymerization activity and a narrow molecular weight distribution. Further, since the polymerization activity is high, the residence time can be shortened.

  FIG. 1 shows a process for preparing an olefin polymerization catalyst used in the present invention. In the present invention, a low molecular weight ethylene (co) polymer is obtained by homopolymerizing ethylene in the presence of the olefin polymerization catalyst as described above, or by copolymerizing ethylene and an olefin having 3 or more carbon atoms. An ethylene-based wax is produced.

  Examples of olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene and 1-nonene. , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, and the like can be mentioned. Two or more of these olefins having 3 or more carbon atoms can be used.

  The ethylene content in the polymerization raw material olefin in the polymerization reaction is usually in the range of 60 to 100 mol%, preferably 70 to 100 mol%, and the content of the olefin having 3 or more carbon atoms is usually 0 to 40 mol. %, Preferably in the range of 0 to 30 mol%.

In the present invention, the polymerization reaction is carried out in a hydrocarbon medium. Specific examples of such hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic carbons such as cyclopentane, cyclohexane, and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as hydrogen, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and petroleum fractions such as gasoline, kerosene and light oil. Furthermore, the olefin used for superposition | polymerization can also be used.

In the present invention, the polymerization is carried out in the presence of the olefin polymerization catalyst as described above. In this case, the transition metal compound (A) is usually 10 ⁻ as the concentration of transition metal atoms in the polymerization reaction system. It is used in an amount ranging from ⁸ to 10 ⁻² gram atoms / liter, preferably from 10 ⁻⁷ to 10 ⁻³ gram atoms / liter.

  The compound (B) which reacts with the transition metal compound (A) to form an ion pair is usually about 1 to 50 mol, preferably 1 with respect to 1 mol of the transition metal atom in the transition metal compound (A). It is used in such an amount that it becomes ˜20 mol.

  The organoaluminum compound (C) is usually about 1 to 500 mol, preferably about 1 to 300 mol, per 1 mol of the compound (B) that reacts with the transition metal compound (A) to form an ion pair. Is used in such an amount that

  In the present invention, ethylene polymerization or copolymerization of ethylene and an olefin having 3 or more carbon atoms is usually 100 ° C. or higher, preferably 100 to 250 ° C., more preferably 120 to 250 ° C., particularly preferably 130 to It is performed in the range of 200 ° C.

  When the polymerization temperature is within the above range, the heat removal of the polymerization system is easy, and the heat removal apparatus can be miniaturized. Moreover, in the same heat removal apparatus, the heat removal efficiency is increased, so that productivity can be improved. Furthermore, since the polymerization is performed at a high temperature, even if the polymer concentration is increased, the solution viscosity is not so high and the stirring power can be reduced, and the polymerization can be performed at a high concentration, so that productivity is improved.

  Usually, when (co) polymerizing ethylene, heat removal is performed by circulating a solvent or the like in order to stabilize the polymerization temperature. In the heat removal apparatus used here, if the amount of heat removal is the same, the heat transfer area can be reduced as the polymerization temperature is higher, and the effect varies depending on the selection of conditions such as the cooling medium. When a simple counter-current heat exchanger using water is used, when the polymerization temperature is 100 ° C., the required heat transfer area is about 2 minutes compared to when the polymerization temperature is 70 ° C. It is also possible to set to 1. When the polymerization temperature is increased in this manner, the necessary heat transfer area can be reduced and the heat removal apparatus can be reduced in size, so that the equipment cost can be reduced.

The average residence time (polymerization time) is 1 hour or less, preferably 40 minutes or less, more preferably 30 minutes or less, and preferably 5 to 20 minutes.
The polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg / cm ^2, more preferably atmospheric pressure ~40kg / cm ² range.

  The molecular weight of the obtained ethylene wax can be adjusted by the amount of hydrogen supplied to the polymerization reaction system and / or the polymerization temperature. The amount of hydrogen supplied to the polymerization reaction system is usually in the range of 0.01 to 2, preferably 0.05 to 1, as the molar ratio of hydrogen to ethylene.

In the present invention, an ethylene-based wax can be obtained by treating the polymerization reaction mixture after the completion of the polymerization reaction by a conventional method.
The ethylene-based wax thus obtained is a homopolymer of ethylene or a copolymer of ethylene and olefin, and its intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.40 dl / g or less. The range is preferably 0.005 to 0.40 dl / g, more preferably 0.005 to 0.35 dl / g, and particularly preferably 0.01 to 0.30 dl / g. In this ethylene-based wax, the content of ethylene component units is 80 to 100 mol%,
Preferably, it is in the range of 85 to 100 mol%, more preferably 90 to 100 mol%, and the content of the olefin component unit having 3 or more carbon atoms is 0 to 20 mol%, preferably 0 to 15 mol%, More preferably, it is the range of 0-10 mol%.

  The molecular weight distribution (Mw / Mn) of ethylene wax measured by gel permeation chromatography (GPC) is usually 3 or less, preferably 2.5 or less, and the melting point is 132 ° C. or less, preferably 130. It is -40 degreeC, More preferably, it is the range of 128-50 degreeC.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

A stainless steel autoclave with an internal volume of 2 liters that was sufficiently purged with nitrogen was charged with 1 liter of hexane, and hydrogen was introduced to ² kg / cm ² -G. Next, after raising the temperature in the system to 130 ° C., 0.5 mmol of triisobutylaluminum, 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate and bis (n-butylcyclopentadienyl) zirconium Polymerization was initiated by injecting 0.001 mmol of dichloride with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 30 kg / cm ² -G, and polymerization was carried out at 140 ° C. for 15 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol to precipitate a polymer. The polymer was collected by filtration and dried overnight at 80 ° C. under reduced pressure. As a result, 44.9 g of an ethylene polymer having an intrinsic viscosity [η] of 0.15 dl / g, Mw / Mn of 2.05, and a melting point of 120.5 was obtained. The results are shown in Table 1.

[Examples 2 and 3, Reference Examples 1 to 5]
Type and amount of transition metal compound [component (A)], compound [component (B)] and organoaluminum compound [component (C)] that react with transition metal compound (A) to form ion pairs, and polymerization conditions An ethylene polymer was produced in the same manner as in Example 1 except that as shown in Table 1. The results are shown in Table 1.

[Example 4]
800 ml of hexane and 200 ml of 4-methyl-1-pentene were charged into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and hydrogen was introduced to 8 kg / cm ² -G. Subsequently, after raising the temperature in the system to 130 ° C., 0.5 mmol of triisobutylaluminum, 0.002 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate and 0.001 mmol of ethylenebis (indenyl) zirconium dichloride The polymerization was started by press-fitting with ethylene. Thereafter, only ethylene was continuously supplied to keep the total pressure at 30 kg / cm ² -G, and polymerization was carried out at 140 ° C. for 15 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol to precipitate a polymer. The polymer was collected by filtration and dried overnight at 80 ° C. under reduced pressure. As a result, ethylene 4-methyl- having an intrinsic viscosity [η] of 0.13 dl / g, Mw / Mn of 2.11, a melting point of 108 ° C., and an ethylene content of 96.4 mol%. 54.8 g of 1-pentene copolymer was obtained. The results are shown in Table 1.

[Comparative Example 1]
A stainless steel autoclave with an internal volume of 2 liters that was sufficiently purged with nitrogen was charged with 1 liter of hexane, and hydrogen was introduced to 5 kg / cm ² -G. Next, after raising the temperature in the system to 130 ° C., polymerization was started by injecting 2 mmol of methylaluminoxane (MAO) and 0.01 mmol of bis (n-butylcyclopentadienyl) zirconium dichloride with ethylene. did. Thereafter, only ethylene was continuously fed to keep the total pressure at 30 kg / cm ² -G, and polymerization was carried out at 140 ° C. for 40 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The obtained polymer solution was put into a large excess of methanol to precipitate a polymer. The polymer was collected by filtration and dried overnight at 80 ° C. under reduced pressure. The results are shown in Table 2.

[Comparative Example 2]
Comparative Example except that ethylenebis (indenyl) zirconium dichloride was used instead of bis (n-butylcyclopentadienyl) zirconium dichloride, and the amount of transition metal compound and methylaluminoxane were changed as shown in Table 2. In the same manner as in No. 1, an ethylene-based wax was produced. The results are shown in Table 2.

It is explanatory drawing which shows the preparation process of the olefin polymerization catalyst used by this invention.

Claims (3)

(A) Transition metal compound represented by the following formula: R ¹ R ² R ³ R ⁴ M (I ′)
(In the formula, M is zirconium , and R ¹ and R ² are alkyl-substituted cyclopentadienyl groups (provided that the cyclopentadienyl skeleton of R ¹ and R ² is not bonded except for the zirconium atom). , R ³ and R ⁴ may be the same or different from each other, and may be an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a halogen atom, a trialkylsilyl group, —SO ₃ R or a hydrogen atom. And)
(B) a compound that reacts with the transition metal compound (A) to form an ion pair;
(C) Ethylene or ethylene and an olefin having 3 or more carbon atoms in the presence of an olefin polymerization catalyst comprising an organoaluminum compound, the amount of hydrogen supplied to the polymerization reaction system is a molar ratio of hydrogen to ethylene As an ethylene (co) polymer having an intrinsic viscosity [η] of 0.01 to 0.40 dl / g by homopolymerization or copolymerization in the range of 0.01 to 2 A method for producing a wax.   The method for producing an ethylene-based wax according to claim 1, wherein the polymerization temperature is 100 ° C or higher. The method for producing an ethylene-based wax according to claim 1 or 2, wherein an average residence time is 1 hour or less.