JP5158304B2 - Method for producing polyethylene - Google Patents

Description

  The present invention relates to a method for producing polyethylene.

  Low density polyethylene (LDPE) produced by the high pressure radical method is a branched polyolefin, and its side chain has a non-linear dendritic structure. Such a structure is excellent in molding processability such as melt fluidity and melt tension, and is advantageous when the polymer is melt-processed. On the other hand, it has a drawback of reducing the mechanical strength of the solid polymer.

  For this reason, linear high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) obtained with Ziegler catalysts or metallocene catalysts are generally used in applications that require the mechanical strength of solid polymers. . However, these HDPE and LLDPE do not have good moldability, which is an advantage of LDPE.

  As a technique for improving the molding processability of HDPE and LLDPE by a polyethylene production method, for example, (a) a method of broadening the molecular weight distribution by a multistage polymerization method using a conventional Ziegler catalyst (see, for example, Patent Documents 1 to 3). (B) a method for producing a polyethylene having a long chain branch using a traditional Cr-based catalyst, and (c) a method for producing a polyethylene having a long chain branch by polymerizing ethylene using a specific metallocene catalyst (for example, , See Patent Document 4). However, the moldability of polyethylene obtained by these methods is still not sufficient. Further, the polyethylene obtained by the methods (a) and (b) has a problem that the mechanical strength is lowered due to the broadening of the molecular weight distribution. Furthermore, the polyethylene obtained by the method (c) has a problem in the particle shape and cannot be produced by a slurry process or a gas phase process.

  On the other hand, it is already known to use a catalyst system comprising a combination of a transition metal compound and an organometallic compound as a method for producing a polyolefin by polymerization of olefin. Kaminsky et al. Discloses that a catalyst using a metallocene and methylaluminoxane exhibits high activity when producing an olefin polymer containing propylene (see, for example, Patent Document 5).

  However, although the catalyst system disclosed in Patent Document 5 is excellent in polymerization activity, since the catalyst system is soluble in the reaction system, a solution polymerization system is often adopted, which not only limits the production process. In order to produce a polymer exhibiting industrially useful physical properties, it is necessary to use a large amount of a relatively expensive methylaluminoxane. For this reason, when these catalyst systems are used, there are problems such as a cost problem and a large amount of aluminum remaining in the polymer.

  On the other hand, a catalyst system using a clay compound ion-exchanged with an organic cation as a co-catalyst is disclosed (see, for example, Patent Documents 6 to 8), and in a slurry process, a polymer having high polymerization activity and good morphology is disclosed. Manufacturing has been realized.

JP-A-2-53811 JP-A-2-132109 JP-A-10-182742 US Pat. No. 5,272,236 JP 58-19309 A JP 7-224106 A Japanese Patent Laid-Open No. 10-324708 JP 11-335408 A

  The present invention has been made in order to solve the above-mentioned problems of the prior art, and has an economical production of polyethylene having a good morphology and having a good moldability of LDPE and a mechanical strength of HDPE and LLDPE. A method is provided.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention
(A) a density is at 0.890 g / cm ³ or more 0.980 g / cm ³ or less,
(B) The weight average molecular weight (Mw) is 30,000 to 10,000,000,
(C) The ratio (Mw / Mn) of Mw to number average molecular weight (Mn) is 2 or more and 20 or less,
(D) A method for producing polyethylene having a long chain branch number of 0.01 to 3 per 1,000 carbon atoms, the production method comprising at least a transition metal compound (component (a)) and a transition The present invention relates to a method for producing polyethylene, characterized in that ethylene and optionally an olefin having 3 or more carbon atoms are polymerized using a catalyst containing a metal compound (component (b)) as a main component.

The density (d) (g / cm ³ ) of the polyethylene produced in the present invention is a value measured by a density gradient tube method in accordance with JIS K6760 (1995), and is 0.890 g / cm ³ or more and 0.980 g. / Cm ³ or less.

  The weight average molecular weight (Mw) of the polyethylene produced by the present invention is 30,000 or more and 10,000,000 or less, preferably 40,000 or more and 8,000,000 or less, more preferably 50,000. More than 5,000,000.

  Mw / Mn of the polyethylene produced in the present invention is 2 or more and 20 or less, preferably 2 or more and 15 or less, and more preferably 2 or more and 12 or less.

The number of long chain branches of the polyethylene produced by the present invention is the number of branches of hexyl groups or more detected by ¹³ C-NMR measurement, and is 0.01 or more and 3 or less per 1,000 carbon atoms. Yes, preferably from 0.01 to 1, more preferably from 0.01 to less than 0.1.

  The shrinkage factor (g ′ value) of the polyethylene produced by the present invention evaluated by GPC / intrinsic viscometer is preferably 0.1 or more and less than 0.9, more preferably 0.1 or more and 0.8 or less. Yes, more preferably from 0.1 to 0.7. The g ′ value is a parameter representing the degree of long-chain branching, and is the ratio of the intrinsic viscosity of this polyethylene and HDPE having no branching at an absolute molecular weight of 700,000 or 3 times the weight average molecular weight (Mw). . Further, there is a relationship between the g ′ value and the contraction factor (g value) evaluated by the GPC / light scatterometer, preferably by the formula (14), more preferably by the formula (14) ′. In addition, g value is ratio of the square average of the inertial radius of this polyethylene and HDPE in absolute molecular weight 700,000 or the absolute molecular weight 3 times Mw.

0.2 <log (g ′) / log (g) <1.3 (14)
0.5 <log (g ′) / log (g) <1.0 (14) ′
Note that log (g ′) / log (g) is a parameter representing the form of long-chain branching, and it is close to 1.5 for a short comb-shaped branch, and a small value for a star-shaped branch. Author, New Polymer Experimental Science 1, Basics of Polymer Experiment, Molecular Characterization, “3-4. Molecular shape and morphology ", 295 (1994)". The polyethylene produced by the present invention shows a value smaller than 1.3 in order to show a shape close to a star shape. Further, g-value in an absolute molecular weight three times Mw of _{(g 3M)} and g values of the absolute molecular weight of 1 × Mw between _{(g M),} preferably of formula (15), particularly preferably the formula (15) 'More preferably, there is a relationship represented by the formula (15)'.

0 <g _3M / g _M ≦ 1 (15)
0 <g _3M / g _M ≦ 0.9 (15) ′
0 <g _3M / g _M ≦ 0.8 (15) ''
The (E) powder bulk density of the polyethylene produced in the present invention, measured by a method based on JIS K6760 (1995), is preferably 0.15 g / cm ³ or more and 0.70 g / cm ³ or less, more preferably 0. 0.15 g / cm ³ or more and 0.50 g / cm ³ or less, particularly preferably 0.17 g / cm ³ or more and 0.50 g / cm ³ or less, more preferably 0.20 g / cm ³ or more and 0.50 g / cm ³ or less. cm ³ or less.

  Examples of the olefin having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, Α-olefins such as eicosene, 4-methyl-1-pentene, 3-methyl-1-butene or vinylcycloalkane; cyclic olefins such as norbornene or norbornadiene; dienes such as butadiene or 1,4-hexadiene or styrene It can be illustrated. Two or more of these olefins can be mixed and used.

The transition metal compound (component (a)) in the present invention is copolymerized with ethylene or ethylene and an olefin having 3 or more carbon atoms by the production method of the present invention using a catalyst containing only the component (a) as a main component. By
(F) Mn is preferably 5,000 or more, particularly preferably 10,000 or more, more preferably 15,000 or more,
(G) Mw is preferably 10,000 or more, particularly preferably 15,000 or more, further preferably 20,000 or more,
(H) Mw / Mn is preferably 2 or more and 5 or less, particularly preferably 2 or more and 4 or less, more preferably 2 or more and 3.5 or less,
(I) The following general formula (16)
Z = X / (X + Y) × 2 (16)
(Where X is the number of vinyl ends per 1,000 macromer main chain methylene carbons and Y is the number of saturated ends per 1,000 macromer main chain methylene carbons.)
Z represented by is preferably 0.25 or more and 1 or less, particularly preferably 0.50 or more and 1 or less,
(J) Preferably the powder bulk density is 0.15 g / cm ³ or more and 0.50 g / cm ³ or less,
(K) Transition metal that produces a macromer, preferably having a long chain branch (ie, a branch of a hexyl group or higher detected by ¹³ C-NMR measurement) of less than 0.01 per 1,000 main chain methylene carbons A compound is preferable, and two or more kinds of transition metal compounds may be mixed and used.

  The transition metal compound (component (a)) used in the present invention is preferably represented by the general formula (1)

で表される遷移金属化合物である。

It is a transition metal compound represented by these.

M ¹ in the component (a) represented by the general formula (1) used in the present invention is a titanium atom, a zirconium atom or a hafnium atom, and each X ¹ is independently a hydrogen atom, a halogen atom, 20 hydrocarbon group, C1-C20 silicon atom-containing hydrocarbon group, C1-C20 nitrogen atom-containing hydrocarbon group or C1-C20 oxygen atom-containing hydrocarbon group.

Examples of the halogen in X ¹ include chlorine, fluorine, bromine and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, norbornyl group, phenyl group, styryl group, biphenylyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group , Dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, Diphenylethyl group, di Examples thereof include phenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like. For example, methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group, dibutylsilyl group, diphenylsilyl group Group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, trimethylsilylmethyl group, trimethyl Silylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, Examples of the nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, and the like. Phenylamino, benzylamino, phenylethylamino, phenylpropylamino, phenylbutylamino, naphthylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino Group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethylamino) ethyl Group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group, etc. Examples of the oxygen atom-containing hydrocarbon group of methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butylphenoxy group, biphenoxy group, methoxymethyl Group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, Examples include butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, phenoxyphenyl group, etc. It is done.

In the general formula (1), R ¹ and R ² are the general formula (2), (3) or (4).

で表され、それぞれ同じでも異なっていてもよく、Ｍ^１とともにサンドイッチ構造を形成する。一般式（２）、（３）または（４）におけるＲ^４は各々独立して水素原子、ハロゲン原子、炭素数１〜２０の炭化水素基、炭素数１〜２０のケイ素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０の酸素原子含有炭化水素基である。

Each of which may be the same or different and forms a sandwich structure with M ¹ . R ⁴ in the general formula (2), (3) or (4) is each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, A nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms.

Examples of the halogen of R ^{4 in} the general formula (2), (3) or (4) include chlorine, fluorine, bromine, iodine and the like. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, norbornyl, phenyl, styryl, biphenylyl, naphthyl, tolyl, ethylphenyl, propyl Phenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl Group, phenylpropyl group, phenylbutyl group, diphenyl Rumethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like. As the atom-containing hydrocarbon group, for example, methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group , Dibutylsilyl group, diphenylsilyl group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, Limethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, Examples thereof include bis (trimethylsilyl) phenyl group and triphenylsilylmethyl group. Examples of the nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino group, ethylamino group, propylamino group, butylamino group, and pentyl. Amino group, hexylamino group, phenylamino group, benzylamino group, phenylethylamino group, phenylpropylamino group, phenylbutylamino group, naphthylamino group, dimethylamino group, diethylamino group Dipropylamino group, dibutylamino group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group Bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group, etc. Examples of the oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butylphenoxy Group, biphenoxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, ethoxy Propyl group, propoxypropyl group, butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group And a phenoxyphenyl group.

Specific examples of R ¹ and R ^{2 in} the general formula (1) include, for example, cyclopentadienyl group, methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethyl Cyclopentadienyl, ethylcyclopentadienyl, diethylcyclopentadienyl, triethylcyclopentadienyl, tetraethylcyclopentadienyl, propylcyclopentadienyl, dipropylcyclopentadienyl, tri Propylcyclopentadienyl group, tetrapropylcyclopentadienyl group, butylcyclopentadienyl group, dibutylcyclopentadienyl group, tributylcyclopentadienyl group, tetrabutylcyclopentadienyl group, phenylcyclopentadienyl group , Diphenyl Clopentadienyl, naphthylcyclopentadienyl, methoxycyclopentadienyl, trimethylsilylcyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, trimethylindenyl, tetramethylindenyl , Pentamethyl indenyl group, hexamethyl indenyl group, ethyl indenyl group, diethyl indenyl group, triethyl indenyl group, tetraethyl indenyl group, pentaethyl indenyl group, hexaethyl indenyl group, propyl indenyl group, Dipropyl indenyl group, tripropyl indenyl group, tetrapropyl indenyl group, pentapropyl indenyl group, hexapropyl indenyl group, butyl indenyl group, dibutyl indenyl group, tributyl indenyl group, tetrabutyl ind Examples thereof include a denyl group, a pentabutylindenyl group, a hexabutylindenyl group, a phenylindenyl group, a diphenylindenyl group, a benzoindenyl group, a naphthylindenyl group, a methoxyindenyl group, and a trimethylsilylindenyl group. .

In addition, the crosslinking group R ³ for crosslinking R ¹ and R ² in the general formula (1) is represented by the general formula (5).

で表され、置換基Ｒ^５は各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のケイ素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０の酸素原子含有炭化水素基であり、Ｙ^１は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子であり、その中でも好ましくは炭素原子、ケイ素原子であり、ｌは１から５の整数である。

Each of the substituents R ⁵ is independently a hydrogen atom, halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom having 1 to 20 carbon atoms. A hydrocarbon group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, Y ¹ is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom, and l is It is an integer from 1 to 5.

Halogen in R ⁵ of general formula (5), a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or 1 carbon atom Examples of the ˜20 oxygen atom-containing hydrocarbon group include the same as those described above for R ⁴ .

  Specific examples of the general formula (5) include, for example, a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and methylethyl. Methylene group, methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) Methylene group, bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenol) E) methylene group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group Di (biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group Group, bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, Vinylsilane-diyl group, diallyl silane diyl group, (methyl) (vinyl) silanediyl group, and (allyl) (methyl) silanediyl group.

As specific compounds represented by the general formula (1) used in the present invention, when M ¹ is a zirconium atom and X ¹ is a chlorine atom, for example, methylenebis (cyclopentadienyl) zirconium dichloride, isopropylidenebis ( Cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (cyclopentadienyl) zirconium dichloride, diphenylmethylenebis (cyclopentadienyl) zirconium dichloride, ethylenebis (cyclopentadienyl) zirconium dichloride, methylenebis (methyl) Cyclopentadienyl) zirconium dichloride, isopropylidenebis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (methylcyclopentadienyl) di Konium dichloride, diphenylmethylenebis (methylcyclopentadienyl) zirconium dichloride, ethylenebis (methylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, isopropylidene (cyclo Pentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (methylcyclopentadiyl) Enyl) zirconium dichloride, ethylene (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, methylene bis (2,4-dimethyl cyclide) Lopentadienyl) zirconium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylmethylenebis (2,4 -Dimethylcyclopentadienyl) zirconium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (indenyl) Zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (indenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (Indenyl) zirconium dichloride, ethylene (cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride, diethylsilanediylbis (cyclopentadienyl) zirconium dichloride, di (n-propyl) ) Silanediylbis (cyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (cyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (cyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride, Di (p-tolyl) silanediylbis (cyclopentadienyl) zirconium dichloride, divinylsilane dii Bis (cyclopentadienyl) zirconium dichloride, diallylsilanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (vinyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (allyl) (methyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (cyclopentadi) Enyl) zirconium dichloride, (cyclohexyl) (methyl) bis (cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanedi Irbis (cyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diethylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (methylcyclopentadiyl) Enyl) zirconium dichloride, diisopropylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediylbis (methylcyclopentadienyl) zirconium dichloride, (ethyl) (Methyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) Randiylbis (methylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) ) Silanediylbis (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diethylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, Di (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diisopropylsila Diyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (methylcyclopentadienyl) Enyl) zirconium dichloride, (ethyl) (methyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) Zirconium dichloride, (methyl) (isopropyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) (cycline Lopentadienyl) (methylcyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silanediyl (cyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride, dimethylsilanediylbis (2,4-dimethylcyclopentadienyl) Zirconium dichloride, diethylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, di (n-propyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diisopropylsilanediylbis (2,4 -Dimethylcyclopentadienyl) zirconium dichloride, dicyclohexylsilanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, diphenylsilanedi Rubis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (methyl) (n-propyl) silanediylbis (2,4- Dimethylcyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) bis (2,4-dimethylcyclopentadienyl) zirconium dichloride (Methyl) (phenyl) silanediylbis (2,4-dimethylcyclopentadienyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di Tylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, di (n-propyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, diisopropylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, dicyclohexylsilanediyl (Cyclopentadienyl) (indenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, (ethyl) (methyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, (methyl) ( n-propyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, (methyl) (isopropyl) silanediyl ( Cyclopentadienyl) (indenyl) zirconium dichloride, (cyclohexyl) (methyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, (methyl) (phenyl) silanediyl (cyclopentadienyl) (indenyl) zirconium dichloride, etc. It can be illustrated. The compounds obtained by substituting X ¹ of the above transition metal compounds fluorine atom, a bromine atom or an iodine atom can be exemplified. Furthermore, the M ¹ of the transition metal compound can also be exemplified compounds obtained by replacing the titanium atom or a hafnium atom.

  In the present invention, the transition metal compound (component (b)) contained as a main component is produced by using the catalyst containing only the component (b) as a main component, and in the production method of the present invention, in the presence of the macromer, It is preferably a transition metal compound that produces polyethylene satisfying (A) to (D), preferably (E), by copolymerizing an olefin having 3 or more carbon atoms, and two or more transition metal compounds are mixed. It can also be used.

  The transition metal compound (component (b)) used in the present invention is preferably represented by the general formula (6)

で表される遷移金属化合物である。

It is a transition metal compound represented by these.

M ² in the component (b) represented by the general formula (6) used in the present invention is a titanium atom, a zirconium atom or a hafnium atom, and each X ² is independently a hydrogen atom, a halogen, a carbon number of 1 to 20 hydrocarbon group, C1-C20 silicon atom-containing hydrocarbon group, C1-C20 nitrogen atom-containing hydrocarbon group or C1-C20 oxygen atom-containing hydrocarbon group.

Examples of the halogen in X ² include chlorine, fluorine, bromine, and iodine. Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group, nonyl group, decyl group, norbornyl group, phenyl group, styryl group, biphenylyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group , Dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, Diphenylethyl group, di Examples thereof include phenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like. For example, methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group, dibutylsilyl group, diphenylsilyl group Group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, trimethylsilylmethyl group, trimethyl Silylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis (trimethylsilyl) phenyl group, Examples of the nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, and the like. Phenylamino, benzylamino, phenylethylamino, phenylpropylamino, phenylbutylamino, naphthylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino Group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethylamino) ethyl Group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group, etc. Examples of the oxygen atom-containing hydrocarbon group of methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butylphenoxy group, biphenoxy group, methoxymethyl Group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, Examples include butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, phenoxyphenyl group, etc. It is done.

In the general formula (6), R ⁷ represents the general formula (7), (8) or (9).

で表され、置換基Ｒ^１０は各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のケイ素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０の酸素原子含有炭化水素基である。

Each of the substituents R ¹⁰ is independently a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom having 1 to 20 carbon atoms. It is a hydrocarbon group or a C1-C20 oxygen atom containing hydrocarbon group.

Examples of the halogen of R ^{10 in} the general formula (7), (8) or (9) include chlorine, fluorine, bromine, iodine and the like, and examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, Ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, norbornyl, phenyl, styryl, biphenylyl, naphthyl, tolyl, ethylphenyl, propyl Phenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl Group, phenylpropyl group, phenylbutyl group, diphenyl Nylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group, etc., and silicon having 1 to 20 carbon atoms As the atom-containing hydrocarbon group, for example, methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group, hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group , Dibutylsilyl group, diphenylsilyl group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tributylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group Trimethylsilylmethyl group, trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl) propyl group, bis (trimethylsilyl) butyl group, bis ( Trimethylsilyl) phenyl group, triphenylsilylmethyl group and the like. Examples of the nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino group, ethylamino group, propylamino group, butylamino group, and pentylamino group. Hexylamino group, phenylamino group, benzylamino group, phenylethylamino group, phenylpropylamino group, phenylbutylamino group, naphthylamino group, dimethylamino group, diethylamino , Dipropylamino group, dibutylamino group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group, dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl Group, bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis (dimethylamino) phenyl group, phenylaminomethyl group, diphenylaminomethyl group, diphenylaminophenyl group, etc. Examples of the oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butyl Fenoki Si group, biphenoxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, Ethoxypropyl group, propoxypropyl group, butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl Group, phenoxyphenyl group and the like.

Specific examples of R ⁷ in the general formula (6) include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group, and a tetramethylcyclopentadienyl. Group, ethylcyclopentadienyl group, diethylcyclopentadienyl group, triethylcyclopentadienyl group, tetraethylcyclopentadienyl group, propylcyclopentadienyl group, dipropylcyclopentadienyl group, tripropylcyclopentadienyl Enyl, tetrapropylcyclopentadienyl, butylcyclopentadienyl, dibutylcyclopentadienyl, tributylcyclopentadienyl, tetrabutylcyclopentadienyl, phenylcyclopentadienyl, diphenylcyclopent Interdienyl group, naphthylcyclopentadienyl group, methoxycyclopentadienyl group, trimethylsilylcyclopentadienyl group, indenyl group, methylindenyl group, dimethylindenyl group, trimethylindenyl group, tetramethylindenyl group, pentamethyl Indenyl, hexamethylindenyl, ethylindenyl, diethylindenyl, triethylindenyl, tetraethylindenyl, pentaethylindenyl, hexaethylindenyl, propylindenyl, dipropylindenyl Nyl group, tripropyl indenyl group, tetrapropyl indenyl group, pentapropyl indenyl group, hexapropyl indenyl group, butyl indenyl group, dibutyl indenyl group, tributyl indenyl group, tetrabutyl indenyl , Mention may be made of penta-butyl indenyl group, hexa-butyl indenyl group, phenylindenyl group, diphenyl indenyl group, benzoindenyl group, naphthyl indenyl group, a methoxy indenyl group, a trimethylsilyl indenyl group.

R ⁸ in the general formula (6) is the general formula (10).

で表され、置換基Ｒ^１１は各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のケイ素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０の酸素原子含有炭化水素基であり、具体的には、例えば前記Ｒ^４と同じものを挙げることができる。

Each of the substituents R ¹¹ independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom having 1 to 20 carbon atoms. a hydrocarbon group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, specifically, can be for example include the same meanings as defined above R ^4.

Specific examples of R ⁸ in the general formula (6) include, for example, a fluorenyl group, a methyl fluorenyl group, a dimethyl fluorenyl group, a trimethyl fluorenyl group, a tetramethyl fluorenyl group, and pentamethyl fluorenyl. Group, hexamethylfluorenyl group, heptamethylfluorenyl group, octamethylfluorenyl group, ethylfluorenyl group, diethylfluorenyl group, triethylfluorenyl group, tetraethylfluorenyl group, pentaethylfluoride Olenyl group, hexaethylfluorenyl group, heptaethylfluorenyl group, octaethylfluorenyl group, propylfluorenyl group, dipropylfluorenyl group, tripropylfluorenyl group, tetrapropylfluorenyl Group, pentapropylfluorenyl group, hexapropylfluorenyl group, Putapropyl fluorenyl group, octapropyl fluorenyl group, butyl fluorenyl group, dibutyl fluorenyl group, tributyl fluorenyl group, tetrabutyl fluorenyl group, pentabutyl fluorenyl group, hexabutyl fluorenyl group Nyl group, heptabutylfluorenyl group, octabutylfluorenyl group, phenylfluorenyl group, diphenylfluorenyl group, benzylfluorenyl group, dibenzylfluorenyl group, benzofluorenyl group, dimethylamino Examples include fluorenyl group, bis (dimethylamino) fluorenyl group, methoxyfluorenyl group, dimethoxyfluorenyl group and the like.

In the general formula (6), the bridging group R ⁹ that crosslinks R ⁷ and R ⁸ is represented by the general formula (11).

で表され、置換基Ｒ^１２は各々独立して水素原子、ハロゲン、炭素数１〜２０の炭化水素基、炭素数１〜２０のケイ素原子含有炭化水素基、炭素数１〜２０の窒素原子含有炭化水素基または炭素数１〜２０の酸素原子含有炭化水素基であり、Ｙ^２は炭素原子、ケイ素原子、ゲルマニウム原子または錫原子であり、その中でも好ましくは炭素原子、ケイ素原子等であり、ｍは１から５の整数である。

Each of the substituents R ¹² independently represents a hydrogen atom, a halogen, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom having 1 to 20 carbon atoms. A hydrocarbon group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, Y ² is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom, a silicon atom or the like, m Is an integer from 1 to 5.

R ¹² halogen in formula (11), C 1-20 hydrocarbon group, C 1-20 silicon atom-containing hydrocarbon group, C 1-20 nitrogen atom-containing hydrocarbon group, or C 1 Examples of the ˜20 oxygen atom-containing hydrocarbon group include the same as R ⁵ .

  Specific examples of the general formula (11) include a methylene group, an ethylidene group, an ethylene group, a propylidene group, a propylene group, a butylidene group, a butylene group, a pentylidene group, a pentylene group, a hexylidene group, an isopropylidene group, and methylethyl. Methylene group, methylpropylmethylene group, methylbutylmethylene group, bis (cyclohexyl) methylene group, methylphenylmethylene group, diphenylmethylene group, phenyl (methylphenyl) methylene group, di (methylphenyl) methylene group, bis (dimethylphenyl) Methylene group, bis (trimethylphenyl) methylene group, phenyl (ethylphenyl) methylene group, di (ethylphenyl) methylene group, bis (diethylphenyl) methylene group, phenyl (propylphenyl) methylene group, di (propylphenyl) Nyl) methylene group, bis (dipropylphenyl) methylene group, phenyl (butylphenyl) methylene group, di (butylphenyl) methylene group, phenyl (naphthyl) methylene group, di (naphthyl) methylene group, phenyl (biphenyl) methylene group Di (biphenyl) methylene group, phenyl (trimethylsilylphenyl) methylene group, bis (trimethylsilylphenyl) methylene group, bis (pentafluorophenyl) methylene group, silanediyl group, disilanediyl group, trisilanediyl group, tetrasilanediyl group, dimethylsilanediyl group Group, bis (dimethylsilane) diyl group, diethylsilanediyl group, dipropylsilanediyl group, dibutylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group It can be mentioned.

Specific examples of the compound represented by the general formula (6) used in the present invention include M ² Zirconium atom, X ² Is a chlorine atom and the bridging group R ⁹ Is a diphenylmethylene group, for example, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-Methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Tylene (2,3,4-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride Diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenyl Tylene (2,4-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene ( 3,4-diethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene ( 2,3,5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Me Tylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Methylene (3-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dipropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2, 5-dipropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dipropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene ( , 3,4-tripropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tripropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Diphenylmethylene (3,4,5-tripropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrapropyl-1-cyclopentadienyl) (9 -Fluorenyl) zirconium dichloride, diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, Phenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-Diisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenyl Methylene (2,3,5-triisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) (9-fur Oleenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium Dichloride, diphenylmethylene (2-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2 , 4-Diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium Chloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) ( 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (9- (Luolenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethyle (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) ( 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclo) Pentadienyl (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclo) Pentadienyl) (2,7-dimethyl-9 Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, Diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-dimethyl) -9-Fluorenyl) zirconium Loride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2 , 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3 , 5-triethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-dimethyl -9-fluorenyl) zirconium dichloride, diphenyl Tylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-propyl-1-cyclopentadienyl) (2, 7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dipropyl-1- Cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dipropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (3,4-dipropyl 1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tripropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (2,3,5-tripropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tripropyl-1) -Cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrapropyl-1-cyclopentadienyl) (2,7-dimethyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (2-isopropyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride
Diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7- Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl-1- Cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium Dichloride, gif Nilmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclopentadienyl) ) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, Diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene ( -Phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene ( 2,3,5-triphenyl-1 -Cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl-1-cyclopentadi) Enyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4 -Bis (trimethylsilane L) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris) (Trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium di Loride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis ( Trimethylsilyl) -1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-Methyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) ) Zirconium dichloride, diphe Nilmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-cyclopentadienyl) (2,7- Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-trimethyl-) 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (3,4,5 Trimethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadienyl) (2,7-diethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Diethyl-1-cyclopentadieny ) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2, 3,4-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7- Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4, 5-tetraethyl-1-cyclopentadienyl) (2 , 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-propyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-propyl-1-cyclo) Pentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dipropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dipropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dipropyl-1-cyclopentadienyl) (2,7-diethyl -9-fluorenyl) zyl Nium dichloride, diphenylmethylene (2,3,4-tripropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tripropyl-1- Cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tripropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (2,3,4,5-tetrapropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-isopropyl-1-cyclopentadienyl) ) (2,7-diethyl-9-fluorenyl) di Conium dichloride, diphenylmethylene (3-isopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2 , 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) Zirconium Mudichloride, diphenylmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1-cyclo) Pentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) zirconium dichloride, di Enylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopenta) Dienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, Diphenylmethylene (2, 3, -Triphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl-1-cyclopentadienyl) (2,7-diethyl -9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl- 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (2,4- Bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7- Diethyl-9-fluorenyl) zirconium
Mudichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1 -Cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9- Fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5) -Tetrakis (trimethylsilyl) 1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (2-methyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene ( 2,5-dimethyl-1-cyclopentadienyl) (2,7-di- -Butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3 , 4-Trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-trimethyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-trimethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (2,3,4,5-tetramethyl-1-cyclopentadi Enyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-ethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (3-ethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (3,4-diethyl-1-cyclopentadienyl) (2,7- -T-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-triethyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triethyl-1-cyclopentadi) Enyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraethyl-1-cyclopentadienyl) (2,7-di-t-butyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2-propyl-1-cyclopenta) Enyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (2,4-dipropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dipropyl-1-cyclopentadi) Enyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dipropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (2,3,4-tripropyl-1-cyclopente) Tadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,5-tripropyl-1-cyclopentadienyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tripropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3 , 4,5-tetrapropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-isopropyl-1-cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-iso (Lopyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diisopropyl-1-cyclopentadienyl) (2,7-di-) t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3 4-diisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triisopropyl-1-cyclopentadienyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diph Nilmethylene (2,3,5-triisopropyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triisopropyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraisopropyl-1-cyclopentadienyl) (2,7-di -T-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-cyclo) Pentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dic Loride, diphenylmethylene (3-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (3,4-diphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-triphenyl-1- Cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Chloride, diphenylmethylene (2,3,5-triphenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-triphenyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetraphenyl-1-cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-trimethylsilyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene ( 3-Trimethylsilyl-1-cyclopentadienyl) (2,7-di-t-butyl 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5 -Bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-bis (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4-tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3 , 5-Tris (trimethylsilyl) -1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4,5-tris (trimethylsilyl) -1-cyclo Pentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3,4,5-tetrakis (trimethylsilyl) -1-cyclopentadienyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene ( 3-methyl-1-indenyl) ( -Fluorenyl) zirconium dichloride, diphenylmethylene (4-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (5-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (6-methyl) -1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (7-methyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride Diphenylmethylene (3-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) Zirconium dichloride, diphenylmethylene (5-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (6-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (7-phenyl-1- Indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-indenyl) (9-fluorenyl) zirconium Dichloride, diphenylmethylene (2,5-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2,6-dimethyl-1-indenyl) (9-fluoride) Rhenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethyl
Len (3,5-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,6-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3,7-dimethyl- 1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4,6-dimethyl-1-indenyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (4,7-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (5,6-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride Diphenylmethylene (5,7-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (6,7-dimethyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl) -4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-5) , 6-Benzo-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (α-naphthyl) -1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl) -4- (β-naphthyl) -1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1) -Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-methyl-1) -Indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-methyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6-methyl-1) -Indeni ) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (7-methyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-indenyl) ) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) ) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6-phenyl-1-indene) Nyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (7-phenyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3-dimethyl- 1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2, 5-Dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (2 7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (3,5-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (3,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-dimethyl-1-indenyl) (2,7-dimethyl- 9-fluorenyl) zirconium di Lido, diphenylmethylene (4,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,7-dimethyl-1-indenyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (5,6-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5,7-dimethyl-1-indenyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6,7-dimethyl-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1- Indenyl) (2,7-dimethyl) -9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-5,6- Benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (α-naphthyl) -1-indenyl) (2,7-dimethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (2-methyl-4- (β-naphthyl) -1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenyl Methylene (2-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (4-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (6-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (7-methyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenyl Michile (2-Phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-Phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6-Phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (7-phenyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenyl Tylene (2,3-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) Zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,6-dimethyl-1-indenyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-indenyl) (2, 7-diethyl-9-fluorenyl) zirco Nium dichloride, diphenylmethylene (3,5-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,6-dimethyl-1-indenyl) (2,7-diethyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (3,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-dimethyl-1-indenyl) (2, 7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,7-dimethyl-1-indenyl) ) (2,7-die Ru-9-fluorenyl) zirconium dichloride, diphenylmethylene (5,6-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5,7-dimethyl-1-indenyl) ( 2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6,7-dimethyl-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl) -1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, Diphenylmethylene ( -Methyl-5,6-benzo-1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (α-naphthyl) -1-indenyl) (2,7 -Diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (β-naphthyl) -1-indenyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene ( 3-methyl-1-indenyl) (2,7-di-t-butyl-9- (Luolenyl) zirconium dichloride, diphenylmethylene (4-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-methyl-1-indenyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6-methyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (7-methyl-1) -Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, Diphenylmethylene (3-phenyl-1-indenyl ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5-phenyl-1-indenyl)
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (6-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene ( 7-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,3-dimethyl-1-indenyl) (2,7-di-t-butyl- 9-fluorenyl) zirconium dichloride, diphenylmethylene (2,4-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,5-dimethyl-1-indenyl) ) (2,7-di-t-butyl-9-fluorenyl) zirconium dichlorine Diphenylmethylene (2,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-1-indenyl) (2,7- Di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,5 -Dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (3,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (3,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,5-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenyl Methylene (4,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (4,7-dimethyl-1-indenyl) (2,7-di-) t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5,6-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (5,7-dimethyl) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium Dichloride, diphenylmethylene (6,7-dimethyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenyl-1-indenyl) (2 , 7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride Diphenylmethylene (2-methyl-5,6-benzo-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (α-naphthyl) -1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride dichloride Enirumechiren (2-methyl-4-(beta-naphthyl) -1-indenyl) (2,7-di -t- butyl-9-fluorenyl) can be exemplified zirconium dichloride and the like. X of the above transition metal compound ² A compound in which is substituted with a fluorine atom, a bromine atom or an iodine atom can also be exemplified. In addition, R of the above transition metal compound ⁹ Examples include compounds in which is substituted with a methylene group, ethylene group, isopropylidene group, methylphenylmethylene group, dimethylsilanediyl group, diphenylsilanediyl group, silacyclobutanediyl group, silacyclohexanediyl group, and the like. Further, M of the above transition metal compound ² A compound in which is substituted with a titanium atom or a hafnium atom can also be exemplified.

The amount of component (b) with respect to component (a) in the method for producing polyethylene of the present invention is not particularly limited, and is preferably 0.0001 to 100 times mol, particularly preferably 0.001 to 10 times mol. It is.
As a catalyst containing component (a) and component (b) as main components used in the production method of the present invention, component (a), component (b) and the following general formula (12)
AlR ¹³ ₃ (12)
A catalyst comprising an organoaluminum compound (component (d)) represented by: a catalyst further comprising water,
Component (a), Component (b), and the following general formula (19)
MgR ¹⁶ ₃ (19)
A catalyst comprising an organomagnesium compound represented by (component (e)), and a catalyst further comprising component (d),
Component (a), Component (b) and the following general formula (20)
LiR ¹⁷ (20)
A catalyst comprising an organolithium compound represented by (component (f)), and a catalyst further comprising component (d),
Component (a), Component (b), and the following general formula (21)

および／または下記一般式（２２）

And / or the following general formula (22)

で表されるアルミノオキサン（成分（ｇ））からなる触媒、さらに成分（ｄ）、成分（ｅ）および／または成分（ｆ）を含んでなる触媒、
成分（ａ）と成分（ｂ）と下記一般式（２３）
［Ｒ^１９Ｒ^２０ _ｙ−１Ｍ^５Ｈ］［Ｍ^６Ａｒ_４］ （２３）
で表されるプロトン酸塩（成分（ｈ））、下記一般式（２４）
［Ｃ］［Ｍ^７Ａｒ_４］ （２４）
で表されるルイス酸塩（成分（ｉ）］または下記一般式（２５）
［Ｍ^８Ｌ^２ _ｚ］［Ｍ^９Ａｒ_４］ （２５）
で表される金属塩（成分（ｊ））から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、
成分（ａ）と下記一般式（２６）
Ｍ^１０Ａｒ_３ （２６）
で表されるルイス酸（成分（ｋ）］からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、
成分（ａ）と成分（ｂ）と成分（ｋ）と成分（ｈ）、成分（ｉ）、成分（ｊ）から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、成分（ａ）と成分（ｂ）と塩化マグネシウム（成分（ｌ））からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、成分（ａ）と成分（ｂ）とスルホン酸塩（成分（ｍ））からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、成分（ａ）と成分（ｂ）とカルボン酸（成分（ｎ））からなる触媒、さらに成分（ｄ）および／または成分（ｇ）を含んでなる触媒、成分（ａ）と成分（ｂ）と成分（ｇ）と無機酸化物（成分（ｏ））からなる触媒、さらに成分（ｄ）、成分（ｅ）および／または成分（ｆ）を含んでなる触媒、成分（ａ）と成分（ｂ）と成分（ｏ）と成分（ｈ）、成分（ｉ）、成分（ｊ）から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｄ）、成分（ｅ）および／または成分（ｆ）を含んでなる触媒、成分（ａ）と成分（ｂ）と無機ハロゲン化物（成分（ｐ））と成分（ｈ）、成分（ｉ）、成分（ｊ）から選ばれる少なくとも１種類の塩からなる触媒、さらに成分（ｄ）、成分（ｅ）および／または成分（ｆ）を含んでなる触媒、成分（ａ）と成分（ｂ）と粘土鉱物（成分（ｑ））と成分（ｄ）からなる触媒、成分（ａ）と成分（ｂ）と有機化合物で処理された粘土鉱物（成分（ｃ））からなる触媒、さらに成分（ｄ）、成分（ｅ）および／または成分（ｆ）を含んでなる触媒等を例示することができ、その中でも好ましくは成分（ａ）と成分（ｂ）と有機化合物で処理された粘土鉱物（成分（ｃ））からなる触媒、さらに成分（ｄ）を含んでなる触媒を用いることができる。

A catalyst comprising an aluminoxane represented by (component (g)), a catalyst further comprising component (d), component (e) and / or component (f),
Component (a), Component (b) and the following general formula (23)
_{^{[R 19 R 20 y-1}} M 5 H] [M 6 Ar 4] (23)
Protonate (component (h)) represented by the following general formula (24)
[C] [M ⁷ Ar ₄ ] (24)
A Lewis acid salt represented by the formula (component (i)) or the following general formula (25)
[M ⁸ L ² _z ] [M ⁹ Ar ₄ ] (25)
A catalyst comprising at least one salt selected from metal salts (component (j)) represented by: a catalyst further comprising component (d) and / or component (g),
Component (a) and the following general formula (26)
M ¹⁰ Ar ₃ (26)
A catalyst comprising a Lewis acid (component (k)) represented by: a catalyst further comprising component (d) and / or component (g),
Catalyst comprising at least one salt selected from component (a), component (b), component (k), component (h), component (i) and component (j), and further component (d) and / or component A catalyst comprising (g), a catalyst comprising component (a), component (b) and magnesium chloride (component (l)), and a catalyst comprising component (d) and / or component (g), component A catalyst comprising (a), component (b) and sulfonate (component (m)), further comprising a component (d) and / or component (g), component (a) and component (b) Catalyst comprising carboxylic acid (component (n)), catalyst comprising component (d) and / or component (g), component (a), component (b), component (g) and inorganic oxide (component) (O)), a component (d), a component (e) and / or a component (f) A catalyst comprising at least one salt selected from component (a), component (b), component (o), component (h), component (i), and component (j); d), a catalyst comprising component (e) and / or component (f), component (a), component (b), inorganic halide (component (p)), component (h), component (i), Catalyst comprising at least one salt selected from component (j), catalyst comprising component (d), component (e) and / or component (f), component (a), component (b) and clay A catalyst composed of mineral (component (q)) and component (d), a catalyst composed of clay mineral (component (c)) treated with component (a), component (b) and an organic compound, further component (d), Examples of the catalyst and the like comprising the component (e) and / or the component (f) can be exemplified. Can be preferably used a catalyst comprising components (a) and (b) the organic compound treated clay mineral (component (c)) catalyst comprising further component (d).

  The clay mineral that can be used as the component (c) in the present invention is a fine particle mainly composed of a microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and it can be mentioned that the layers have negative charges of various sizes. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals are generally of a large layer charge, with pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is from about 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here contains various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Examples of these clay minerals include naturally occurring clay minerals, clay minerals with few impurities obtained by artificial synthesis, etc. In the present invention, these clay minerals can be obtained by natural clay minerals and artificial synthesis shown here. All of the clay minerals can be used, and any of those not included in the above description but belonging to the definition of clay minerals can be used. Among these, clay minerals belonging to the smectite group and the mica group are preferable. Furthermore, a mixture of a plurality of the above clay minerals can be used. Moreover, these clay minerals may be used as they are, or may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment.

  The organic compound treatment in component (c) refers to introducing an organic ion between the previous clay mineral layers to form an ionic complex. As the organic compound used in the organic compound treatment, a compound represented by the following general formula (13), (17) or (18) can be used, and among them, a compound represented by the general formula (13) is particularly preferable. It can be preferably used.

[R ¹⁴ R ¹⁵ _y-1 M ³ H] _a [A] _b (13)
[C] _a [A] _b (17)
[M ⁴ L ¹ _z ] _a [A] _b (18)
[A] in the compounds represented by the general formulas (13), (17) and (18) is an anion, for example, fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion. Perchlorate ions, oxalate ions, citrate ions, succinate ions, tetrafluoroborate ions, hexafluorophosphate ions, and the like.

  In the compounds represented by the general formulas (13), (17) and (18), a and b are integers selected so that charges are balanced.

[R ¹⁴ R ¹⁵ _y-1 M ³ H] in the compound represented by the general formula (13) is a cation, M ³ is an element selected from Group 15 or Group 16 of the periodic table, and R ¹⁴ is a hydrocarbon group having 1 to 30 carbon atoms, R ¹⁵ is each independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and y is y = 3 when M ³ is a Group 15 element. And y = 2 when M ³ is a Group 16 element.

Here, M ³ is an element selected from Group 15 or Group 16 of the periodic table, and examples thereof include oxygen, nitrogen, sulfur, phosphorus, etc., and those having 1 to 30 carbon atoms used for R ¹⁴ and R ¹⁵ Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl group, 3,3-dimethyl-2-butyl group, 1 1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl Group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert-octyl group, 2,3-dimethylcyclohexyl group, 2- (1-cyclohexenyl) ethyl group, n- Nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-henecosi Group, n-docosyl group, n-tricosyl group, oleyl group, behenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4- Ethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-tert-butylphenyl group, 4-n-butylphenyl group, 4-sec-butylphenyl group, 4-tert- Butylphenyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,6- Diethylphenyl group, 2-isopropyl-6-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 3- Bromophenyl group, 4-bromophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 1-naphthyl group 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 2,3-dihydroinden-5-yl group, 2-biphenyl group, 4-biphenyl group, p- A trimethylsilylphenyl group etc. can be illustrated. R ¹⁴ and R ¹⁵ may be bonded to each other.

Among the compounds represented by the general formula (13), those in which M ³ is a nitrogen atom include, for example, methylamine hydrochloride, ethylamine hydrochloride, n-propylamine hydrochloride, isopropylamine hydrochloride , N-butylamine hydrochloride, isobutylamine hydrochloride, tert-butylamine hydrochloride, n-pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tert-pentylamine hydrochloride N-hexylamine hydrochloride, isohexylamine hydrochloride, n-heptylamine hydrochloride, n-octylamine hydrochloride, n-nonylamine hydrochloride, n-decylamine hydrochloride, n-undecylamine hydrochloride, n- Dodecylamine hydrochloride, n-tetradecylamine hydrochloride, n-hexadecylamine hydrochloride Salt, n-octadecylamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine Hydrochloride, 2-aminoheptane hydrochloride, 3-aminoheptane hydrochloride, n-heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, n-octylamine hydrochloride, tert -Octylamine hydrochloride, nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, hepta Decylamine hydrochloride Octadecylamine hydrochloride, nonadecylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexyl Amine hydrochloride, cyclododecylamine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, Dioctylamine hydrochloride, didecylamine hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tert-butylcyclohexylamine Acid salt, N-allylcyclohexylamine hydrochloride, N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyl-n- Tetradecylamine hydrochloride, N, N-dimethyl-n-hexadecylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride, N, N-dimethyl-n-eicosylamine hydrochloride, N, N -Dimethyl-n-docosylamine hydrochloride, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecyl Amine hydrochloride, tridodecylamine hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylcyclohexylamine hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride, pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2- Methylpiperidine hydrochloride, 3-methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2-ethylpiperidine Hydrochloride, 2,2,6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2,2 Hydrochloric acid hydrochlorides such as 1,6,6-pentamethylpiperidine hydrochloride, aniline hydrochloride N-methylaniline hydrochloride, N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N -Methyl-o-toluidine hydrochloride, N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride, N-ethyl-o-toluidine hydrochloride, N-ethyl-m-toluidine hydrochloride, N -Ethyl-p-toluidine hydrochloride, N-allyl-o-toluidine hydrochloride, N-allyl-m-toluidine hydrochloride, N-allyl-p-toluidine hydrochloride, N-propyl-o-toluidine hydrochloride, N -Propyl-m-toluidine hydrochloride, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5- Methylaniline hydrochloride, 2,6-dimethylaniline hydrochloride, 3,4-dimethylaniline hydrochloride, 3,5-dimethylaniline hydrochloride, 2-ethylaniline hydrochloride, 3-ethylaniline hydrochloride, 4-ethylaniline Hydrochloride, N, N-diethylaniline hydrochloride, 2-isopropylaniline hydrochloride, 4-isopropylaniline hydrochloride, 2-tert-butylaniline hydrochloride, 4-n-butylaniline hydrochloride, 4-sec-butylaniline Hydrochloride, 4-tert-butylaniline hydrochloride, 2,6-diethylaniline hydrochloride, 2-isopropyl-6-methylaniline hydrochloride, 2-chloroaniline hydrochloride, 3-chloroaniline hydrochloride, 4-chloroaniline Hydrochloride, 2-bromoaniline hydrochloride, 3-bromoaniline hydrochloride, 4-bromoaniline hydrochloride, o-a Nicidin hydrochloride, m-anisidine hydrochloride, p-anisidine hydrochloride, o-phenetidine hydrochloride, m-phenetidine hydrochloride, p-phenetidine hydrochloride, 1-aminonaphthalene hydrochloride, 2-aminonaphthalene hydrochloride, 1- Aminofluorene hydrochloride, 2-aminofluorene hydrochloride, 3-aminofluorene hydrochloride, 4-aminofluorene hydrochloride, 5-aminoindan hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N, 2 , 3-Trimethylaniline hydrochloride, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethylaniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride Salt, N, 3,5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N-methyl-3-e Ruaniline hydrochloride, N-methyl-4-ethylaniline hydrochloride, N-methyl-6-ethyl-o-toluidine hydrochloride, N-methyl-2-isopropylaniline hydrochloride, N-methyl-4-isopropylaniline hydrochloride N-methyl-2-tert-butylaniline hydrochloride, N-methyl-4-n-butylaniline hydrochloride, N-methyl-4-sec-butylaniline hydrochloride, N-methyl-4-tert-butylaniline Hydrochloride, N-methyl-2,6-diethylaniline hydrochloride, N-methyl-2-isopropyl-6-methylaniline hydrochloride, N-methyl-p-anisidine hydrochloride, N-ethyl-2,3-anisidine Hydrochloride, N, N-dimethyl-o-toluidine hydrochloride, N, N-dimethyl-m-toluidine hydrochloride, N, N-dimethyl-p-toluidine hydrochloride N, N, 2,3-tetramethylaniline hydrochloride, N, N, 2,4-tetramethylaniline hydrochloride, N, N, 2,5-tetramethylaniline hydrochloride, N, N, 2,6- Tetramethylaniline hydrochloride, N, N, 3,4-tetramethylaniline hydrochloride, N, N, 3,5-tetramethylaniline hydrochloride, N, N-dimethyl-2-ethylaniline hydrochloride, N, N -Dimethyl-3-ethylaniline hydrochloride, N, N-dimethyl-4-ethylaniline hydrochloride, N, N-dimethyl-6-ethyl-o-toluidine hydrochloride, N, N-dimethyl-2-isopropylaniline hydrochloride Salt, N, N-dimethyl-4-isopropylaniline hydrochloride, N, N-dimethyl-2-tert-butylaniline hydrochloride, N, N-dimethyl-4-n-butylaniline hydrochloride, N, N-dimethyl -4-sec-butylaniline hydrochloride, N, N-dimethyl-4-tert-butylaniline hydrochloride, N, N-dimethyl-2,6-diethylaniline hydrochloride, N, N-dimethyl-2-isopropyl- 6-methylaniline hydrochloride, N, N-dimethyl-2-chloroaniline hydrochloride, N, N-dimethyl-3-chloroaniline hydrochloride, N, N-dimethyl-4-chloroaniline hydrochloride, N, N- Dimethyl-2-bromoaniline hydrochloride, N, N-dimethyl-3-bromoaniline hydrochloride, N, N-dimethyl-4-bromoaniline hydrochloride, N, N-dimethyl-o-anisidine hydrochloride, N, N -Dimethyl-m-anisidine hydrochloride, N, N-dimethyl-p-anisidine hydrochloride, N, N-dimethyl-o-phenetidine hydrochloride, N, N-dimethyl-m-phenetidine hydrochloride N, N-dimethyl-p-phenetidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride Salt, N, N-dimethyl-2-aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5-amino Hydrochlorides of aromatic amines such as indane hydrochloride, N, N-dimethyl-2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl-p-trimethylsilylaniline hydrochloride Examples thereof include compounds obtained by substituting hydrochlorides of the above compounds with hydrofluoric acid salts, hydrobromide salts, hydroiodide salts or sulfates.

Among the compounds represented by the general formula (13), those in which M ³ is an oxygen atom include, for example, methyl ether hydrochloride, ethyl ether hydrochloride, n-butyl ether hydrochloride, tetrahydrofuran hydrochloride, phenyl ether hydrochloride and the like. And a compound obtained by substituting the hydrochloride of the above compound with a hydrofluoride, hydrobromide, hydroiodide, or sulfate.

Among the compounds represented by the general formula (13), those in which M ³ is a sulfur atom include, for example, diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, chloride Examples thereof include dimethylsulfonium, dimethylsulfonium bromide, dimethylsulfonium iodide and the like.

Among the compounds represented by the general formula (13), those in which M ³ is a phosphorus atom include, for example, triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, and tri (p-tolyl) phosphine hydrochloride. Examples thereof include compounds such as trimesitylphosphine hydrochloride and the like, and compounds obtained by substituting hydrochlorides of the above compounds with hydrofluoric acid salts, hydrobromide salts, hydroiodide salts or sulfate salts.

  [C] in the compound represented by the general formula (17) is a carbonium cation or a tropylium cation. Specific examples of the compound represented by the general formula (17) include trityl bromide, trityl chloride, Examples include trityl tetrafluoroborate, trityl hexafluorophosphate, tropylium bromide, tropylium chloride, tropylium tetrafluoroborate, tropylium hexafluorophosphate, and the like.

M ⁴ in the compound represented by the general formula (18) is a cation of a lithium atom, an iron atom and a silver atom, and L ¹ is a Lewis such as ethers, aliphatic amines, aromatic amines, phosphines and the like. A base, a substituted or unsubstituted cyclopentadienyl group, and the like, z is 0 ≦ z ≦ 2, and specific examples of the compound represented by the general formula (18) include ferrocenium bromide and ferrocenium chloride. And ferrocenium tetrafluoroborate, ferrocenium hexafluorophosphate, and the like.

  In the organic compound treatment in the component (c), it is preferable to carry out the treatment by selecting the conditions of a clay mineral concentration of 0.1 to 30% by weight and a treatment temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay mineral and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay mineral. Examples of the processing solvent include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene and toluene; alcohols such as ethyl alcohol and methyl alcohol; ethers such as ethyl ether and n-butyl ether. Halogenated hydrocarbons such as methylene chloride or chloroform; acetone; 1,4-dioxane; tetrahydrofuran or water can be used, among which alcohols or water can be used alone or one component of a solvent can be preferably used. .

  The catalyst comprising component (a), component (b) and component (c) used in the present invention is obtained by bringing component (a), component (b) and component (c) into contact in an organic solvent. As the contact method, for example, the method of adding the component (b) to the contact product of the component (a) and the component (c), the component (a) to the contact product of the component (b) and the component (c) A method of adding, a method of adding the component (c) to the contact product of the component (a) and the component (b), a method of adding the contact product of the component (a) and the component (b) to the component (c), etc. Can be illustrated.

  Examples of the solvent used for contact include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; ethyl ether Or, ethers such as n-butyl ether; halogenated hydrocarbons such as methylene chloride or chloroform; 1,4-dioxane; acetonitrile or tetrahydrofuran can be exemplified.

  The temperature at the time of contact is preferably selected from 0 to 200 ° C. for treatment.

  The amount of each component used is preferably 0.0001 to 100 mmol, particularly preferably 0.001 to 10 mmol, per 1 g of component (c). Moreover, 0.0001-100 mmol is preferable per 1 g of component (c), and, as for a component (b), Most preferably, it is 0.001-10 mmol.

  The contact product of component (a), component (b), and component (c) prepared in this manner may be used without washing, or may be used after washing.

  The catalyst comprising component (a), component (b), component (c) and component (d) brings component (a), component (b), component (c) and component (d) into contact in an organic solvent. As a contact method at that time, for example, a method of adding the component (b) to the component (c) after adding the contact product of the components (a) and (d); and the component (c) After adding the component (a) to the method, the contact product of the component (b) and the component (d) is added; after the contact product of the component (a) and the component (d) is added to the component (c) A method of adding a contact product of component (b) and component (d); a method of adding component (b) after adding component (a) to a contact product of component (c) and component (d) A method of adding the component (b) to the contact product of the component (c) and the component (d) after adding the contact product of the component (a) and the component (d); a method of adding the contact product of component (b) and component (d) after adding component (a) to the contact product of c) and component (d); contact of component (c) and component (d) A method of adding a contact product of component (b) and component (d) after adding a contact product of component (a) and component (d) to the product; contact of component (a) and component (d) Method of adding component (c) after adding component (b) to the product; adding component (c) to component (a) after adding the contact product of component (b) and component (d) A method of adding the component (b) and the component (d) to the contact product of the component (a) and the component (d) and then adding the component (c); a component of the component (a) Method of adding the contact product of component (c) and component (d) after adding (b); After adding component (b) to the contact product of component (a) and component (d) Method of adding the contact product of component (c) and component (d); After adding the contact product of component (b) and component (d) to component (a), component (c) and component (d) Adding the contact product of component (b) and component (d) to the contact product of component (a) and component (d), and then adding component (c) and component (d) A method of adding a contact product of component (a) and component (c) after adding component (b) to component (c) and then adding component (d); component (b) and component (c) A method in which component (a) is added to the contact product of step (b), and then component (d) is added; component (c) is added to the contact product of component (a) and component (b), and then component (d) A method in which the contact product of component (a) and component (b) is added to component (c) and then component (d) is added; component (a) and component in component (b) Method of adding the component (d) after adding the contact product of (c); adding the component (d) after adding the contact products of the component (b) and the component (c) to the component (a) A method of adding the component (d) to the contact product of the component (a) and the component (c) after adding the contact product of the component (b) and the component (c) can be exemplified. .

R ¹³ in the component (d) represented by the general formula (12) used in the present invention is each independently a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms used for R ¹³ in the component (d) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2 -Butyl group, n-pentyl group, isopentyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group Examples thereof include a syl group, an n-octadecyl group, a phenyl group, and a cyclohexyl group.

  Specific examples of the component (d) include trimethylaluminum, dimethylaluminum hydride, triethylaluminum, diethylaluminum hydride, tri-n-propylaluminum, di-n-propylaluminum hydride, triisopropylaluminum, diisopropylaluminum hydride, tri- n-butylaluminum, di-n-butylaluminum hydride, triisobutylaluminum, diisobutylaluminum hydride, tri-tert-butylaluminum, di-tert-butylaluminum hydride, tri-n-hexylaluminum, di-n-hexylaluminum hydride , Triisohexyl aluminum, diisohexyl aluminum hydride, tri-n-octyl aluminum, di-n-octyl Aluminum hydride, tri-isooctyl aluminum, can be exemplified diisooctyl aluminum hydride or the like.

  The amount of component (d) used in the present invention is preferably 0.1 to 10,000 mol, particularly preferably 1 to 1000 mol, per mol of the sum of the number of moles of component (a) and component (b).

R ¹⁶ in the component (e) represented by the general formula (19) used in the present invention is each independently a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of them is 1 carbon atom. ˜20 hydrocarbon groups.

Examples of the halogen atom used for R ¹⁶ in the component (e) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group Group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3 , 3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, n-pentyl group, isopentyl group N-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, phenyl group, cyclohexyl group and the like.

  Specific components (e) include, for example, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, ethyl butyl magnesium, methyl magnesium chloride, methyl magnesium bromide, ethyl magnesium chloride, ethyl magnesium bromide, isopropyl magnesium chloride, isopropyl magnesium bromide, butyl magnesium. Examples include chloride and butyl magnesium bromide.

  The amount of component (e) used in the present invention is preferably 0.1 to 10,000 mol, particularly preferably 1 to 1000 mol, per mol of the sum of the number of moles of component (a) and component (b).

R ¹⁷ in the component (f) represented by the general formula (20) used in the present invention is a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 20 carbon atoms used for R ¹⁷ in the component (f) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl-2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2 -Butyl group, n-pentyl group, isopentyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group Examples thereof include a syl group, an n-octadecyl group, a phenyl group, and a cyclohexyl group.

  Specific examples of the component (f) include methyl lithium, ethyl lithium, butyl lithium and the like.

  The amount of the component (f) used in the present invention is preferably 0.1 to 10000 mol, particularly preferably 1 to 1000 mol, per mol of the sum of the number of moles of the component (a) and the component (b).

R ¹⁸ in the component (g) represented by the general formula (21) or (22) used in the present invention is each independently a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms, and q is 2 to 2. 60.

Examples of the hydrocarbon group having 1 to 20 carbon atoms used in R ¹⁸ in the component (g), for example a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, can be exemplified t- butyl group . Furthermore, component (g) may contain a monomer, dimer and oligomer of an organoaluminum compound.

  These components (g) can generally be obtained by reacting an organoaluminum compound and water in an organic solvent, or by reacting an organoaluminum compound and a salt or oxide hydrate in an organic solvent, by a known method. What was manufactured can be used.

  The amount of the component (g) used in the present invention is preferably 0.01 to 1,000,000 moles, particularly preferably 1 to 100,000 moles per mole of the sum of the moles of the component (a) and the component (b).

[R ¹⁹ R ²⁰ _y-1 M ⁵ H] in the component (h) represented by the general formula (23) used in the present invention is a cation, and [M ⁶ Ar ₄ ] is an anion.

M ⁵ in the component (h) is an element selected from Group 15 or 16 of the periodic table, R ¹⁹ is a hydrocarbon group having 1 to 30 carbon atoms, and R ²⁰ is independently a hydrogen atom. Or a hydrocarbon group having 1 to 30 carbon atoms, y is y = 3 when M ⁵ is a Group 15 element, y = 2 when M ⁵ is a Group 16 element, M ⁶ is boron, Aluminum or gallium, and each Ar is independently a halogen-substituted aryl group having 6 to 20 carbon atoms.

Examples of the hydrocarbon group having 1 to 30 carbon atoms used for R ¹⁹ and R ²⁰ in the component (h) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, and isobutyl. Group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1-ethylpropyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl Group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl- 2-butyl, 1,1-dimethylbutyl, 2,3-dimethyl-2-butyl, cyclohexyl, n-heptyl, cyclo Butyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert- Octyl group, 2,3-dimethylcyclohexyl group, 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group Group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group Group, n-tricosyl group, oleyl group, behenyl group, phenyl group, o-tolyl group, m-tril Group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2-isopropylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 2-tert-butylphenyl Group, 4-n-butylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6 -Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,6-diethylphenyl group, 2-isopropyl-6-methylphenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group 2-bromophenyl group, 3-bromophenyl group, 4-bromophenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-metho Siphenyl group, 2-ethoxyphenyl group, 3-ethoxyphenyl group, 4-ethoxyphenyl group, 1-naphthyl group, 2-naphthyl group, 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group 2,3-dihydroinden-5-yl group, 2-biphenyl group, 4-biphenyl group, p-trimethylsilylphenyl group and the like. R ¹⁹ and R ²⁰ may be bonded to each other.

  Examples of the halogen-substituted aryl group having 6 to 20 carbon atoms used for Ar in component (h) include a pentafluorophenyl group.

  Specific examples of the component (h) include diethyloxonium tetrakis (pentafluorophenyl) borate, dimethyloxonium tetrakis (pentafluorophenyl) borate, tetramethylene oxonium tetrakis (pentafluorophenyl) borate, hydronium tetrakis (penta). Fluorophenyl) borate, trimethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, diethyloxonium tetrakis ( Pentafluorophenyl) aluminate, dimethyloxonium tetrakis (pentafluorophenyl) aluminate, tetramethyle Oxonium tetrakis (pentafluorophenyl) aluminate, hydronium tetrakis (pentafluorophenyl) aluminate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) aluminate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) ) Aluminate and the like can be exemplified.

[C] in the component (i) represented by the general formula (24) used in the present invention is a carbonium cation or a tropylium cation, and M ⁷ is boron, aluminum or gallium.

  Specific examples of the component (i) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis (pentafluorophenyl) aluminate. Etc. can be illustrated.

In the component (j) represented by the general formula (25) used in the present invention, M ⁸ is a cation of a lithium atom, an iron atom and a silver atom, and L ² is an ether, aliphatic amine, aromatic Lewis bases such as amines and phosphines, or substituted or unsubstituted cyclopentadienyl groups, z is 0 ≦ z ≦ 2, and M ⁹ is boron, aluminum, or gallium.

  Specific examples of the component (j) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate; or ether complexes thereof; ferrocenium tetrakis (pentafluorophenyl) borate, Examples include ferrocenium salts such as ferrocenium tetrakis (pentafluorophenyl) aluminate; silver salts such as silver tetrakis (pentafluorophenyl) borate and silver tetrakis (pentafluorphenyl) aluminate.

In the component (k) represented by the general formula (26) used in the present invention, M ¹⁰ is boron or aluminum. Specific examples of the component (k) include tris (pentafluorophenyl) borane and tris ( 2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (pentafluorophenyl) ) Borane, tris (3,4,5-trifluorophenyl) aluminum and the like can be exemplified.

  The component (m) used in the present invention is a sulfonate, and examples of the sulfonate include lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, and bis (trifluoromethanesulfonate). Calcium, bis (trifluoromethanesulfonate) barium, tris (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) titanium, tetrakis (trifluoromethanesulfonate) zirconium, tetrakis (trifluoromethanesulfonate) hafnium, pentakis (trifluoro) Lomethanesulfonate) niobium, pentakis (trifluoromethanesulfonate) tantalum, tris (trifluoromethanesulfurate) Nato) iron, trifluoromethanesulfonate silver, tris (trifluoromethanesulfonate) boron, tris (trifluoromethanesulfonate) aluminum, tris (trifluoromethanesulfonate) gallium, tetrakis (trifluoromethanesulfonate) tin, pentafluorobenzenesulfone Sodium lithium, pentafluorobenzenesulfonate sodium, potassium pentafluorobenzenesulfonate, bis (pentafluorobenzenesulfonate) magnesium, bis (pentafluorobenzenesulfonate) calcium, bis (pentafluorobenzenesulfonate) barium, tris (penta Fluorobenzenesulfonate) titanium, tetrakis (pentafluorobenzenesulfonate) zirconium, Tet Kis (pentafluorobenzene sulfonate) hafnium, pentakis (pentafluorobenzene sulfonate) niobium, pentakis (pentafluorobenzene sulfonate) tantalum, tris (pentafluorobenzene sulfonate) iron, pentafluorobenzene sulfonate silver, tris (penta Fluorobenzenesulfonate) boron, tris (pentafluorobenzenesulfonate) aluminum, tris (pentafluorobenzenesulfonate) gallium, tetrakis (pentafluorobenzenesulfonate) tin, bis (trifluoromethanesulfonate) magnesium, pentakis (trifluoromethane) Sulfonate) niobium, bis (pentafluorobenzenesulfonate) magnesium, tetrakis (pentafluorobenzenes) (Rufonate) titanium and pentakis (pentafluorobenzenesulfonate) niobium.

  The component (n) used in the present invention is a carboxylic acid, and examples of the carboxylic acid include trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluorobenzoic acid, tetrafluorotoluic acid, 2,4- (trifluoro Examples thereof include methyl) benzoic acid and pentafluorophenylacetic acid.

  The amount of component (h), component (i), component (j), component (k), component (m), and component (n) used in the present invention is the number of moles of component (a) and component (b). Is preferably from 0.1 to 1000 mol, particularly preferably from 0.3 to 100 mol, per mol of the sum.

  Component (l) used in the present invention is magnesium chloride, which is prepared by a known method, and the amount of component (l) is the sum of the number of moles of component (a) and component (b) 1 0.01 to 10000 kg per mole is preferred, and 0.1 to 1000 kg is particularly preferred. Further, using organic aluminum halide, organic magnesium, or the like, magnesium chloride can be produced in the system during polymerization or catalyst preparation and used for the polymerization.

The component (o) used in the present invention is an inorganic oxide, and the inorganic oxide preferably has an average particle size of 1 to 300 μm, particularly a fine porous particle in the range of 10 to 200 μm. Particles are preferred because they are easy to handle during catalyst preparation and polymerization processes. Specific examples of the inorganic oxide include inorganic oxides of typical elements such as silica, alumina, and magnesia; inorganic oxides of transition metal elements such as titania and zirconia, and mixtures of silica-alumina, silica-magnesia, and the like. . These inorganic oxides usually contain alkali metal or alkaline earth metal salts such as Na ₂ O, K ₂ CO ₃ and BaSO ₄ as impurities. The fine particle inorganic oxide may be used in a state containing these impurities, but it is preferable to use an inorganic oxide that has been previously subjected to an operation for removing these impurities. Such porous fine-particle inorganic oxides have different properties depending on the kind and production method. In the present invention, the specific surface area is 10 to 1000 m ² / g, particularly 50 to 800 m ² / g, pores. The one having a volume of 0.1 to 3 mL / g is preferable because a large amount of a transition metal compound-supporting component can be supported. These inorganic oxides are used after being calcined at 100 to 1000 ° C. under reduced pressure or in a gas stream as necessary.

Moreover, the hydroxyl group of these inorganic oxides can be substituted with halogen. As a method of substituting the hydroxyl group of the inorganic oxide with a halogen, a method of reacting with a reactive agent having a halogen exchangeable with the surface hydroxyl group is preferable. Examples of the reactant include halogens such as fluorine, chlorine, bromine and iodine; hydrogen halides such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide: phosgene, thionyl chloride, ammonium fluoride, ammonium chloride, And halogen-containing compounds such as ammonium iodide, carbon tetrachloride, chloroform, and chlorofluorocarbon. These inorganic compounds may be subjected to heat treatment under reduced pressure or gas flow at 100 to 1000 ° C. for the purpose of removing H ₂ O, which is a by-product, after replacing some or all of the hydroxyl groups with halogen. Good.

  The inorganic oxide may be contacted with a metal compound in advance for the purpose of post-treatment of the —OH residue prior to contact with other catalyst components. The metal compound used here is not particularly limited, and preferably component (d), component (e) and / or component (f) is used. The method for bringing the inorganic oxide into contact with the above metal compound is not particularly limited. For example, the method in which the oxide is insoluble in the organic solvent in which the metal compound is soluble, and the organic compound in which both are soluble. Examples include a method of contacting in a solvent and a method of contacting with a ball mill or the like in a substantially solvent-free condition.

  As a method for preparing a catalyst comprising component (a), component (b), component (g) and component (o) used in the present invention, for example, after contacting component (g) and component (o), Method of adding (a) and component (b); Method of adding component (o) after contacting component (a), component (b) and component (g); Component (a) and component (g) ) And the component (o) are contacted and then the method of adding the component (b) can be exemplified.

  The amount of component (a) in the catalyst comprising component (a), component (b), component (g) and component (o) is preferably 0.005 to 1 mmol, particularly preferably 1 g of component (o). The amount of Al atoms contained in the component (g) is 0.05 to 0.5 mmol, and it is preferable that a better polymerization activity can be obtained by using it in a proportion of 10 to 200 mol with respect to 1 mol of the component (a). is there.

  As a method for preparing a catalyst comprising at least one salt selected from component (a), component (b), component (o), component (h), component (i) and component (j) used in the present invention, For example, a method of adding component (a) and component (b) after contacting component (o) with at least one salt selected from component (h), component (i) and component (j); A method of adding component (o) after contacting at least one salt selected from (a), component (b), component (h), component (i), and component (j); component (a) Examples thereof include a method of adding the component (b) after contacting at least one salt selected from the component (o), the component (h), the component (i) and the component (j).

  Component (a) with respect to 1 mol of component (a) in a catalyst comprising at least one salt selected from component (a), component (b), component (o), component (h), component (i), and component (j) The amount of the anionic component in at least one salt selected from (h), component (i), and component (j) is preferably 0.01 to 1000 mol because good polymerization activity is obtained. Preferably it is 0.2-500 mol. Furthermore, the amount of the component (a) relative to 1 kg of the component (o) is preferably 0.001 to 1 mol, particularly preferably 0.001 to 0.5 mol, and further preferably 0.001 to 0.3. The range of moles.

  The component (p) used in the present invention is an inorganic halide. Examples of the inorganic halide include halides of alkaline earth metals such as magnesium chloride, halides of Group 13 elements of the periodic table such as aluminum chloride, and the like. It can be illustrated.

  As a method for preparing a catalyst comprising at least one salt selected from component (a), component (b), component (p), component (h), component (i) and component (j) used in the present invention. For example, a method of adding component (a) and component (b) after contacting at least one salt selected from component (p) and component (h), component (i), component (j); Method of adding component (p) after contacting at least one salt selected from (a), component (b), component (h), component (i), and component (j); component (a) Examples thereof include a method of adding the component (b) after contacting at least one salt selected from the component (p), the component (h), the component (i), and the component (j).

  Component (a) with respect to 1 mol of component (a) in a catalyst comprising at least one salt selected from component (a), component (b), component (p), component (h), component (i), and component (j) The amount of the anionic component in at least one salt selected from (h), component (i), and component (j) is preferably 0.01 to 1000 mol because good polymerization activity is obtained. Preferably it is 0.2-500 mol. Furthermore, the amount of the component (a) relative to 1 kg of the component (p) is preferably 0.001 to 1 mol, particularly preferably 0.001 to 0.5 mol, more preferably 0.001 to 0.3. The range of moles.

  The component (q) in the present invention is a clay mineral, and the clay mineral is a fine particle mainly composed of a microcrystalline silicate. Most of the clay minerals have a layered structure as a structural feature, and it can be mentioned that the layers have negative charges of various sizes. In this respect, it is greatly different from a metal oxide having a three-dimensional structure such as silica or alumina. These clay minerals are generally of a large layer charge, with pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is from about 0.25). 0.6), vermiculite group (negative charge per chemical formula is approximately 0.6 to 0.9), mica group (negative charge per chemical formula is approximately 1), brittle mica group (negative charge per chemical formula is approximately 2) It is classified. Each group shown here includes various clay minerals, and examples of the clay mineral belonging to the smectite group include montmorillonite, beidellite, saponite, hectorite and the like. Moreover, although these clay minerals exist naturally, a thing with few impurities can be obtained by artificial synthesis. In the present invention, all of the natural clay minerals shown here and clay minerals obtained by artificial synthesis can be used, and those not listed above but belonging to the definition of clay minerals can be used. it can. Furthermore, a mixture of a plurality of the above clay minerals can be used.

  The component (q) in the present invention may be used as it is, or may be used after newly adsorbing and adsorbing water, or after heat dehydration treatment.

  The component (q) is preferably subjected to chemical treatment such as alkali treatment and salt treatment. The alkali treatment uses an alkali such as sodium hydroxide to destroy the crystal structure of the component (q) and bring about a structural change. For example, lithium chloride, sodium phosphate, sodium sulfate, sodium acetate, sodium formate, sodium citrate, sodium nitrate, sodium oxalate, magnesium chloride, magnesium sulfate, magnesium phosphate, magnesium perchlorate, magnesium oxalate Swells by replacing the exchangeable ions between layers (q) with other ions using salts such as magnesium nitrate, magnesium acetate, magnesium succinate, aluminum sulfate, aluminum phosphate, aluminum oxalate, aluminum nitrate Increase the distance and interlayer distance.

  In the production method of the present invention, when producing polyethylene by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms, there are no particular restrictions on polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration. The temperature is preferably −100 to 120 ° C., and considering the productivity, it is preferably 20 to 120 ° C., more preferably 60 to 120 ° C. The polymerization time is preferably in the range of 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of normal pressure to 300 MPa. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. In addition, polyethylene can be obtained by separating and recovering from the polymerization solvent by a conventionally known method after completion of the polymerization and drying.

  In the production method of the present invention, the polymerization can be carried out by any of the known slurry method process, gas phase method process, solution method process, and high pressure method process. Can efficiently and stably produce an olefin polymer having a uniform particle shape. The solvent to be used may be any organic solvent that is generally used. Specific examples include benzene, toluene, xylene, propane, isobutane, pentane, hexane, heptane, cyclohexane, gasoline, and the like. Olefin itself such as butene, 1-hexene and 1-octene can be used as a solvent.

  The polyethylene produced in the present invention is, for example, heat-resistant stabilizer, weather-resistant stabilizer, antistatic agent, anti-fogging agent, anti-blocking agent, slip agent, lubricant, nucleating agent, pigment, carbon black, talc, glass powder, glass fiber. And other known additives such as inorganic fillers or reinforcing agents, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents.

  The polyethylene produced in the present invention can be used by mixing with other thermoplastic resins, such as HDPE, LLDPE, LDPE, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene It can be mixed with a vinyl acetate copolymer, an ethylene / vinyl alcohol copolymer, polystyrene, or a maleic anhydride graft product thereof.

The flow activation energy (E _a ) of the polyethylene produced in the present invention is a value obtained by substituting the shift factor obtained by dynamic viscoelasticity measurement at 160 to 230 ° C. into the Arrhenius equation, and is 30 kJ / mol. It is preferably 100 kJ / mol or less, particularly preferably 35 kJ / mol or more and 80 kJ / mol or less, and further preferably 40 kJ / mol or more and 70 kJ / mol or less.

The melt tension (MS) of polyethylene produced in the present invention is a die having a length (L) of 8 mm and a diameter (D) of 2.095 mm, an inflow angle of 90 °, and a shear rate of 10.8 s ^−1. The value measured at a stretch ratio of 47, and when the maximum stretch ratio was less than 47, the value measured at the highest stretch ratio that did not break was taken as MS. The melt flow rate (MFR) is a value measured at 190 ° C. and a 2.16 kg load. MS (mN) and MFR (g / 10 min., 190 ° C.) of the polyethylene of the present invention are the following formulas (27) or (28):
MS ₁₉₀ > 22 × MFR ^−0.88 (27)
(In the formula, MS ₁₉₀ is MS measured at 190 ° C.)
MS ₁₆₀ > 110-110 × log (MFR) (28)
(In the formula, MS ₁₆₀ is MS measured at 160 ° C.)
It is preferable to satisfy any one of the following, more preferably the formula (28) or the following formula (27) ′
MS ₁₉₀ > 30 × MFR− ^0.88 (27) ′
And particularly preferably satisfies both the formula (27) and the formula (28), more preferably satisfies both the formula (27) ′ and the formula (28), and preferably further satisfies the formula (27) ′. And the following formula (28) ′
MS ₁₆₀ > 130-110 × log (MFR) (28) ′
And most preferably the formula (27) ′ and the following formula (28) ″
MS ₁₆₀ > 150-110 × log (MFR) (28) ″
There is a relationship that satisfies both.

The non-linearity parameter (λ) of the extensional viscosity of the polyethylene produced in the present invention is preferably 1.2 or more and 100 or less, particularly preferably 2.0 or more and 100 or less, more preferably 2.0 or more and 30 or less. is there. The λ is obtained by dividing the maximum value of the extension viscosity measured at 160 ° C. under a strain rate of 0.07 to 0.1 s ⁻¹ by the extension viscosity in the linear region at that time using a Meissner type uniaxial extension viscometer. As described in “M. Yamaguchi et al. Polymer Journal 32, 164 (2000)”, the elongational viscosity in the linear region can be calculated from dynamic viscoelasticity.

The maximum draw ratio (DR) of the polyethylene produced in the present invention is a die having a length (L) of 8 mm and a diameter (D) of 2.095 mm, an inflow angle of 90 °, 160 ° C., and a shear rate of 10 The stretching ratio at break when the take-up speed is increased by 20 m / min per minute under the condition of .8s ⁻¹ , and the MS ₁₆₀ and DR of the polyethylene of the present invention are preferably represented by the following formula (29) There is a relationship.

log (DR)> 5-1.33 × log (MS ₁₆₀ ) (29)

  According to the present invention, it is possible to economically produce polyethylene having both good moldability of LDPE with good morphology and mechanical strength of HDPE and LLDPE.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, commercially available reagents were used.

  Preparation of component (c), preparation of solid catalyst component, preparation of polyethylene production catalyst, production of polyethylene and solvent purification were all carried out under an inert gas atmosphere. Preparation of component (c), preparation of polyethylene production catalyst, solvent used for the production of polyethylene and the like were all purified, dried and deoxygenated by known methods in advance. Components (a) and (b) were synthesized and identified by known methods. Tosoh Finechem Co., Ltd. was used for the triisobutylaluminum hexane solution (0.714M) and the methylaluminoxane toluene solution (brand name: PMAO; Al: 2.39M).

  Further, various physical properties of polyethylene in the examples were measured by the following methods.

  The weight average molecular weight (Mw), the number average molecular weight (Mn) and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) were measured by gel permeation chromatography (GPC). Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC apparatus, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 140 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

  The shrinkage factor (g ′ value) was determined by measuring the [η] of polyethylene fractionated by GPC, and the [η] at an absolute molecular weight of 700,000 or 3 times the Mw of HDPE with no branching. The value divided by [η]. Tosoh Co., Ltd. HLC-8121GPC / HT is used as the GPC device, Tosoh Co., Ltd. TSKgel GMHhr-H (20) HT is used as the column, the column temperature is set to 145 ° C., and 1 is used as the eluent. Measurement was performed using 2,4-trichlorobenzene. A measurement sample was prepared at a concentration of 2.0 mg / ml, and 0.3 ml was injected and measured. As a viscometer, a capillary differential pressure viscometer 210R + manufactured by Viscotek was used.

  The shrinkage factor (g value) was determined by a method of measuring the radius of inertia of polyethylene separated by GPC by light scattering. The root mean square of the radius of inertia at 700,000 absolute molecular weight of the polyethylene of the present invention or 3 times the absolute molecular weight of Mw is the mean square of the radius of inertia at 700,000 absolute molecular weight of HDPE without branching or 3 times the absolute molecular weight of Mw. It is the value divided. As the light scattering detector, a multi-angle light scattering detector DAWV EOS manufactured by Wyatt Technology was used, and the wavelength of 690 nm was 29.5 °, 33.3 °, 39.0 °, 44.8 °, 50.7. °, 57.5 °, 64.4 °, 72.3 °, 81.1 °, 90.0 °, 98.9 °, 107.7 °, 116.6 °, 125.4 °, 133.2 Measurements were made at detection angles of °, 140.0 °, and 145.8 °.

The terminal structure of the polymer such as vinyl terminal and saturated terminal was measured by ¹³ C-NMR using a JNM-ECA400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. The solvent is tetrachloroethane -d _2. The number of vinyl ends was determined from the average value of peaks at 114 ppm and 139 ppm as the number per 1,000 main chain methylene carbons (chemical shift: 30 ppm). Similarly, the number of saturated terminals was determined from the average value of peaks at 32.3 ppm, 22.9 ppm, and 14.1 ppm. Z (= X / (X + Y) × 2) was determined from the number of vinyl ends (X) and the number of saturated ends (Y).

  The density (d) was measured by a density gradient tube method in accordance with JIS K6760 (1995).

The number of long-chain branches was determined by ¹³ C-NMR using a JNM-GSX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. The solvent is benzene-d ₆ / orthodichlorobenzene (volume ratio 30/70). The number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).

Polyethylene used for measurement of flow activation energy (E _a ), melt tension (MS), maximum draw ratio (DR), and elongational viscosity is Irganox 1010 ^™ (manufactured by Ciba Specialty Chemicals) as a heat-resistant stabilizer. , 500ppm, Irgafos 168 ^™ (Ciba Specialty Chemicals Co., Ltd.) with 1,500ppm added, using an internal mixer (Toyo Seiki Seisakusho, trade name: Labo Plast Mill), rotating at 190 ° C under nitrogen flow What knead | mixed for several minutes at several 30 rpm was used.

The activation energy (E _a ) of the flow was measured using a cone-disk rheometer (Rheometrics, trade name: SR2000) at a temperature of 160 ° C., 190 ° C., and 230 ° C. at a frequency of 0.01 to 100 Hz. The shear storage elastic modulus G ′ and the shear loss elastic modulus G ”of the range were obtained, the shift factor of the horizontal axis at the reference temperature of 160 ° C. was obtained, and“ Science of Polymer Science, Volume 8 Polymer Properties (1 ), 369 (1997) ”, the activation energy of the flow was calculated.

The extensional viscosity was measured using a Meissner type uniaxial extensional viscometer (trade name: Melten Rheometer manufactured by Toyo Seiki Seisakusho) set at a temperature of 160 ° C. The non-linear parameter (λ) was obtained as a value obtained by dividing the maximum value of the extensional viscosity measured under the condition of strain rate of 0.07 to 0.1 s ⁻¹ by the extensional viscosity in the linear region at that time. In addition, the value of the extensional viscosity in the linear region was calculated using an approximate expression from dynamic viscoelasticity according to the method described in “M. Yamaguchi et al. Polymer Journal 32, 164 (2000)”.

  The melt tension (MS) and maximum draw ratio (DR) were as follows: a capillary viscometer (Toyo Seiki Seisakusho, trade name: Capillograph) with a barrel diameter of 9.55 mm, a length (L) of 8 mm, and a diameter (D) of 2. A 095 mm die was mounted and measured such that the inflow angle was 90 °. For MS, the temperature was set to 160 ° C. or 190 ° C., the piston lowering speed was set to 10 mm / min, the stretch ratio was set to 47, and the load (mN) required for take-up was MS. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was defined as MS. In DR, the temperature was set to 160 ° C., the take-up speed was increased by 20 m / min per minute, and the draw ratio at break was taken as DR. In addition, taking over was performed in the thermostatic chamber set to 23 degreeC.

Example 1
[Preparation of component (c)]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 6.6 g (0.022 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride solution was prepared. To this solution was added 20 g of hectorite. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, the modified hectorite (component (c)) with an average particle diameter of 5.2 micrometers was obtained by drying at 60 degreeC and 10 < ^-3 > torr for 24 hours, and grind | pulverizing with a jet mill.

[Preparation of polyethylene production catalyst]
4.0 g of the above modified hectorite is suspended in 10 mL of hexane, 17 mL of a hexane solution of triisobutylaluminum (0.714 M) (component (d)) is added, and the mixture is stirred at 60 ° C. for 1 hour, whereby the component (c ) And component (d) contact product. Meanwhile, 6 mL of a hexane solution (0.714 M) of triisobutylaluminum was added to a suspension of 55.8 mg (160 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride (component (a)) in 4 mL of hexane. The solution was added to the contact product of component (c) and component (d). After stirring at 60 ° C. for 3 hours, the mixture was allowed to stand to remove the supernatant, and washed with a hexane solution (0.03M) of triisobutylaluminum. Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  To the catalyst precursor slurry prepared above, 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) with respect to dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. ) A solution of 4.7 mg (8.4 μmol) of hexane (7.2 mL) and triisobutylaluminum in hexane (0.714 M) (1.2 mL) was added and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, 0.4 mL of the catalyst slurry was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 159 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 1
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst precursor slurry prepared in Example 1 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 150 g of polymer was obtained. The obtained polymer had Mn = 11,000 and Mw / Mn = 2.50, and the terminal structure of the polymer was analyzed by ¹³ C-NMR. 57. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

Comparative Example 2
[Preparation of polyethylene production catalyst]
4.0 g of the modified hectorite prepared in Example 1 [Preparation of component (c)] was suspended in 10 mL of hexane, and 17 mL of a hexane solution of triisobutylaluminum (0.714 M) (component (d)) was added. By stirring at 60 ° C. for 1 hour, a contact product of component (c) and component (d) was obtained. On the other hand, 89.1 mg (160 μmol) of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) suspended in 4 mL of hexane was suspended in a hexane solution of triisobutylaluminum (0. 714M) 6 mL was added and the solution was added to the contact product of component (c) and component (d). After stirring at 60 ° C. for 3 hours, the mixture was allowed to stand to remove the supernatant, and washed with a hexane solution (0.03M) of triisobutylaluminum. Further, a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a catalyst slurry of 100 g / L.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 200 g of polymer was obtained. ^When the terminal structure of the polymer was analyzed by ¹³ C-NMR, no vinyl terminal was detected. Further, no long chain branching was detected.

Comparative Example 3
[Preparation of polyethylene production catalyst]
4.0 g of the modified hectorite prepared in Example 1 [Preparation of component (c)] was suspended in 10 mL of hexane, and 17 mL of a hexane solution of triisobutylaluminum (0.714 M) (component (d)) was added. By stirring at 60 ° C. for 1 hour, a contact product of component (c) and component (d) was obtained. Meanwhile, 6 mL of a hexane solution (0.714 M) of triisobutylaluminum was added to a suspension of 46.8 mg (160 μmol) of bis (cyclopentadienyl) zirconium dichloride in 4 mL of hexane, and this solution was added to the component (c). And component (d) to the contact product. After stirring at 60 ° C. for 3 hours, the mixture was allowed to stand to remove the supernatant, and washed with a hexane solution (0.03M) of triisobutylaluminum. Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  3. 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) with respect to bis (cyclopentadienyl) zirconium dichloride is added to the catalyst precursor slurry prepared above. 7 mg (8.4 μmol) was added to a solution of 7.2 mL of hexane and 1.2 mL of a hexane solution of triisobutylaluminum (0.714 M) and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 75 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 4
[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst precursor slurry prepared in Comparative Example 3 [Preparation of polyethylene production catalyst] was used. As a result, 70 g of polymer was obtained. ^When the terminal structure of the polymer was analyzed by ¹³ C-NMR, no vinyl terminal was detected. Further, no long chain branching was detected.

Comparative Example 5
[Preparation of polyethylene production catalyst]
4.0 g of the modified hectorite prepared in Example 1 [Preparation of component (c)] was suspended in 10 mL of hexane, and 17 mL of a hexane solution of triisobutylaluminum (0.714 M) (component (d)) was added. By stirring at 60 ° C. for 1 hour, a contact product of component (c) and component (d) was obtained. Meanwhile, 6 mL of a hexane solution of triisobutylaluminum (0.714 M) was added to a suspension of 58.9 mg (160 μmol) of dimethylsilanediyltetramethylcyclopentadienyl-t-butylamidotitanium dichloride in 4 mL of hexane, The solution was added to the contact product of component (c) and component (d). After stirring at 60 ° C. for 3 hours, the mixture was allowed to stand to remove the supernatant, and washed with a hexane solution (0.03M) of triisobutylaluminum. Further, a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a catalyst slurry of 100 g / L.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 75 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Example 2
[Preparation of polyethylene production catalyst]
As component (b), diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) is used instead of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride. ) Prepared in the same manner as in Example 1 except that zirconium dichloride was used.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that the prepared catalyst was used. As a result, 174 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 6
[Preparation of polyethylene production catalyst]
4.0 g of the modified hectorite prepared in Example 1 [Preparation of component (c)] was suspended in 10 mL of hexane, and 17 mL of a hexane solution of triisobutylaluminum (0.714 M) (component (d)) was added. By stirring at 60 ° C. for 1 hour, a contact product of component (c) and component (d) was obtained. On the other hand, 107.0 mg (160 μmol) of diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (component (b)) suspended in 4 mL of hexane 6 mL of a hexane solution of triisobutylaluminum (0.714 M) was added to the contact product of components (c) and (d). After stirring at 60 ° C. for 3 hours, the mixture was allowed to stand to remove the supernatant, and washed with a hexane solution (0.03M) of triisobutylaluminum. Further, a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a catalyst slurry of 100 g / L.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 230 g of polymer was obtained. ^When the terminal structure of the polymer was analyzed by ¹³ C-NMR, no vinyl terminal was detected. Further, no long chain branching was detected.

Example 3
[Preparation of polyethylene production catalyst]
55.8 mg (160 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride (component (a)) was suspended in 17.6 mL of hexane, and a hexane solution of triisobutylaluminum (component (d)) (0.714 M) ) 22.4 mL was added to obtain a contact product of component (a) and component (d). 4.0 g of the modified hectorite (component (c)) was added to the contact product, and the mixture was stirred at 60 ° C. for 3 hours, and then allowed to stand to remove the supernatant, and a hexane solution of triisobutylaluminum (0.03 M ). Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  To the catalyst precursor slurry prepared above, 5 mol% of diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) based on dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. A solution of 4.7 mg (8.4 μmol) of zirconium dichloride (component (b)) in 7.2 mL of hexane and 1.2 mL of a hexane solution of triisobutylaluminum (0.714 M) was added and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that the prepared catalyst was used. As a result, 215 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 7
[Preparation of polyethylene production catalyst]
115.0 mg (160 μmol) of diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride (component (b)) was suspended in 17.6 mL of hexane, and triisobutylaluminum ( 22.4 mL of a hexane solution (0.714M) of component (d)) was added to obtain a contact product of component (a) and component (d). To this contact product, 4.0 g of the modified hectorite (component (c)) prepared in Example 1 [Preparation of component (c)] was added, stirred at 60 ° C. for 3 hours, and then allowed to stand to obtain a supernatant. And washed with a hexane solution of triisobutylaluminum (0.03M). Further, a hexane solution (0.15 M) of triisobutylaluminum was added to finally obtain a catalyst slurry of 100 g / L.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 250 g of polymer was obtained. ^When the terminal structure of the polymer was analyzed by ¹³ C-NMR, no vinyl terminal was detected. Further, no long chain branching was detected.

Example 4
[Preparation of polyethylene production catalyst]
Example 1 except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was added as a component (b) in an amount of 10 mol% based on dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. Prepared in a similar manner.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that the prepared catalyst was used. As a result, 205 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Example 5
[Preparation of polyethylene production catalyst]
It was prepared in the same manner as in Example 1 except that ethylene bis (cyclopentadienyl) zirconium dichloride was used as component (a) instead of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that 0.3 mL of the prepared catalyst slurry was used. As a result, 167 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, long chain branching number, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Comparative Example 8
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 5 except that 0.4 mL of the catalyst precursor slurry prepared in Example 5 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 160 g of polymer was obtained. The obtained polymer had Mn = 18,000 and Mw / Mn = 2.50. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 45. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

Example 6
[Preparation of polyethylene production catalyst]
As component (b), the same as in Example 1 except that 10 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was added to ethylenebis (cyclopentadienyl) zirconium dichloride. Prepared by method.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that 0.3 mL of the prepared catalyst slurry was used. As a result, 130 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Example 7
[Preparation of polyethylene production catalyst]
As component (b), the same as Example 1 except that 15 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was added to ethylenebis (cyclopentadienyl) zirconium dichloride. Prepared by method.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 1 except that 0.3 mL of the prepared catalyst slurry was used. As a result, 125 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Example 8
[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, 0.4 mL of the catalyst slurry prepared in Example 1 was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released, and then the internal temperature of the autoclave was raised to 90 ° C., and ethylene was introduced until the partial pressure reached 0.3 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 0.3 MPa, and the polymerization temperature was controlled at 90 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 173 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, long chain branching number, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 9
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 6 except that the catalyst slurry prepared in Example 4 was added instead of the catalyst slurry prepared in Example 1. As a result, 184 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS of the obtained polyethylene.

Example 10
[Preparation of component (c)]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 7.78 g (0.022 mol) of N, N-dimethyl-behenylamine was added to the resulting solution and heated to 60 ° C. N, N-dimethyl-behenylamine hydrochloride solution was prepared. To this solution was added 20 g of hectorite. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, the modified hectorite (component (c)) with an average particle diameter of 5.2 micrometers was obtained by drying at 60 degreeC and 10 < ^-3 > torr for 24 hours, and grind | pulverizing with a jet mill.

[Preparation of polyethylene production catalyst]
75.6 mg (160 μmol) of diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride (component (a)) was suspended in 17.6 mL of hexane, and a hexane solution of triisobutylaluminum (component (d)) (0.714 M) ) 22.4 mL was added to obtain a contact product of component (a) and component (d). 4.0 g of the modified hectorite (component (c)) was added to the contact product, and the mixture was stirred at 60 ° C. for 3 hours, and then allowed to stand to remove the supernatant, and a hexane solution of triisobutylaluminum (0.03 M ). Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  To the catalyst precursor slurry prepared above, 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) with respect to diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride. ) A solution of 4.7 mg (8.4 μmol) of hexane (7.2 mL) and triisobutylaluminum in hexane (0.714 M) (1.2 mL) was added and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, 0.4 mL of the catalyst slurry was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 128 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 9
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 10 except that 0.4 mL of the catalyst precursor slurry prepared in Example 10 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 120 g of polymer was obtained. The obtained polymer had Mn = 12,000 and Mw / Mn = 2.50. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 53. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

Example 11
[Preparation of polyethylene production catalyst]
As component (b), diphenylmethylene (3-trimethylsilyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was used in place of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride. Except for this, it was prepared in the same manner as in Example 10.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 10 except that the prepared catalyst was used. As a result, 90 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the obtained polyethylene.

Example 12
[Preparation of polyethylene production catalyst]
It was prepared in the same manner as in Example 10 except that divinylsilanediylbis (cyclopentadienyl) zirconium dichloride was used as component (a) instead of diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 10, except that 0.2 mL of the prepared catalyst slurry was used. As a result, 216 g of polymer was obtained. Table 1 shows the density, Mw, Mw / Mn, long chain branching number, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Comparative Example 10
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 12 except that 0.4 mL of the catalyst precursor slurry prepared in Example 12 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 205 g of polymer was obtained. The obtained polymer had Mn = 19000 and Mw / Mn = 2.60. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 30. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

実施例１３
［ポリエチレン製造触媒の調製］
成分（ａ）として、ジフェニルシランジイルビス（シクロペンタジエニル）ジルコニウムジクロリドのかわりにエチレンビス（シクロペンタジエニル）ジルコニウムジクロリドを用いたこと以外は実施例１０と同様の方法で調製した。

Example 13
[Preparation of polyethylene production catalyst]
It was prepared in the same manner as in Example 10 except that ethylenebis (cyclopentadienyl) zirconium dichloride was used as component (a) instead of diphenylsilanediylbis (cyclopentadienyl) zirconium dichloride.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 10, except that 0.2 mL of the prepared catalyst slurry was used. As a result, 136 g of a polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 11
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 13 except that 0.4 mL of the catalyst precursor slurry prepared in Example 13 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 120 g of polymer was obtained. The obtained polymer had Mn = 18,000 and Mw / Mn = 2.50. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 45. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

Example 14
[Preparation of polyethylene production catalyst]
Example 12 with the exception that 10 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was added as a component (b) to divinylsilanediylbis (cyclopentadienyl) zirconium dichloride. Prepared in a similar manner.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 12 except that the prepared catalyst was used. As a result, 175 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 15
[Preparation of polyethylene production catalyst]
The same as Example 13 except that 2 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride is added as a component (b) to ethylenebis (cyclopentadienyl) zirconium dichloride. Prepared by method.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 13 except that the prepared catalyst was used. As a result, 144 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 16
[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To this autoclave, 0.1 mL of the catalyst slurry prepared in Example 14 was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released, and then the internal temperature of the autoclave was raised to 90 ° C., and ethylene was introduced until the partial pressure reached 0.3 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 0.3 MPa, and the polymerization temperature was controlled at 90 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 98 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 17
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 16 except that 0.2 mL of the catalyst slurry prepared in Example 15 was added instead of the catalyst slurry prepared in Example 14. As a result, 157 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 18
[Preparation of component (c)]
After adding 60 mL of ethanol and 2.0 mL of 37% concentrated hydrochloric acid to 60 mL of water, 6.55 g (0.022 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. N, N-dimethyloctadecylamine hydrochloride solution was prepared. To this solution, 20 g of montmorillonite was added. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 1 L of 60 ° C. water. Then, the modified montmorillonite (component (c)) with an average particle diameter of 5.2 micrometers was obtained by drying at 60,10 < ^-3 > torr for 24 hours, and grind | pulverizing with a jet mill.

[Preparation of polyethylene production catalyst]
55.8 mg (160 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride (component (a)) was suspended in 17.6 mL of hexane, and a hexane solution of triisobutylaluminum (component (d)) (0.714 M) ) 22.4 mL was added to obtain a contact product of component (a) and component (d). 4.0 g of the above modified montmorillonite (component (c)) was added to the contact product, and the mixture was stirred at 60 ° C. for 3 hours. Washed with. Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  To the catalyst precursor slurry prepared above, 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) with respect to dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. ) A solution of 4.7 mg (8.4 μmol) of hexane (7.2 mL) and triisobutylaluminum in hexane (0.714 M) (1.2 mL) was added and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. To the autoclave, 0.4 mL of the catalyst slurry was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 125 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Comparative Example 12
[Manufacture of macromonomer]
Ethylene was polymerized in the same manner as in Example 18 except that 0.4 mL of the catalyst precursor slurry prepared in Example 18 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 120 g of polymer was obtained. The obtained polymer had Mn = 13,000 and Mw / Mn = 2.40. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 65. In addition, 0.52 methyl branches per 1,000 carbon atoms and 1.22 ethyl branches per 1,000 carbon atoms were detected. Furthermore, no long chain branching was detected.

Example 19
[Preparation of polyethylene production catalyst]
As component (b), diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) is used instead of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride. ) Prepared in the same manner as in Example 18 except that zirconium dichloride was used.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 18 except that the above prepared catalyst was used. As a result, 136 g of a polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 20
[Preparation of polyethylene production catalyst]
As component (b), diphenylmethylene (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride instead of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride It was prepared in the same manner as in Example 18 except that was used.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 18 except that the above prepared catalyst was used. As a result, 152 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Example 21
[Preparation of polyethylene production catalyst]
Example 18 except that diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride was added as a component (b) in an amount of 10 mol% based on dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. Prepared in a similar manner.

[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 18 except that the above prepared catalyst was used. As a result, 138 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 22
[Preparation of Contact Product of Component (o) and Component (j)]
To a 3 L flask, 53 g of silica (Davison 948, baked under reduced pressure at 200 ° C. for 5 hours), 1 L of toluene and 20 g (91 mmol) of (pN, N-dimethylaminophenyl) trimethoxysilane were added and stirred at 110 ° C. for 16 hours. did. After completion of the reaction, it was washed 4 times with toluene. The carbon content in the silica (component (o)) modified with the obtained silane compound was 4.2 wt%. Silica modified with 18.7 g of this silane compound was suspended in 500 mL of ether, hydrogen chloride gas was blown in at room temperature for 30 minutes, washed with hexane, and dried under reduced pressure. This was further suspended in 600 mL of methylene chloride, and then a solution of lithium tetrakis (pentafluorophenyl) borate (component (j)) 6.0 g (8.7 mmol) in methylene chloride (400 mL) was added and stirred at room temperature for 3 hours. did. After washing with methylene chloride three times, it was vacuum dried to obtain a solid catalyst. The carbon content in the obtained solid catalyst component was 10.8 wt%.

[Preparation of polyethylene production catalyst]
1.0 g of the contact product of component (o) and component (j) prepared above was dispersed in 100 mL of hexane, 1.4 mL of a hexane solution of triisobutylaluminum (0.714M), dimethylsilanediylbis (cyclopenta). Dienyl) zirconium dichloride (component (a)) 17.4 mg (50 μmol), 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) with respect to dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride ) Zirconium dichloride (component (b)) 1.5 mg (2.6 μmol) was added and stirred at room temperature for 1 hour to prepare a catalyst slurry.

[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. 100 mg of the catalyst slurry as a solid component was added to the autoclave, and ethylene was introduced until the partial pressure reached 1.2 MPa. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 1.2 MPa, and the polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 107 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 23
[Preparation of contact product of component (o) and component (g)]
To a 500 mL flask, 10.5 g of silica (Davison 948, baked under reduced pressure at 200 ° C. for 5 hours) (component (o)) and 200 mL of toluene were added to form a suspension. Thereto was added 66 mL of a toluene solution (2.39 M) of methylaluminoxane (component (g)), and the mixture was stirred at room temperature for 1 hour.

[Preparation of polyethylene production catalyst]
To the contact product slurry of the above component (o) and component (g), 174 mg (500 μmol) of dimethylsilanediylbis (cyclopentadienyl) dichloride (component (a)), dimethylsilanediylbis (cyclopentadienyl) dichloride On the other hand, 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) 15.0 mg (26 μmol) was added and stirred at room temperature for 1 hour to prepare a catalyst slurry.

[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane and 1.0 mL of a hexane solution of triisobutylaluminum (0.714 M) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. 100 mg of the catalyst slurry as a solid component was added to the autoclave, and ethylene was introduced until the partial pressure reached 1.2 MPa. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 1.2 MPa, and the polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 84 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 24
[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane, 1.0 mL of hexane solution of triisobutylaluminum (0.714M) and 4.0 mL of 1-butene (2.4 g) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. . To this autoclave, 0.2 mL of the catalyst slurry prepared in Example 1 was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 47 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 13
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 24 except that 0.2 mL of the catalyst precursor slurry prepared in Example 1 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 45 g of polymer was obtained. The obtained polymer had Mn = 10,900 and Mw / Mn = 2.49. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 75. Further, no long chain branching was detected.

Example 25
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 24 except that 8.0 mL (4.8 g) of 1-butene was added. As a result, 52 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 14
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 25 except that 0.2 mL of the catalyst precursor slurry prepared in Example 1 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 48 g of polymer was obtained. The obtained polymer had Mn = 10,800 and Mw / Mn = 2.49. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 77. Further, no long chain branching was detected.

Example 26
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 24 except that the catalyst slurry prepared in Example 4 was used instead of the catalyst slurry prepared in Example 1. As a result, 68 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 27
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 25 except that the catalyst slurry prepared in Example 4 was used instead of the catalyst slurry prepared in Example 1. As a result, 67 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Example 28
[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane, 1.0 mL of hexane solution of triisobutylaluminum (0.714M) and 36.0 mL of 1-butene (21.6 g) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. . To this autoclave, 0.2 mL of the catalyst slurry prepared in Example 5 was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 71 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 15
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 28 except that 0.2 mL of the catalyst precursor slurry prepared in Example 5 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 65 g of polymer was obtained. The obtained polymer had Mn = 15,000 and Mw / Mn = 2.41. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0.3. 80. Further, no long chain branching was detected.

Example 29
[Production of polyethylene]
Into a 2 L autoclave, 1,200 mL of hexane, 1.0 mL of hexane solution of triisobutylaluminum (0.714 M) and 14.7 mL of 1-butene (14.8 g) were introduced, and the internal temperature of the autoclave was raised to 85 ° C. . To this autoclave, 0.2 mL of the catalyst slurry prepared in Example 7 was added, and ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 85 ° C. After 90 minutes from the start of the polymerization, the internal pressure of the autoclave was released, and the contents were suction filtered. After drying, 61 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 16
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 29 except that 0.2 mL of the catalyst precursor slurry prepared in Example 7 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 55 g of polymer was obtained. The obtained polymer had Mn = 16,000 and Mw / Mn = 2.45. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 79. Further, no long chain branching was detected.

Example 30
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 29 [Production of polyethylene] except that 18.7 mL (11.2 g) of 1-butene was added. As a result, 56 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Comparative Example 17
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 30, except that 0.2 mL of the catalyst precursor slurry prepared in Example 7 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 47 g of polymer was obtained. The obtained polymer had Mn = 16,500 and Mw / Mn = 2.45. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 78. Further, no long chain branching was detected.

Example 31
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 29 [1 except that 12.7 mL (7.6 g) of 1-butene was added. As a result, 50 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, MFR, and MS ₁₆₀ of the obtained polyethylene.

Comparative Example 18
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 31 except that 0.2 mL of the catalyst precursor slurry prepared in Example 7 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 40 g of polymer was obtained. The obtained polymer had Mn = 17,000 and Mw / Mn = 2.45. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 78. Further, no long chain branching was detected.

Example 32
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 29 except that 8.6 mL (5.2 g) of 1-butene was added. As a result, 122 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 19
[Manufacture of macromonomer]
Ethylene and butene-1 were copolymerized in the same manner as in Example 32 except that 0.2 mL of the catalyst precursor slurry prepared in Example 7 [Preparation of polyethylene production catalyst] was used instead of the catalyst slurry. As a result, 100 g of a polymer was obtained. The obtained polymer had Mn = 18,000 and Mw / Mn = 2.45. When the terminal structure of the polymer was analyzed by ¹³ C-NMR, the ratio (Z) of the number of vinyl terminals to the number of saturated terminals was 0. 77. Further, no long chain branching was detected.

Example 33
[Preparation of polyethylene production catalyst]
55.8 mg (160 μmol) of dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride (component (a)) was suspended in 26.7 mL of hexane, and a hexane solution of triethylaluminum (component (d)) (1.20 M) 13.3 mL was added to obtain a contact product of component (a) and component (d). To this contact product, 4.0 g of the modified hectorite (component (c)) prepared in Example 1 [Preparation of component (c)] was added, stirred at 60 ° C. for 3 hours, and then allowed to stand to obtain a supernatant. And washed with a hexane solution of triisobutylaluminum (0.03M). Further, a hexane solution (0.15M) of triisobutylaluminum was added to obtain a catalyst precursor slurry (100 g / L).

  To the catalyst precursor slurry prepared above, 5 mol% of diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride (component (b)) with respect to dimethylsilanediylbis (cyclopentadienyl) zirconium dichloride. ) A solution of 4.7 mg (8.4 μmol) of hexane (7.2 mL) and triisobutylaluminum in hexane (0.714 M) (1.2 mL) was added and stirred at room temperature for 6 hours. Let stand and remove the supernatant, wash with hexane solution of triisobutylaluminum (0.03M), add hexane solution of triisobutylaluminum (0.15M) and finally add 100g / L catalyst slurry. Obtained.

[Production of polyethylene]
Ethylene was polymerized in the same manner as in Example 1 except that 0.4 mL of the catalyst slurry was used. As a result, 165 g of polymer was obtained. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Example 34
[Production of polyethylene]
In a 2 L autoclave, 200 g of sodium chloride dried at 200 ° C. and 10 ⁻³ torr for 20 hours was added as a catalyst dispersant, and the internal temperature was adjusted to 75 ° C. Then, 1.0 mL of a hexane solution (0.714M) of triisobutylaluminum and 0.4 mL of the catalyst slurry prepared in Example 33 [Preparation of polyethylene production catalyst] were inserted into an autoclave. Immediately, ethylene was introduced until the partial pressure reached 1.2 MPa to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 1.2 MPa. The polymerization temperature was controlled at 80 ° C. After 90 minutes from the start of polymerization, the internal pressure of the autoclave was released, and the contents were washed with pure water, dissolved in salt and dried to obtain 61 g of polymer. Table 2 shows the density, Mw, Mw / Mn, number of long-chain branches, bulk density, and MFR of the obtained polyethylene.

Comparative Example 20
[Evaluation of polyethylene]
Table 2 shows the density, Mw, Mw / Mn, long-chain branching number, bulk density, and MFR of HDPE (Nipolon Hard 8300) obtained by two-stage polymerization using a Ziegler catalyst commercially available from Tosoh Corporation. This polymer deviates from the requirement of formula (28).

Comparative Example 21
[Evaluation of polyethylene]
Table 2 shows the density, Mw, Mw / Mn, long chain branching number, bulk density, and MFR of Cr catalyst HDPE (5003) commercially available from BASF. This polymer deviates from the requirement of formula (28).

Comparative Example 22
[Evaluation of polyethylene]
Table 2 shows the density, Mw, Mw / Mn, number of long chain branches, bulk density, and MFR of the metallocene catalyst ethylene / 1-octene copolymer (EG8100) commercially available from Dow Chemical Company. This polymer deviates from the requirement of formula (28).

Claims (4)

(A) a density is at 0.890 g / cm ³ or more 0.980 g / cm ³ or less,
(B) The weight average molecular weight (Mw) is 30,000 to 10,000,000,
(C) The ratio (Mw / Mn) of Mw to number average molecular weight (Mn) is 2 or more and 20 or less,
(D) A method for producing polyethylene having a long chain branching number of from 0.01 to 3 per 1,000 carbon atoms, the production method comprising the following general formula (1)

[Wherein M ¹ is a zirconium atom, and X ¹ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, a carbon number 1 to 20 nitrogen atom-containing hydrocarbon group or oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, and R ¹ and R ² are represented by the following general formula (2):

(Wherein R ⁴ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon having 1 to 20 carbon atoms) Group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms. )
Wherein R ¹ and R ² form a sandwich structure with M ¹ , and R ³ is represented by the following general formula (5)

(Wherein R ⁵ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon having 1 to 20 carbon atoms. Group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms , and Y ¹ is a carbon atom or a silicon atom.)
And acts to crosslink R ¹ and R ² , where l is an integer from 1 to 5. ]
A transition metal compound (component (a)) represented by the following general formula (6)

[Wherein M ² is a zirconium atom, and each X ² independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 nitrogen atom-containing hydrocarbon group or oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ represents the following general formula (7) or (8):

(Wherein R ¹⁰ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon having 1 to 20 carbon atoms. Group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms.)
R ⁸ is represented by the following general formula (10)

(Wherein R ¹¹ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon having 1 to 20 carbon atoms. Group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms.)
Wherein R ⁷ and R ⁸ form a sandwich structure with M ² , and R ⁹ is represented by the following general formula (11):

(Wherein R ¹² is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon having 1 to 20 carbon atoms. Group or an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms.)
In which R ⁷ and R ⁸ are cross-linked and m is an integer from 1 to 5. ]
A transition metal compound (component (b)) represented by the following general formula (13):
[R ¹⁴ R ¹⁵ _y-1 M ³ H] _a [A] _b (13)
(In the formula, [R ¹⁴ R ¹⁵ _y-1 M ³ H] is a cation, M ³ is an element selected from Group 15 or Group 16 of the periodic table, and R ¹⁴ has 1 to 30 carbon atoms. Each of R ¹⁵ is independently a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is y = 3 when M ³ is a Group 15 element, and M ³ is a 16th group. (When a group element, y = 2, [A] is an anion, and a and b are integers selected so that charges are balanced.)
Modified clay mineral (component (c)) treated with an organic compound represented by the formula:
AlR ¹³ ₃ (12)
(In the formula, R ¹³ is a hydrocarbon group having 1 to 20 carbon atoms.)
A process for producing polyethylene as described above, wherein ethylene or ethylene and 1-butene are polymerized using a catalyst comprising an organoaluminum compound represented by formula (component (d)) . The method for producing polyethylene according to claim 1, wherein ethylene or ethylene and 1-butene are polymerized in a slurry state . (E) The method for producing polyethylene according to claim 1 or 2, wherein the method is a method for producing particulate polyethylene having a powder bulk density of 0.15 g / cm ³ or more and 0.70 g / cm ³ or less. (E) The method for producing polyethylene according to claim 3, which is a method for producing particulate polyethylene having a powder bulk density of 0.15 g / cm ³ or more and 0.50 g / cm ³ or less.