JP5123460B2 - Polyethylene and method for producing the same - Google Patents

Description

  The present invention relates to branched polyethylene and a method for producing the same.

  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 melt-processing a polymer, but on the other hand it reduces the mechanical strength of the solid polymer and the stretchability of the melt polymer. There are drawbacks.

  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 and the stretchability of molten polymers. Has been used. However, these HDPE and LLDPE do not have good moldability, which is an advantage of LDPE.

  Examples of techniques for improving the molding processability of HDPE and LLDPE by a polyethylene production method include, 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), A) A method for producing polyethylene having long chain branches using a traditional Cr-based catalyst, c) A method for producing polyethylene having long chain branches by polymerizing ethylene using a specific metallocene catalyst (for example, patents) Reference 4), d) a method of producing polyethylene having a long chain branch by completely copolymerizing ethylene and a macromonomer using a specific metallocene catalyst (see, for example, Patent Document 5), e) an ethylene macromonomer A method of blending linear polyethylene with a copolymer (for example, see Patent Document 6) has been proposed. However, the moldability of polyethylene obtained by these methods is still not sufficient. Furthermore, 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.

JP-A-2-53811

JP-A-2-132109 JP-A-10-182742 US Pat. No. 5,272,236 Japanese translation of PCT publication No. 8-502303 Special table 2001-511212 gazette

  The present invention has been made to solve the above-mentioned problems of the prior art, and includes a polyethylene having both good moldability of LDPE, mechanical strength of HDPE and LLDPE, and melt stretchability, and a method for producing the same. It is to provide.

The present invention has been found as a result of intensive studies on the above-described object. That is, the present invention relates to an ethylene polymer having a vinyl group at a terminal obtained by polymerizing ethylene, or an ethylene copolymer having a vinyl group at a terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms. Coalesced,
(A) M _n is 5,000 or more,
(B) obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer having M _w / M _n of 2 to 5.
(C) 1% by weight to 99% by weight of a branched polyethylene obtained by copolymerizing ethylene, a macromonomer, and optionally an olefin having 3 or more carbon atoms,
(D) density of the 0.890 g / cm ³ or more 0.980 g / cm ³ or less,
(E) The weight average molecular weight (M _w ) is 30,000 to 10,000,000,
(F) The ratio ( _Mw / _Mn ) of _Mw and number average molecular weight ( _Mn ) is 2 or more and 30 or less,
(G) The number of long chain branches is from 0.01 to 3 per 1,000 carbon atoms,
(H) The present invention relates to a polyethylene having a shrinkage factor (g ′ value) of 0.1 or more and less than 0.9 evaluated by gel permeation chromatography (GPC) / intrinsic viscometer and a method for producing the same.

  Hereinafter, the present invention will be described in detail.

The macromonomer in the present invention is an olefin polymer having a vinyl group at the terminal, preferably an ethylene polymer having a vinyl group at the terminal obtained by polymerizing ethylene, or ethylene and an olefin having 3 or more carbon atoms. It is an ethylene copolymer having a vinyl group at the terminal obtained by polymerization, and more preferably a branch other than a branch derived from an olefin having 3 or more carbon atoms, methyl branch, ethyl branch, propyl branch, butyl branch, Short chain branching such as pentyl branching is less than 0.01 per 1,000 main chain methylene carbons, and long chain branching (that is, branching of a hexyl group or more detected by ¹³ C-NMR measurement) Linear ethylene polymerization with a vinyl group at the end, less than 0.01 per 1,000 main chain methylene carbons Or a linear ethylene copolymer.

  Examples of the olefin having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, α-olefin such as vinylcycloalkane, norbornene, Examples include cyclic olefins such as norbornadiene, dienes such as butadiene or 1,4-hexadiene, and styrene. Two or more of these olefins can be mixed and used.

When an ethylene polymer having a vinyl group at the terminal or an ethylene copolymer having a vinyl group at the terminal is used as the macromonomer, the number average molecular weight (M _n ) is 5,000 or more, preferably 10,000 or more. More preferably, it is 15,000 or more. The weight average molecular weight (M _w ) is 10,000 or more, preferably 15,000 or more, and more preferably greater than 20,000. The ratio of the weight average molecular weight (M _w ) to M _n (M _w / M _n ) is 2 or more and 5 or less, preferably 2 or more and 4 or less, more preferably 2 or more and 3.5 or less. . The amount of terminal vinyl per mol of macromonomer determined by converting the amount of terminal vinyl per 1,000 carbon atoms measured by IR per _Mn is 0.1 mol or more and 1 mol or less, preferably 0.8. It is 5 mol or more and 1 mol or less, More preferably, it is 0.8 mol or more and 1 mol or less.

  Although there is no particular limitation regarding the method for producing the macromonomer in the present invention, when producing an ethylene polymer having a vinyl group at the terminal as the macromonomer, for example, Group 3, Group 4, Group 5 and Group 5 of the periodic table are used. A method of polymerizing ethylene using a catalyst containing a metallocene compound containing a transition metal selected from Group 6 as a main component can be used.

  A polymer newly produced by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of the macromonomer in the present invention is a copolymer of ethylene, a macromonomer and optionally an olefin having 3 or more carbon atoms. And a copolymer of ethylene and optionally an olefin having 3 or more carbon atoms. The copolymer of ethylene, macromonomer and optionally an olefin having 3 or more carbon atoms is 1% by weight or more in the newly formed polymer. 100% by weight or less is contained.

  In addition, the amount of polymer newly produced by copolymerizing ethylene, macromonomer and optionally olefin having 3 or more carbon atoms in the present invention is based on the GPC chart of polyethylene powder and the GPC chart of macromonomer. The ratio of the peak attributed to the newly produced polymer obtained as a result of the peak separation attributed to the peak attributed to the newly produced polymer and the peak attributed to the macromonomer to the total peak, 1% by weight It is 99 wt% or less, preferably 5 wt% or more and 90 wt% or less, more preferably 30 wt% or more and 80 wt% or less.

  The amount of the macromonomer in the polyethylene of the present invention is the amount of the unreacted macromonomer that has not been inserted into the branched polyethylene, and the GPC chart of the polyethylene is converted into the branched polyethylene based on the GPC chart of the macromonomer. The ratio of the peak attributed to the macromonomer to the total peak obtained as a result of the peak separation between the attributed peak and the peak attributed to the macromonomer, which is 1 wt% or more and 99 wt% or less, preferably 10 It is not less than 95% by weight and more preferably not less than 20% by weight and not more than 70% by weight.

Density polyethylene (d) of the present invention is a value measured by a density gradient tube method in conformity with JIS K6760 (1995), is 0.890 g / cm ³ or more 0.980 g / cm ³ or less. In the case where an olefin having 3 or more carbon atoms is not added, the density of the polyethylene and the MFR (g / 10 min., 190 ° C.) with a load of 2.16 kg are expressed by the following formula (13).
d ≧ 0.008 × log (MFR) +0.958 (13)
And preferably the following formula (13) ′
d ≧ 0.007 × log (MFR) +0.960 (13) ′
More preferably, the following formula (13) "
d ≧ 0.005 × log (MFR) +0.964 (13) ”
It is in the relationship shown by.

The weight average molecular weight ( _Mw ) in terms of linear polyethylene of the polyethylene of the present invention is from 30,000 to 10,000,000, preferably from 40,000 to 8,000,000, more preferably. Is from 50,000 to 5,000,000.

_Mw / _Mn of the polyethylene of the present invention is 2 or more and 30 or less, preferably 2 or more and 8 or less, and more preferably 3 or more and 6 or less.

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

The shrinkage factor (g ′ value) evaluated by GPC / intrinsic viscometer of the polyethylene of the present invention is a parameter representing the degree of long-chain branching, and is an absolute molecular weight of 700,000 or an absolute value of 3 times the weight average molecular weight (M _w ). This is the ratio of the intrinsic viscosity of the polyethylene and the HDPE with no branching in molecular weight. The g ′ value of the polyethylene of the present invention is 0.1 or more and less than 0.9, preferably 0.1 or more and 0.8 or less, and more preferably 0.1 or more and 0.7 or less. 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 (1), more preferably by the formula (1) ′. In addition, g value is a ratio of the root mean square of the inertial radius of this polyethylene and HDPE in the absolute molecular weight 700,000 or the absolute molecular weight 3 times _Mw .

0.2 <log (g ′) / log (g) <1.3 (1)
0.5 <log (g ′) / log (g) <1.0 (1) ′
log (g ′) / log (g) is a parameter representing the form of long-chain branching, and it has been clarified that it approaches 1.5 for a short comb-shaped branch and a small value for a star-shaped branch. (See Takeshi Fukuda, New Polymer Experimental Science 1, Basics of Polymer Experiments, Molecular Characterization, “3-4. Molecular Shape and Morphology”, 295 (1994)). The polyethylene of the present invention shows a value smaller than 1.3 in order to show a shape close to a star shape. Further, between the g value in an absolute molecular weight three times the _{M w (g 3M)} and g values of the absolute molecular weight of 1 × _{M w (g M),} preferably of formula (16), more preferably formula ( 16) ′ More preferably, there is a relationship represented by the formula (16) ″.

0 <g _3M / g _M ≦ 1 (16)
0 <g _3M / g _M ≦ 0.9 (16) ′
0 <g _3M / g _M ≦ 0.8 (16) ''
The flow activation energy (E _a ) of the polyethylene of 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 or more and 100 kJ / mol or less, preferably 35 kJ / mol or more and 80 kJ / mol or less, more preferably 40 kJ / mol or more and 70 kJ / mol or less. The E _a is less than 30 kJ / mol, reduces the temperature dependence of the viscosity, moldability is deteriorated.

The melt tension (MS) of the polyethylene of 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 °, a shear rate of 10.8 s ⁻¹ , and a draw ratio. Is a value measured under the condition of 47. When the maximum stretch ratio is less than 47, the value measured at the highest stretch ratio that does not break is defined as MS. MFR is a value measured at 190 ° C. and a load of 2.16 kg. MS (mN) and MFR (g / 10 min., 190 ° C.) of the polyethylene of the present invention are the following formulas (2) or (3)
MS ₁₉₀ > 22 × MFR ^-0.88 (2)
(In the formula, MS ₁₉₀ is MS measured at 190 ° C.)
MS ₁₆₀ > 110-110 × log (MFR) (3)
(In the formula, MS ₁₆₀ is MS measured at 160 ° C.)
Satisfying either of these, preferably the formula (3) or the following formula (2) ′
MS ₁₉₀ > 30 × MFR− ^0.88 (2) ′
More preferably, both the expressions (2) and (3) are satisfied, more preferably both the expressions (2) ′ and (3) are satisfied, more preferably the expressions (2) ′ and the following: Formula (3) '
MS ₁₆₀ > 130-110 × log (MFR) (3) ′
More preferably, the formula (2) ′ and the following formula (3) ″
MS ₁₆₀ > 150-110 × log (MFR) (3) ″
There is a relationship that satisfies both.

When MS ₁₆₀ is in the range of [110−110 × log (MFR)] or less and MS ₁₉₀ is in the range of 22 × MFR− ^0.88 or less, a problem occurs in moldability.

The non-linearity parameter (λ) of the extensional viscosity of the polyethylene of the present invention is the maximum of the extensional viscosity measured at 160 ° C. and a strain rate of 0.07 to 0.1 s ⁻¹ using a Meissner type uniaxial extensional viscometer. The value is a value obtained by dividing the value by the extensional viscosity in the linear region of the time, and is in the range of 1.2 to 100, preferably 2.0 to 100, more preferably 2.0 to 30. Note that M.M. Yamaguchi et al. Polymer Journal 32 , 164 (2000). As described in, the elongational viscosity in the linear region can be calculated from dynamic viscoelasticity. When λ is less than 1.2, the strain hardenability decreases, and a problem arises in moldability in blow molding, foam molding, and the like.

The maximum draw ratio (DR) of the polyethylene of the present invention is as follows: a die having a length (L) of 8 mm and a diameter (D) of 2.095 mm, an inflow angle of 90 ° and 160 ° C., and a shear rate of 10.8 s ⁻ It is the stretch ratio at break when the take-up speed is increased by 20 m / min per minute under the condition of ¹ . MS and DR of the polyethylene of the present invention are preferably in the relationship of the following formula (4).

log (DR)> 5-1.33 × log (MS ₁₆₀ ) (4)
(In the formula, MS ₁₆₀ is MS measured at 160 ° C.)
When log (DR) is in the range of [5-1.33 × log (MS ₁₆₀ )] or less, a problem occurs in stretchability at the time of melting.

  The polyethylene of the present invention uses ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer using a catalyst containing a metallocene compound [component (a)] represented by the general formula (5) as a main component. Is obtained by polymerizing.

式（５）中、Ｍ^１はチタン原子、ジルコニウム原子またはハフニウム原子である。Ｘ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のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基または炭素数１〜２０の窒素原子含有炭化水素基であり、具体的には弗素原子、塩素原子、臭素原子、沃素原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基を例示することができる。Ｒ^２は一般式（６）、（７）または（８）で表されるＭ^１に配位する配位子である。

In formula (5), M ¹ is a titanium atom, a zirconium atom or a hafnium atom. X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. A hydrocarbon group-substituted silyl group, a C1-C20 oxygen atom-containing hydrocarbon group or a C1-C20 nitrogen atom-containing hydrocarbon group, specifically a fluorine atom, a chlorine atom, a bromine atom, an iodine atom Halogen atoms such as 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, 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, vinyl group, propenyl Group, phenyl group, methylphenyl group, naphthyl group, etc., C1-C20 hydrocarbon group, methoxy group, ethoxy group, etc., C1-C20 alkoxy group, dimethylamino group, diethylamino group, di-n- C1-C20 hydrocarbon group-substituted amino group such as propylamino group, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group, diphenylmethylsilyl group and the like C1-C20 hydrocarbon group-substituted silyl group, methoxy C1-C20 oxygen atom-containing hydrocarbon group such as methyl group, 2-methoxyethyl group, dimethylaminoethyl group, dimethylamino Propyl group, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms such as dimethyl aminophenyl group can be exemplified. R ² is a ligand coordinated to M ¹ represented by the general formula (6), (7) or (8).

式中、Ｒ^５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のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基または炭素数１〜２０の窒素原子含有炭化水素基であり、具体的には弗素原子、塩素原子、臭素原子、沃素原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基を例示することができる。Ｒ^３は一般式（９）で表されるＭ^１に配位する配位子であり、

In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 hydrocarbon group-substituted silyl group, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, specifically fluorine atom, chlorine atom, bromine Atoms, halogen atoms such as iodine atoms, 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, 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 , Vinyl group, propenyl group, phenyl group, methylphenyl group, naphthyl group and other hydrocarbon groups having 1 to 20 carbon atoms, methoxy group, ethoxy group and other alkoxy groups having 1 to 20 carbon atoms, dimethylamino group, diethylamino group Hydrocarbon groups having 1 to 20 carbon atoms such as di-n-propylamino group, hydrocarbon groups having 1 to 20 carbon atoms such as substituted amino groups, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group and diphenylmethylsilyl group C1-C20 oxygen atom-containing hydrocarbon group such as substituted silyl group, methoxymethyl group, 2-methoxyethyl group, dimethylaminoethyl group, dimethyl Aminopropyl group, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms such as dimethyl aminophenyl group can be exemplified. R ³ is a ligand coordinated to M ¹ represented by the general formula (9),

式中、Ｒ^６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のアルコキシ基、炭素数１〜２０の炭化水素基置換アミノ基、炭素数１〜２０の炭化水素基置換シリル基、炭素数１〜２０の酸素原子含有炭化水素基または炭素数１〜２０の窒素原子含有炭化水素基であり、具体的には弗素原子、塩素原子、臭素原子、沃素原子等のハロゲン原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基、メトキシ基、エトキシ基等の炭素数１〜２０のアルコキシ基、ジメチルアミノ基、ジエチルアミノ基、ジ−ｎ−プロピルアミノ基等の炭素数１〜２０の炭化水素基置換アミノ基、トリメチルシリル基、トリエチルシリル基、フェニルジメチルシリル基、ジフェニルメチルシリル基等の炭素数１〜２０の炭化水素基置換シリル基、メトキシメチル基、２−メトキシエチル基等の炭素数１〜２０の酸素原子含有炭化水素基、ジメチルアミノエチル基、ジメチルアミノプロピル基、ジメチルアミノフェニル基等の炭素数１〜２０の窒素原子含有炭化水素基を例示することができる。

In the formula, each R ⁶ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, or a carbon number. 1 to 20 hydrocarbon group-substituted silyl group, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms, specifically fluorine atom, chlorine atom, bromine Atoms, halogen atoms such as iodine atoms, 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, 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 , Vinyl group, propenyl group, phenyl group, methylphenyl group, naphthyl group and other hydrocarbon groups having 1 to 20 carbon atoms, methoxy group, ethoxy group and other alkoxy groups having 1 to 20 carbon atoms, dimethylamino group, diethylamino group Hydrocarbon groups having 1 to 20 carbon atoms such as di-n-propylamino group, hydrocarbon groups having 1 to 20 carbon atoms such as substituted amino groups, trimethylsilyl group, triethylsilyl group, phenyldimethylsilyl group and diphenylmethylsilyl group C1-C20 oxygen atom-containing hydrocarbon group such as substituted silyl group, methoxymethyl group, 2-methoxyethyl group, dimethylaminoethyl group, dimethyl Aminopropyl group, a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms such as dimethyl aminophenyl group can be exemplified.

R ² and R ³ form a sandwich structure with M ^1, and R ⁴ is represented by the general formula (10) or (11), and acts to bridge R ² and R ³ .

式中、Ｒ^７は各々独立して水素原子または炭素数１〜２０の炭化水素基であり、具体的にはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、２−メチルブチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ｎ−ヘキシル基、イソヘキシル基、３−メチルペンチル基、４−メチルペンチル基、ネオヘキシル基、２，３−ジメチルブチル基、２，２−ジメチルブチル基、４−メチル−２−ペンチル基、３，３−ジメチル−２−ブチル基、１，１−ジメチルブチル基、２，３−ジメチル−２−ブチル基、シクロヘキシル基、ビニル基、プロペニル基、フェニル基、メチルフェニル基、ナフチル基等の炭素数１〜２０の炭化水素基を例示することができる。Ｍ^２はケイ素原子、ゲルマニウム原子または錫原子である。ｎは１〜５の整数である。

In the formula, each R ⁷ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group. , 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 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, vinyl group, propenyl group, phenyl group, methylphenyl group, naphthyl group, etc. It can be illustrated. M ² is a silicon atom, a germanium atom or a tin atom. n is an integer of 1-5.

As the metallocene compound [component (a)] used in the present invention, (methyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, (Methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) hafnium Dicro Id, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene ( Cyclopentadienyl) (2-dimethylaminofluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene ( Cyclopentadienyl) (2-dimethyl) Ruaminofluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2- Diisopropylaminofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (4- Dimethylaminofluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclo Pentadienyl) (4-dimethylaminofluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2-methoxyfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) ) (2-methoxyfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2-methoxyfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) ( 4-methoxyfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (4 Methoxyfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2, 7-dimethoxyfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-methylcyclopentadiene) Enyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-methylcyclopentadienyl) (full Renyl) hafnium dichloride, (methyl) (phenyl) methylene (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-methylcyclohexane) Pentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) ) Hafnium dichloride, (methyl) (phenyl) methylene (3-ethylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl ) (F Phenyl) methylene (3-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride , (Methyl) (phenyl) methylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-isopropylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-isopropyl Cyclopentadienyl (Fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-isopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-isopropylcyclopentadienyl) (2,7-di -Tert-butylfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) Methylene (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-tert-butylcyclopentadienyl) (fluorenyl) titani Mudichloride, (Methyl) (phenyl) methylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, (Methyl) (phenyl) methylene (3-tert-butylcyclopentadienyl) (fluorenyl) hafnium dichloride , (Methyl) (phenyl) methylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3-tert-butylcyclohexane) Pentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfullyl) Olenyl) Hafnium Dichlor (Methyl) (phenyl) methylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, (Methyl) (phenyl) methylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3-benzylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) ( Phenyl) methylene (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3-benzylcyclopentadienyl) (fluorenyl) hafni Mudichloride, (methyl) (phenyl) methylene (3,4-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride (Methyl) (phenyl) methylene (3,4-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3,4-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, ( Methyl) (phenyl) methylene (3,4-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3,4-diethylcyclopentadienyl) (fluorenyl) hafniu Dichloride, (methyl) (phenyl) methylene (2,3-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (2,3-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, (Methyl) (phenyl) methylene (2,3-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) titanium dichloride, (methyl ) (Phenyl) methylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (3,4-diisopropylcyclopentadienyl) (fluorene) Nyl) hafnium dichloride, (methyl) (phenyl) methylene (indenyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (indenyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (indenyl) (fluorenyl) Hafnium dichloride, (methyl) (phenyl) methylene (tetrahydroindenyl) (fluorenyl) titanium dichloride, (methyl) (phenyl) methylene (tetrahydroindenyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (tetrahydroindenyl) ) (Fluorenyl) hafnium dichloride, (methyl) (phenyl) methylene (2-methylindenyl) (fluorenyl) titanium dichloride (Methyl) (phenyl) methylene (2-methylindenyl) (fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (2-methylindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) ) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethylfluorenyl) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (cyclope Tadienyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2 , 7-Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2 -Dimethylaminofluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2-dimethylaminophenyl) Ruolenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) zirconium dichloride
Rholide, diphenylmethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (4-dimethylaminofluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (4-Dimethylaminofluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (4-dimethylaminofluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2-methoxyfluorenyl) titanium dichloride Diphenylmethylene (cyclopentadienyl) (2-methoxyfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2-methoxyphenyl) Olenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (4-methoxyfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (4-methoxyfluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) ) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) hafnium dichloride, diphenylmethylene (3-methylcyclopentadi) Nyl) (fluorenyl) titanium dichloride, diphenylmethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-methylcyclopenta) Dienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-ethylcyclopentadienyl) (fluoro Rhenyl) titanium dichloride, diphenylmethylene (3-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3- Ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-isopropylcyclopentadienyl) (fluorenyl) titanium di Rholide, diphenylmethylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-isopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-isopropylcyclopentadienyl) (2, 7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (3-isopropylcyclopenta Dienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) Titanium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-tert-butylcyclo Pentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride Diphenylmethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (3- (trimethylsilyl) Cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenyl Methylene (3-benzylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3-benzylcyclopentadienyl) (fluorenyl) hafnium dichloride, Diphenylmethylene (3,4-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenyl Methylene (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3,4-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3,4-diethylcyclopentadienyl) (Fluorenyl) titanium dichloride, diphenylmethylene (3,4-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2,3 -Diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (2,3-diethylcyclopentadienyl) (fluorenyl) zirconi Mudichloride, diphenylmethylene (2,3-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylmethylene (3,4-diisopropylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (indenyl) (fluorenyl) titanium dichloride, diphenylmethylene (indenyl) (fluorenyl) zirconium dichloride , Diphenylmethylene (indenyl) (fluorenyl) hafnium dichloride, diphenylmethylene ( Tetrahydroindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (tetrahydroindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (tetrahydroindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2-methylindenyl) (fluorenyl) titanium dichloride Diphenylmethylene (2-methylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2-methylindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (3-methylindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (3 -Methylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene 3-methylindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (4,5-benzoindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (4,5-benzoindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (4 , 5-Benzoindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) ( Fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-isopropyl) -7-methylindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methyl) Indenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2,3-dimethylindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2,3-dimethylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2,3- Dimethylindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (4-phenylindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (4-phenyl) Enylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (4-phenylindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (fluorenyl) titanium dichloride, diphenylmethylene (4- (1-naphthyl) ) Indenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2 -Methyl-4-phenylindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenylindene) Ru) (fluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) zirconium Dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2-propyl-4- (9-phenanthryl) indenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2 -Propyl-4- (9-phenanthryl) indenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2-propyl-4- (9-phenanthryl) indenyl) (fluoro Nyl) hafnium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (fluorenyl) zirconium dichloride Diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (fluorenyl) titanium dichloride, diphenylmethylene ( 2,7-dimethyl-4,5-benzoindenyl) (fluorenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (fluorenyl) hafnium dichloride, dipheni Rumethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (fluorenyl) titanium dichloride, diphenylmethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (fluorenyl) zirconium dichloride , Diphenylme
Tylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (fluorenyl) hafnium dichloride, diphenylmethylene (indenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (indenyl) (2 , 7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (indenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (tetrahydroindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenyl Methylene (tetrahydroindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (tetrahydroindenyl) (2,7-dimethylfluorenyl) hafnium dichloride Id, diphenylmethylene (2-methylindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2-methylindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2 -Methylindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (3-methylindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (3-methylindenyl) ( 2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (3-methylindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7- Dimethylf Olenyl) titanium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7-dimethylfluorenyl) Hafnium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (2,7 -Dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7- Methylindenyl) (2,7- Dimethylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methylindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7) -Methylindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2,3-dimethylindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2,3-dimethyl) Indenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2,3-dimethylindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (4-phenylindenyl) ( 2 7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (4-phenylindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (4-phenylindenyl) (2,7-dimethylfluorenyl) ) Hafnium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) ) Zirconium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (2,7-dimethylfluore) Nil Titanium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (2,7-dimethylfluorene) Nyl) hafnium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2-propyl-4) -(9-phenant Ryl) indenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2-propyl-4- (9-phenanthryl) indenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2 -Propyl-4- (9-phenanthryl) indenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (2,7-dimethylfluore Nyl) titanium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindene) Nyl) (2,7-dimethylfluoreni ) Hafnium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) ) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (2,7 -Dimethyl-4,5- (2-methylbenzo) indenyl) (2,7-dimethylfluorenyl) titanium dichloride, diphenylmethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (2, 7-dimethylfluorenyl) zirconium dichloride, diphe Rumethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylmethylene (indenyl) (2,7-di-tert-butylfluorenyl) ) Titanium dichloride, diphenylmethylene (indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (indenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (Tetrahydroindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (tetrahydroindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmeth Tylene (tetrahydroindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2-methylindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenyl Methylene (2-methylindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2-methylindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride Diphenylmethylene (3-methylindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (3-methylindenyl) (2,7-di-tert-butylfluorenyl) Zirconium dichloride, diphenylme Len (3-methylindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) Titanium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (4,5-benzoindenyl) (2,7-di-tert) -Butylfluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4, 5-Benzoindenyl) (2,7-di-tert-butylfluoreni ) Zirconium dichloride, diphenylmethylene (2-methyl-4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methyl) Indenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methylindenyl) (2,7-di-tert-butylfluorenyl) ) Zirconium dichloride, diphenylmethylene (2-methyl-4-isopropyl-7-methylindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2,3-dimethylindenyl) ( 2,7-di-tert-butylfluorenyl ) Titanium dichloride, diphenylmethylene (2,3-dimethylindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2,3-dimethylindenyl) (2,7-di-) tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (4-phenylindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (4-phenylindenyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (4-phenylindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (2,7-di-t rt-butylfluorenyl) titanium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (4- (1-naphthyl) indenyl ) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2-Methyl-4-phenylindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4-phenylindenyl) (2,7-di-tert- Butylfluorenyl) hafnium dichloride Diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) ( 2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2-methyl-4- (1-naphthyl) indenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenyl Methylene (2-propyl-4- (9-phenanthryl) indenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2-propyl-4- (9-phenanthryl) indenyl) (2 , 7-Di-tert-butylfluorenyl) zirconium Dichloride, diphenylmethylene (2-propyl-4- (9-phenanthryl) indenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindene Nyl) (2,7-di-tert-
Butylfluorenyl) titanium dichloride, diphenylmethylene (2,6-dimethyl-4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2,6-dimethyl) -4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (2,7-di- tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2,7-dimethyl-4,5-benzoindenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2,7 -Dimethyl-4,5-benzoindenyl) (2,7-di-tert-butyl) Rufluorenyl) hafnium dichloride, diphenylmethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylmethylene (2,7-dimethyl) -4,5- (2-methylbenzo) indenyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (2,7-dimethyl-4,5- (2-methylbenzo) indenyl) ( 2,7-di-tert-butylfluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilane Yl (cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethyl) Fluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylfluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-di-tert-butyl) Tilfluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-dimethylaminofluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-dimethylaminofluorenyl) zirconium dichloride, dimethylsilanediyl (Cyclopentadienyl) (2-dimethylaminofluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2 -Diisopropylaminofluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) hafnium dichloride Dimethylsilanediyl (cyclopentadienyl) (4-dimethylaminofluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopenta) Dienyl) (4-dimethylaminofluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxyfluorene) Nyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) hafnium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxy) (Luolenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxyfluorenyl) hafnium dichloride, dimethylsilanediyl (cyclohexane) Pentadienyl) (2,7-dimethoxyfluorenyl) titanium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethoxyfluorenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2 , 7-Dimethoxyfluorenyl) hafnium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3-methylsilane) Clopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) (2,7-di-tert- Butylfluorenyl) titanium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilanediyl (3-methylcyclopentadienyl) ( 2,7-di-tert-butylfluorenyl) hafnium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3-ethylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) titanium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilanediyl (3-ethylcyclopentadienyl) (2,7 -Di-tert-butylfluorenyl) hafnium dichloride, dimethylsilanediyl (3-isopropylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3-isopropylcyclo) Ntadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3-isopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) titanium dichloride, dimethylsilanediyl (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilanediyl (3-isopropylcyclopentadienyl) (2,7 -Di-tert-butylfluorenyl) hafnium dichloride, dimethylsilanediyl (3-tert-butylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3-tert-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3-tert-butylcyclopentadienyl) ) (2,7-di-tert-butylfluorenyl) titanium dichloride, dimethylsilanediyl (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethyl Silanediyl (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, dimethylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorene L) Titanium dichloride, dimethylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3 -Benzylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3-benzylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethyl Silanediyl (3,4-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3,4) Dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3,4-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) titanium Dichloride, dimethylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (2,3- Diethylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (2,3-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride Rholide, dimethylsilanediyl (2,3-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (3,4-diisopropylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (3,4 Diisopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (3,4-diisopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (indenyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (indenyl) (Fluorenyl) zirconium dichloride, dimethylsilanediyl (indenyl) (fluorenyl) hafnium dichloride, dimethylsila Diyl (tetrahydroindenyl) (fluorenyl) titanium dichloride, dimethylsilanediyl (tetrahydroindenyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (tetrahydroindenyl) (fluorenyl) hafnium dichloride, dimethylsilanediyl (2-methylindenyl) (Fluorenyl) titanium dichloride, dimethylsilanediyl (2-methylindenyl) (fluorenyl) zirconium dichloride, dimethylsilanediyl (2-methylindenyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (fluorenyl) Titanium dichloride, diphenylsilanediyl (cyclopentadienyl) (fluorenyl) zirconium dichloride Ride, Diphenylsilanediyl (cyclopentadienyl) (fluorenyl) hafnium dichloride, Diphenylsilanediyl (cyclopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, Diphenylsilanediyl (cyclopentadienyl) (2 , 7-dimethylfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethylfluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-di-tert -Butylfluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopen Tadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-dimethylaminofluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl) ( 2-dimethyl
Ruaminofluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-dimethylaminofluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) titanium dichloride Diphenylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-diisopropylaminofluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadi) Enyl) (4-dimethylaminofluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-dimethylaminofluorenyl) Zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-dimethylaminofluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) titanium dichloride, diphenylsilanediyl (cyclopenta) Dienyl) (2-methoxyfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2-methoxyfluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-methoxyfluorenyl) ) Titanium dichloride, diphenylsilanediyl (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadiene) ) (4-methoxyfluorenyl) hafnium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethoxyfluorenyl) titanium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethoxy) Fluorenyl) zirconium dichloride, diphenylsilanediyl (cyclopentadienyl) (2,7-dimethoxyfluorenyl) hafnium dichloride, diphenylsilanediyl (3-methylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphe Nylsilanediyl (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylsilanediyl (3-methylcyclopentadienyl) (2,7-di-tert-butylfurful) Oleenyl) zirconium dichloride, diphenylsilanediyl (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylsilanediyl (3-ethylcyclopentadienyl) (fluorenyl) Titanium dichloride, diphenylsilanediyl (3-ethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3-ethylcyclopentadienyl) (fluorenyl) hafnium dichlorine Diphenylsilanediyl (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylsilanediyl (3-ethylcyclopentadienyl) (2,7-di-tert) -Butylfluorenyl) zirconium dichloride, diphenylsilanediyl (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (Fluorenyl) titanium dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (fluorenyl) Hough Um dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (2,7-di -Tert-butylfluorenyl) zirconium dichloride, diphenylsilanediyl (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, diphenylsilanediyl (3-tert-butylcyclo) Pentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3-tert-butyl) Lucyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, diphenylsilanediyl (3-tert) -Butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylsilanediyl (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorene) Nyl) hafnium dichloride, diphenylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) di Conium dichloride, diphenylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (3-benzylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3-benzylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3-benzylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (3,4-dimethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilane Diyl (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3,4) Dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) zirconium Dichloride, diphenylsilanediyl (3,4-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (2,3-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (2,3- Diethylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (2,3-diethylcyclopentadienyl) (fluorenyl) Hough Nium dichloride, diphenylsilanediyl (3,4-diisopropylcyclopentadienyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (3,4-diisopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3,4) -Diisopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (indenyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (indenyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (indenyl) (fluorenyl) hafnium dichloride, diphenyl Silanediyl (tetrahydroindenyl) (fluorenyl) titanium dichloride, di Phenylsilanediyl (tetrahydroindenyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (tetrahydroindenyl) (fluorenyl) hafnium dichloride, diphenylsilanediyl (2-methylindenyl) (fluorenyl) titanium dichloride, diphenylsilanediyl (2- Methylindenyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (2-methylindenyl) (fluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene Lopentadienyl) (2,7-dimethylfluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-dimethylfluorene) Nyl) hafnium dichloride, ethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) Zirconium dichloride, ethylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) titanium dichloride, ethylene (cyclopenta Dienyl) (2-dimethylaminofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2-dimethylaminofluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) titanium Dichloride, ethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2-diisopropylaminofluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (4- Dimethylaminofluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (4-dimethylaminofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) ( -Dimethylaminofluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2-methoxyfluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (2-methoxyfluorenyl) zirconium dichloride, ethylene (cyclopenta Dienyl) (2-methoxyfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (4-methoxyfluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (4-methoxyfluorenyl) zirconium dichloride, Ethylene (cyclopentadienyl) (4-methoxyfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) titanium dichloride, ethylene (Si Lopentadienyl) (2,7-dimethoxyfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-dimethoxyfluorenyl) hafnium dichloride, ethylene (3-methylcyclopentadienyl) (fluorenyl) titanium dichloride , Ethylene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3-methylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3-methylcyclopentadienyl) (2,7-di- tert-butylfluorenyl) titanium dichloride, ethylene (3-methylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (3-methyl Cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, ethylene (3-ethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3-ethylcyclopentadienyl) (fluorenyl) ) Zirconi
Um dichloride, ethylene (3-ethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, ethylene (3- Ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, ethylene (3-ethylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, Ethylene (3-isopropylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3-isopropylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3-isopropylcyclopentadienyl) (fluorine) Nyl) hafnium dichloride, ethylene (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, ethylene (3-isopropylcyclopentadienyl) (2,7-di-tert) -Butylfluorenyl) zirconium dichloride, ethylene (3-isopropylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, ethylene (3-tert-butylcyclopentadienyl) (fluorenyl) ) Titanium dichloride, ethylene (3-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3-tert-butylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethyl (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) titanium dichloride, ethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butyl Fluorenyl) zirconium dichloride, ethylene (3-tert-butylcyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dichloride, ethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) ) Titanium dichloride, ethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3-benzyl) Cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3-benzylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3-benzylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3,4-dimethyl) Cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3,4-dimethylcyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (3,4-dimethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3 , 4-Diethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3,4-diethylcyclopentadienyl) (fluorenyl) zirconium dichloride Ride, ethylene (3,4-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (2,3-diethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (2,3-diethylcyclopentadienyl) (Fluorenyl) zirconium dichloride, ethylene (2,3-diethylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (3,4-diisopropylcyclo) Pentadienyl) (fluorenyl) zirconium dichloride, ethylene (3,4-diisopropylcyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (indenyl ) (Fluorenyl) titanium dichloride, ethylene (indenyl) (fluorenyl) zirconium dichloride, ethylene (indenyl) (fluorenyl) hafnium dichloride, ethylene (tetrahydroindenyl) (fluorenyl) titanium dichloride, ethylene (tetrahydroindenyl) (fluorenyl) zirconium dichloride , Ethylene (tetrahydroindenyl) (fluorenyl) hafnium dichloride, ethylene (2-methylindenyl) (fluorenyl) titanium dichloride, ethylene (2-methylindenyl) (fluorenyl) zirconium dichloride, ethylene (2-methylindenyl) ( Fluorenyl) hafnium dichloride and the like, and dimethyl compounds of the above metallocene compounds, di Examples include ethyl, dihydro, diphenyl, dibenzyl and the like.

The catalyst containing the metallocene compound [component (a)] represented by the general formula (5) used as the main component in the present invention includes the component (a) and the following general formula (17).
AlR ¹⁰ ₃ (17)
(In the formula, each R ¹⁰ independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.)
A catalyst composed of an organoaluminum compound [component (c)], a catalyst further comprising water, component (a) and the following general formula (14)

および／または下記一般式（１５）

And / or the following general formula (15)

（式中、Ｒ^１１は各々独立して水素原子または炭素数１〜２０の炭化水素基であり、ｐは２〜５０の整数である。）
で表されるアルミノキサン［成分（ｄ）］からなる触媒、さらに成分（ｃ）を含んでなる触媒、成分（ａ）と下記一般式（１８）
［Ｒ^８Ｒ^９ _ｙ−１Ｍ^３Ｈ］［Ｍ^４Ａｒ_４］ （１８）
（式中、［Ｒ^８Ｒ^９ _ｙ−１Ｍ^３Ｈ］はカチオンであり、Ｍ^３は周期表の第１５族または第１６族から選ばれる元素であり、Ｒ^８は炭素数１〜３０の炭化水素基であり、Ｒ^９は各々独立して水素原子または炭素数１〜３０の炭化水素基であり、ｙはＭ^３が第１５族元素の時ｙ＝３であり、Ｍ^３が第１６族元素の時ｙ＝２であり、［Ｍ^４Ａｒ_４］はアニオンであり、Ｍ^４はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるプロトン酸塩［成分（ｅ）］、下記一般式（１９）
［Ｃ］［Ｍ^４Ａｒ_４］ （１９）
（式中、Ｃはカルボニウムカチオンまたはトロピリウムカチオンであり、Ｍ^４はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるルイス酸塩［成分（ｆ）］または下記一般式（２０）
［Ｍ^５Ｌ^１ _ｚ］［Ｍ^４Ａｒ_４］ （２０）
（式中、Ｍ^５は周期表の第１族、第８族、第９族、第１０族または第１１族の金属の陽イオンであり、Ｌ^１はルイス塩基またはシクロペンタジエニル基であり、ｚは０≦ｚ≦２であり、Ｍ^４はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表される金属塩［成分（ｇ）］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（ｃ）および／または成分（ｄ）を含んでなる触媒、成分（ａ）と下記一般式（２１）
Ｍ^４Ａｒ_３ （２１）
（式中、Ｍ^４はホウ素、アルミニウムまたはガリウムであり、Ａｒは各々独立して炭素数６〜２０のハロゲン置換アリール基である。）
で表されるルイス酸［成分（ｈ）］からなる触媒、さらに成分（ｃ）および／または成分（ｄ）を含んでなる触媒、成分（ａ）と成分（ｈ）と成分（ｅ）、成分（ｆ）、成分（ｇ）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（ｃ）および／または成分（ｄ）を含んでなる触媒、成分（ａ）と粘土鉱物［成分（ｉ）］からなる触媒、さらに成分（ｃ）を含んでなる触媒、成分（ａ）と有機化合物で処理された粘土鉱物［成分（ｂ）］からなる触媒、さらに成分（ｃ）を含んでなる触媒を用いることができるが、好ましくは成分（ａ）と成分（ｂ）からなる触媒を用いることである。

(In the formula, each R ¹¹ is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and p is an integer of 2 to 50.)
A catalyst comprising aluminoxane [component (d)], a catalyst further comprising component (c), component (a) and the following general formula (18)
_{^{[R 8 R 9 y-1}} M 3 H] [M 4 Ar 4] (18)
(In the formula, [R ⁸ R ⁹ _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 ⁸ has 1 to 30 carbon atoms. a hydrocarbon group, ^{R 9} are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is when y = 3 of ^{M 3} group 15 element, ^{M 3} is 16 In the case of a group element, y = 2, [M ⁴ Ar ₄ ] is an anion, M ⁴ is boron, aluminum or gallium, and Ar is independently a halogen-substituted aryl group having 6 to 20 carbon atoms. .)
Protonate [component (e)] represented by the following general formula (19)
[C] [M ⁴ Ar ₄ ] (19)
(Wherein C is a carbonium cation or tropylium cation, M ⁴ is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
A Lewis acid salt [component (f)] represented by the following general formula (20)
[M ⁵ L ¹ _z ] [M ⁴ Ar ₄ ] (20)
(Wherein M ⁵ is a metal cation of Group 1, Group 8, Group 9, Group 10 or Group 11 of the Periodic Table; L ¹ is a Lewis base or a cyclopentadienyl group; Z is 0 ≦ z ≦ 2, M ⁴ is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
A catalyst comprising at least one salt selected from metal salts represented by the formula [component (g)], a catalyst comprising component (c) and / or component (d), component (a) and the following general formula: (21)
M ⁴ Ar ₃ (21)
(Wherein M ⁴ is boron, aluminum or gallium, and Ar is each independently a halogen-substituted aryl group having 6 to 20 carbon atoms.)
A catalyst comprising a Lewis acid [component (h)], a catalyst further comprising component (c) and / or component (d), component (a), component (h), component (e), component (F), a catalyst comprising at least one salt selected from component (g), a catalyst further comprising component (c) and / or component (d), component (a) and clay mineral [component (i) A catalyst comprising component (c), a catalyst comprising component (a) and a clay mineral [component (b)] treated with an organic compound, and a catalyst comprising component (c). Although it can be used, it is preferable to use a catalyst comprising component (a) and component (b).

  The clay mineral used for the component (b) 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 generally have a large layer charge, and the pyrophyllite, kaolinite, dickite and talc groups (negative charge per chemical formula is approximately 0), smectite groups (negative charge per chemical formula is approximately 0.25 to 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 exemplified 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 organic compound treatment in the component (b) of the present invention refers to introducing an organic ion between clay mineral layers to form an ion complex. As the organic compound used in the organic compound treatment, a compound represented by the following general formula (12), (22) or (23), preferably (12) can be used.

[R ⁸ R ⁹ _y-1 M ³ H] _a [A] _b (12)
[C] _a [A] _b (22)
[M ⁶ L ² _z ] _a [A] _b (23)
(In the formula, [R ⁸ R ⁹ _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 ⁸ has 1 to 30 carbon atoms. a hydrocarbon group, ^{R 9} are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is when y = 3 of ^{M 3} group 15 element, ^{M 3} is 16 When the group element is y = 2, C is a carbonium cation or tropylium cation, M ⁶ is a group 8 metal cation of the periodic table, L ² is a cyclopentadienyl group, z is 0 ≦ z ≦ 2, [A] is an anion, and a and b are integers selected so that charges are balanced.)
Here, as [A], for example, fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetrafluoro ion Examples thereof include, but are not limited to, borate ion and hexafluorophosphate ion.

Examples of M ³ in the formula (12) include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. Examples of the hydrocarbon group having 1 to 30 carbon atoms of R ⁸ and R ⁹ include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, and 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-dimethyl group Butyl group, 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, 2-methylcyclohexyl 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-dimethyl Cyclohexyl 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-heneicosyl group, n-docosyl group, n-tricosyl group, oleyl Group, behenyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylpheny group 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-methoxyphenyl group, 2-ethoxyphenyl 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-dihydroindene- Examples include 5-yl group, 2-biphenyl group, 4-biphenyl group, and p-trimethylsilylphenyl group. R ⁸ and R ⁹ may be bonded to each other.

Among the compounds represented by the formula (12), those in which M ³ is a nitrogen atom include 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, n-octadecylamine Hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2-amino Heptane 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, heptadecylamine hydrochloride, octadecyl Amine hydrochloride Nonadecylamine hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride, cyclohexane Dodecylamine 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 hydrochloride, N-allylcyclohexyl Silamine 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 Salt, N, N-dimethyloleylamine hydrochloride, N, N-dimethylbehenylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tridodecylamine Hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylcyclohex Silamine 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, 1,2,2,6,6-penta Hydrochloric acid hydrochlorides such as methylpiperidine 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 Salt, 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 Salt, 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 Salt, N-propyl-p-toluidine hydrochloride, 2,3-dimethylaniline hydrochloride, 2,4-dimethylaniline hydrochloride, 2,5-dimethylaniline 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-anisidine hydrochloride, m-anisi Gin 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-aminoindane hydrochloride, 2-aminobiphenyl hydrochloride, 4-aminobiphenyl hydrochloride, N, 2,3-trimethylaniline hydrochloride Salt, N, 2,4-trimethylaniline hydrochloride, N, 2,5-trimethylaniline hydrochloride, N, 2,6-trimethylaniline hydrochloride, N, 3,4-trimethylaniline hydrochloride, N, 3 5-trimethylaniline hydrochloride, N-methyl-2-ethylaniline hydrochloride, N-methyl-3-ethylaniline 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-tetrame Ruaniline 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, 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-butylanily 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- Enethidine hydrochloride, N, N-dimethyl-1-aminonaphthalene hydrochloride, N, N-dimethyl-2-aminonaphthalene hydrochloride, N, N-dimethyl-1-aminofluorene hydrochloride, N, N-dimethyl-2 -Aminofluorene hydrochloride, N, N-dimethyl-3-aminofluorene hydrochloride, N, N-dimethyl-4-aminofluorene hydrochloride, N, N-dimethyl-5-aminoindan hydrochloride, N, N-dimethyl Fluorinated aromatic amine hydrochlorides such as 2-aminobiphenyl hydrochloride, N, N-dimethyl-4-aminobiphenyl hydrochloride, N, N-dimethyl-p-trimethylsilylaniline hydrochloride and hydrochlorides of the above compounds Examples include, but are not limited to, compounds replaced with hydrate, hydrobromide, hydroiodide or sulfate.

Among the compounds represented by formula (12), those in which M ³ is an oxygen atom include compounds such as methyl ether hydrochloride, ethyl ether hydrochloride, n-butyl ether hydrochloride, tetrahydrofuran hydrochloride, and phenyl ether hydrochloride Examples thereof include, but are not limited to, compounds in which the hydrochloride of the above compound is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

Among the compounds represented by formula (12), those in which M ³ is a sulfur atom include diethylsulfonium fluoride, diethylsulfonium chloride, diethylsulfonium bromide, diethylsulfonium iodide, dimethylsulfonium fluoride, and dimethylsulfonium chloride. Examples thereof include, but are not limited to, dimethylsulfonium bromide and dimethylsulfonium iodide.

Among the compounds represented by the formula (12), those in which M ³ is a phosphorus atom include triphenylphosphine hydrochloride, tri (o-tolyl) phosphine hydrochloride, tri (p-tolyl) phosphine hydrochloride, trimesi Examples thereof include compounds such as tilphosphine hydrochloride, and compounds obtained by replacing hydrochlorides of the above compounds with hydrofluoric acid salts, hydrobromide salts, hydroiodide salts or sulfate salts, but are not limited thereto. It is not something.

  Examples of the compound represented by the formula (22) include trityl bromide, trityl chloride, trityl tetrafluoroborate, trityl hexafluorophosphate, tropylium bromide, tropylium chloride, tropylium tetrafluoroborate, and tropylium hexafluorophosphate. Although it can illustrate, it is not limited to these.

  Examples of the compound represented by the general formula (23) include, but are not limited to, ferrocenium bromide, ferrocenium chloride, ferrocenium tetrafluoroborate, and ferrocenium hexafluorophosphate.

  In the organic compound treatment, 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. As the treatment solvent, aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or n-butyl ether, Halogenated hydrocarbons such as methylene chloride or chloroform, acetone, 1,4-dioxane, tetrahydrofuran or water can be used, but alcohols or water are preferably used alone or as a component of a solvent.

  The catalyst comprising component (a) and component (b) used in the present invention can be obtained by bringing component (a) and component (b) into contact in an organic solvent.

  As the contact solvent, aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, nonane, decane, cyclopentane or cyclohexane, aromatic hydrocarbons such as benzene, toluene or xylene, ethyl ether or n-butyl ether And ethers such as methylene chloride and chloroform, 1,4-dioxane, acetonitrile and tetrahydrofuran.

  About a contact temperature, it is preferable to select between 0-200 degreeC and to process.

  As for the usage-amount of each component, the component (a) is 0.0001-100 mmol per 1g of component (b), Preferably it is 0.001-10 mmol.

  The contact product of component (a) and component (b) thus prepared may be used without washing or may be used after washing. Further, when the component (a) is a dichloro compound, it is preferable to further add the component (c). Moreover, a component (c) can be added for the purpose of removing the impurities in a component (b), a polymerization solvent, and an olefin.

R ¹⁰ of component (c) is 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, 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, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, phenyl, cyclo A hexyl group can be exemplified.

  Component (c) includes 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 Dorido, triisooctyl aluminum, diisooctyl aluminum hydride can be exemplified.

  The amount of component (c) added to the catalyst comprising component (a) and component (b) is such that component (c) is 0.001 to 10,000 mmol, preferably 0.01 to 1000 mmol per gram of component (b). is there. The molar ratio of component (a) to component (c) is 1: 0.1 to 10,000, preferably 1: 1 to 1000.

  The method for adding component (c) to the catalyst comprising component (a) and component (b) is not particularly limited, but component (c) is added after contacting component (a) and component (b). The component (b) and the component (c) are contacted, and then the component (a) is added to the contact product of the component (b) and the component (c). The method of adding the contact product of) can be illustrated.

  The polyethylene of the present invention is obtained by polymerizing ethylene and optionally an olefin having 3 or more carbon atoms in the presence of a macromonomer using the above catalyst.

  The polymerization solvent may be any organic solvent that is generally used. Specifically, halogenated hydrocarbons such as chloroform, methylene chloride, and carbon tetrachloride, propane, n-butane, isobutane, n-pentane, n -C3-C20 aliphatic hydrocarbons such as hexane, n-heptane, n-octane, n-nonane, n-decane, aromatic hydrocarbons having 6-20 carbon atoms such as benzene, toluene, xylene, etc. The olefin itself can be used as a solvent.

  The polymerization temperature is in the range of -70 to 300 ° C, preferably 0 to 250 ° C, more preferably 20 to 150 ° C. The ethylene partial pressure is in the range of 0.001 to 300 MPa, preferably 0.005 to 50 MPa, and more preferably 0.01 to 10 MPa. Further, hydrogen may be present as a molecular weight regulator in the polymerization system.

  In the present invention, when ethylene and an olefin having 3 or more carbon atoms are polymerized in the presence of a macromonomer, an ethylene / olefin having 3 or more olefins (molar ratio) is used as a supply ratio of ethylene and the olefin having 3 or more carbon atoms. 1 to 200, preferably 3 to 100, and more preferably 5 to 50 can be used.

  The polyethylene of the present invention is an inorganic filler such as a heat stabilizer, a weather stabilizer, an antistatic agent, an antifogging agent, an antiblocking agent, a slip agent, a lubricant, a nucleating agent, a pigment, carbon black, talc, glass powder, and glass fiber. Known additives such as an agent or a reinforcing agent, an organic filler or a reinforcing agent, a flame retardant, and a neutron shielding agent can be blended.

  The polyethylene of the present invention can also be used by mixing with other thermoplastic resins. Examples of these include HDPE, LLDPE, LDPE, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, polystyrene, and anhydrous thereof. A maleic acid graft product etc. can be illustrated.

  According to the method for producing polyethylene of the present invention, polyethylene having both LDPE molding processability, HDPE and LLDPE mechanical strength, and melt stretchability can be obtained.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

  Preparation of the macromonomer synthesis catalyst, synthesis of the macromonomer, preparation of the component (b), preparation of the catalyst for polyethylene production, production of polyethylene and solvent purification were all carried out under an inert gas atmosphere. Preparation of macromonomer synthesis catalyst, macromonomer synthesis, preparation of component (b), preparation of polyethylene production catalyst, solvent used for production of polyethylene, etc. were all purified, dried and deoxygenated in advance by known methods. A thing was used. Biscyclopentadienylzirconium dichloride (zirconocene dichloride) manufactured by Wako Pure Chemical Industries, Ltd. was used. Component (a) was synthesized and identified by a known method. The toluene solution (trade name: PMAO; Al: 2.4 mol / L) of methylaluminoxane and the toluene solution (0.848 M) of triisobutylaluminum were manufactured by Tosoh Finechem Corporation.

  Furthermore, various physical properties of polyethylene in Examples and Comparative Examples were measured by the following methods.

The weight average molecular weight (M _w ), the number average molecular weight (M _n ), and the ratio of the weight average molecular weight to the number average molecular weight (M _w / M _n ) 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 is 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) is obtained by a method of measuring [η] of polyethylene fractionated by GPC. The absolute molecular weight of 700,000 or the absolute molecular weight of 3 times _Mw is calculated as [η]. 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 square of the radius of inertia at 700,000 absolute HD of unbranched HDPE or 3 times the absolute molecular weight of _Mw. The value divided by the average. 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 density (d) was measured by a density gradient tube method in accordance with JIS K6760 (1995).

The number of long chain branches was measured by ¹³ C-NMR using a JNM-GSX270 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd.

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 shear loss elastic modulus G ″ in the range were obtained, the shift factor on the horizontal axis at the reference temperature of 160 ° C. was obtained, and the activation energy of the flow was calculated by a known method. There is no movement.

  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.

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 is taken by Takeshi Fukuda, New Polymer Experimental Science 1, Basics of Polymer Experiment, Molecular Characteristic Analysis, “3-4. Molecular Shape and Form”, 295 (1994). According to the method described in the above, calculation was performed using an approximate expression from dynamic viscoelasticity.

Macromonomer synthesis example 1
[Catalyst preparation]
To 16.1 mg (55.2 μmol) of biscyclopentadienylzirconium dichloride, 19.5 mL of toluene and 0.5 mL of a solution of methylaluminoxane in toluene (Al: 2.4 mol / L) are added and stirred at 25 ° C. for 1 hour. Thus, a catalyst for synthesizing a macromonomer was prepared.

[Macromonomer synthesis]
1200 mL of toluene was introduced into a 2 L autoclave, and the internal temperature of the autoclave was raised to 90 ° C. Next, ethylene was introduced until the partial pressure reached 0.25 MPa. Polymerization was started by adding the entire amount of the catalyst to the autoclave. During the polymerization, ethylene was continuously introduced so that the partial pressure was kept at 0.25 MPa. The polymerization temperature was controlled at 80 ° C. 90 minutes after the start of the polymerization, the internal pressure of the autoclave was depressurized to 0 MPa, the contents of the autoclave were filtered, and the resulting ethylene polymer was dried at 90 ° C. under reduced pressure for 12 hours. As a result, 140 g of macromonomer was obtained. The obtained macromonomer had M _n = 20,000 and M _w / M _n = 2.6. Further, the amount of terminal vinyl per 1 mol of the macromonomer was 0.97 mol. ^{In 13} C-NMR, methyl branch, ethyl branch, propyl branch, butyl branch, pentyl branch and branch beyond hexyl group were not detected.

Macromonomer synthesis example 2
[Catalyst preparation]
To 26.6 mg (91.0 μmol) of biscyclopentadienylzirconium dichloride, 19.1 mL of toluene and 0.9 mL of a toluene solution of methylaluminoxane (Al: 2.4 mol / L) were added and stirred at 25 ° C. for 1 hour. Thus, a catalyst for synthesizing a macromonomer was prepared.

[Macromonomer synthesis]
Ethylene was polymerized in the same manner as in Macromonomer Synthesis Example 1 [Macromonomer Synthesis] except that the ethylene partial pressure was changed to 0.10 MPa using the above catalyst, and as a result, 150 g of macromonomer was obtained. M _n of the obtained macromonomer was 9,000, and M _w / M _n = 2.5. The amount of terminal vinyl per 1 mol of the macromonomer was 0.95 mol. ^{In 13} C-NMR, methyl branch, ethyl branch, propyl branch, butyl branch, pentyl branch and branch beyond hexyl group were not detected.

Macromonomer synthesis example 3
[Catalyst preparation]
1-benzoyl-1- (triphenylphosphoranylidene) sodium methanesulfonate (21.7 mg, 45.0 μmol), toluene (20 mL) and bis (1,5-cyclooctadiene) nickel (37.1 mg, 134.9 μmol) The resulting mixture was stirred at 25 ° C. for 15 minutes to prepare a catalyst for synthesizing a macromonomer.

[Macromonomer synthesis]
500 mL of toluene was introduced into a 2 L autoclave, and the internal temperature of the autoclave was raised to 70 ° C. Next, ethylene was introduced until the partial pressure reached 1.0 MPa. Polymerization was started by adding the entire amount of the catalyst to the autoclave. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 1.0 MPa. The polymerization temperature was controlled at 70 ° C. After 45 minutes from the start of polymerization, the internal pressure of the autoclave was depressurized to 0 MPa, the contents of the autoclave were filtered, and the resulting ethylene polymer was dried at 90 ° C. under reduced pressure for 12 hours. As a result, 160 g of macromonomer was obtained. M _n of the obtained macromonomer was 4,500, and M _w / M _n = 3.0. Further, the amount of terminal vinyl per 1 mol of the macromonomer was 0.98 mol. ^{In 13} C-NMR, methyl branch, ethyl branch, propyl branch, butyl branch, pentyl branch and branch beyond hexyl group were not detected.

Example 1
[Preparation of component (b)]
After adding 150 mL of ethanol and 8.3 mL of 37% concentrated hydrochloric acid to 350 mL of water, 29.7 g (0.1 mol) of N, N-dimethyloctadecylamine was added to the resulting solution and heated to 60 ° C. N, N-dimethyloctadecylamine hydrochloride solution was prepared. To this solution, 100 g of hectorite 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, it dried at 60 degreeC and 10 < ^-3 > torr for 24 hours, and the modified | denatured hectorite with an average particle diameter of 5.2 micrometers was obtained by grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of N, N-dimethyloctadecyl ammonium ion per gram of modified hectorite was 0.848 mmol.

[Catalyst preparation]
A contact product of component (b) and component (c) was obtained by adding 60 mL of a hexane solution (0.714M) of triisobutylaluminum to 8.0 g of the modified hectorite and stirring at room temperature for 1 hour. . Meanwhile, 8.8 mL of n-hexane and 11.2 mL (8 mmol) of hexane solution of triisobutylaluminum (0.714 M) were added to 178.1 mg (320 μmol) of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride. By stirring at room temperature for 30 minutes, a contact product of component (a) and component (c) was obtained. The total contact product of component (a) and component (c) was added to the total contact product of component (b) and component (c), and the mixture was stirred at 60 ° C. for 6 hours to remove the supernatant. Then, it wash | cleaned with 80 mL n-hexane, and the contact product of the component (a), the component (b), and the component (c) was obtained. The obtained contact product was diluted with 80 mL of n-hexane to obtain a catalyst slurry (100 g / L).

[Production of polyethylene]
Into a 2 L autoclave, 135.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 1, 1200 mL of toluene, and 2.4 mL of a toluene solution of triisobutylaluminum (0.848 mol / L) were introduced, and the internal temperature of the autoclave was adjusted to 90 ° C. The temperature rose. Next, ethylene was introduced until the partial pressure reached 0.1 MPa. To the autoclave, 2.5 mL of the catalyst slurry was added to initiate polymerization. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 0.1 MPa. The polymerization temperature was controlled at 90 ° C. After 30 minutes from the start of polymerization, the internal pressure of the autoclave was depressurized to 0 MPa, the contents of the autoclave were filtered, and the resulting ethylene polymer was dried at 90 ° C. under reduced pressure for 12 hours. As a result, 161.9 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n , the number of long chain branches and the g ′ value of the obtained polyethylene. The melt properties are shown in Table 2.

Example 2
[Catalyst preparation]
To 2.8 mg (5.0 μmol) of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was added 19.4 mL of toluene and 0.59 mL of a toluene solution of triisobutylaluminum (0.848 mol / L), and the temperature was 25 ° C. For 30 minutes. A catalyst for polyethylene production was prepared by adding 4.8 mg (6.0 μmol) of tetrakis (pentafluorophenylborate) N, N-dimethylanilinium salt to the obtained solution and stirring at 25 ° C. for 30 minutes. .

[Production of polyethylene]
Into a 2 L autoclave, 135.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 1, 1200 mL of toluene, and 2.4 mL of a toluene solution of triisobutylaluminum (0.848 mol / L) were introduced, and the internal temperature of the autoclave was adjusted to 90 ° C. The temperature rose. Next, ethylene was introduced until the partial pressure reached 0.1 MPa. Polymerization was started by adding the entire amount of the catalyst to the autoclave. During the polymerization, ethylene was continuously introduced so that the partial pressure was maintained at 0.1 MPa. The polymerization temperature was controlled at 90 ° C. After 30 minutes from the start of polymerization, the internal pressure of the autoclave was depressurized to 0 MPa, the contents of the autoclave were filtered, and the resulting ethylene polymer was dried at 90 ° C. under reduced pressure for 12 hours. As a result, 161.9 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n , the number of long chain branches, the g ′ value, and the density of the obtained polyethylene. The melt properties are shown in Table 2.

Example 3
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 2 [Production of polyethylene] except that the polymerization time was 16 minutes. As a result, 151.4 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n , the number of long chain branches, the g ′ value, and the density of the obtained polyethylene. The melt properties are shown in Table 2.

Example 4
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 2 [Production of polyethylene] except that the polymerization time was 8 minutes. As a result, 143.5 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n , the number of long chain branches, the g ′ value, and the density of the obtained polyethylene. The melt properties are shown in Table 2.

Example 5
[Production of polyethylene]
Polymerization was performed in the same manner as in Example 2 [Production of polyethylene] except that the polymerization time was 60 minutes. As a result, 168.7 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n and the number of long chain branches of the obtained polyethylene. The melt properties are shown in Table 2.

Comparative Example 3
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 2 [Production of polyethylene] except that 270.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 1 was used and that the polymerization time was 90 minutes. As a result, 297.0 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n and the number of long chain branches of the obtained polyethylene. The melt properties are shown in Table 2.

Example 6
[Production of polyethylene]
Polymerization was performed in the same manner as in Example 2 [Production of polyethylene] except that 45.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 2 was used and the polymerization time was 11 minutes. As a result, 78.5 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n and the number of long chain branches of the obtained polyethylene. The melt properties are shown in Table 2.

Comparative Example 4
[Production of polyethylene]
Except that 135.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 1 was used, 7 g of 1-butene was added, and the polymerization time was 30 minutes, the same as in Example 2 [Production of polyethylene] Polymerization was carried out by the method. As a result, 161 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n and the number of long chain branches of the obtained polyethylene. The melt properties are shown in Table 2.

Comparative Example 1
[Production of polyethylene]
Polymerization was carried out in the same manner as in Example 2 [Production of polyethylene], except that 20.0 g of the macromonomer synthesized in Macromonomer Synthesis Example 3 was used and the polymerization time was 12 minutes. As a result, 45.8 g of polyethylene was obtained. Table 1 shows the macromonomer content, M _w , M _w / M _n and the number of long chain branches of the obtained polyethylene. The melt properties are shown in Table 2. When the _{Mn of the} macromonomer is less than 5,000, the requirement of formulas (2) and (3) is lost.

Comparative Example 2
[Evaluation of polyethylene]
Table 1 shows M _w , M _w / M _n and the number of long chain branches of the metallocene catalyst ethylene / 1-octene copolymer (EG8100) commercially available from Dow Chemical. The melt properties are shown in Table 2. The polymer, _{E a} is less than 40 kJ / mol, with λ is less than 2, is outside the requirements of the formula (2) and (3).

  Tables 1 and 2 show the structural analysis results and melt physical property evaluation results in the above Examples and Comparative Examples.

Claims (12)

An ethylene polymer having a vinyl group at a terminal obtained by polymerizing ethylene, or an ethylene copolymer having a vinyl group at a terminal obtained by copolymerizing ethylene and an olefin having 3 or more carbon atoms;
(A) The number average molecular weight (M _n ) is 9,000 to 20,000 ,
(B) In the presence of a macromonomer having a ratio ( _Mw / _Mn ) of weight average molecular weight ( _Mw ) to number average molecular weight ( _Mn ) of 2 or more and 3.5 or less , ethylene and optionally 3 carbon atoms Obtained by polymerizing the above olefins,
(C) 35% by weight or more and 84% by weight or less of branched polyethylene obtained by copolymerizing ethylene, a macromonomer, and optionally an olefin having 3 or more carbon atoms,
(D) density of the 0.890 g / cm ³ or more 0.980 g / cm ³ or less,
(E) _Mw is 62,000 to 116,000 ,
(F) _Mw / _Mn is 3 or more and 4.5 or less ,
(G) The number of long chain branches is from 0.05 to 0.15 per 1,000 carbon atoms,
(H) The shrinkage factor (g ′ value) at an absolute molecular weight 3 times the weight average molecular weight (Mw) evaluated by gel permeation chromatography (GPC) / intrinsic viscometer is 0.59 to 0.74 ,
(I) A polyethylene containing 16% by weight or more and 65% by weight or less of a macromonomer. Macromonomer
(J) The polyethylene according to claim 1 , which is a linear polymer. (G) 'The polyethylene according to any one of claims 1 to 2 , wherein the number of long-chain branches is 0.05 or more and less than 0.1 per 1,000 carbon atoms. (K) The g ′ value at an absolute molecular weight 3 times the weight average molecular weight (Mw) and the contraction factor (g value) evaluated by GPC / light scattering are represented by the following formula (1).
0.31 ≦ log (g ′) / log (g) <0.77 (1)
The polyethylene according to any one of claims 1 to 3 , wherein the polyethylene has a relationship represented by the following formula. (L) polyethylene according to claim 1, fluidized activation energy _{(E a)} is equal to or less than 30 kJ / mol or more 50 kJ / mol. (M) 2.16 kg load MFR (g / 10 min., 190 ° C.) is 0.12 or more and 0.35 or less, and melt tension (MS ₁₉₀ ) measured at 190 ° C. is 160 mN or more and 170 mN or less. The polyethylene according to any one of claims 1 to 5 . (M) ′ MFR (g / 10 min., 190 ° C.) of 2.16 kg load is 0.12 or more and 0.85 or less, and melt tension (MS ₁₆₀ ) measured at 160 ° C. is 215 mN or more and 255 mN or less. The polyethylene according to any one of claims 1 to 6 , wherein: (N) The non-linearity parameter (λ) of elongational viscosity is 1.8 or more and 2.7 or less, polyethylene according to any one of claims 1 to 7 . (O) Maximum draw ratio (DR) and MS are the following formula (4)
log (DR)> 5-1.33 × log (MS ₁₆₀ ) (4)
(In the formula, MS ₁₆₀ is MS measured at 160 ° C.)
The polyethylene according to any one of claims 1 to 8 , wherein the polyethylene has a relationship represented by the following formula. General formula (5)

[Wherein, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, carbon A hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, a hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms And R ² is represented by the general formula (6), (7) or (8).

(In the formula, each R ⁵ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted hydrocarbon group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms.)
R ³ is a ligand coordinated to M ¹ represented by the general formula (9)

(In the formula, each R ⁶ independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group-substituted amino group having 1 to 20 carbon atoms, carbon, A hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms, an oxygen atom-containing hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen atom-containing hydrocarbon group having 1 to 20 carbon atoms.)
In a ligand coordinating to ^{M 1} represented, ^{R 2} and ^{R 3} form a sandwich structure together with ^{M 1, R 4} is formula (10) or (11)

(In the formula, each R ⁷ is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and M ² is a silicon atom, a germanium atom or a tin atom.)
And R ² and R ³ are cross-linked and n is an integer of 1 to 5. ]
2. An ethylene and optionally an olefin having 3 or more carbon atoms are polymerized in the presence of a macromonomer using a catalyst containing a metallocene compound represented by the formula [component (a)] as a main component. polyethylene method according to any one of 1-9. The method for producing polyethylene according to claim 10 , wherein the catalyst containing component (a) as a main component is a catalyst comprising a clay mineral treated with components (a) and (b) an organic compound. Component (b) is represented by the following general formula (12)
[R ⁸ R ⁹ _y-1 M ³ H] _a [A] _b (12)
(In the formula, [R ⁸ R ⁹ _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 ⁸ has 1 to 30 carbon atoms. a hydrocarbon group, ^{R 9} are each independently hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, y is when y = 3 of ^{M 3} group 15 element, ^{M 3} is 16 (When a group element, y = 2, [A] is an anion, and a and b are integers selected so that charges are balanced.)
The method for producing polyethylene according to claim 11 , which is a clay mineral treated with an organic compound represented by the formula: